WO2015195402A1 - Procédés et appareils pour le retrait d'amines dans des courants d'hydrocarbures extraits - Google Patents

Procédés et appareils pour le retrait d'amines dans des courants d'hydrocarbures extraits Download PDF

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Publication number
WO2015195402A1
WO2015195402A1 PCT/US2015/034805 US2015034805W WO2015195402A1 WO 2015195402 A1 WO2015195402 A1 WO 2015195402A1 US 2015034805 W US2015034805 W US 2015034805W WO 2015195402 A1 WO2015195402 A1 WO 2015195402A1
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Prior art keywords
stream
extraction
hydrocarbon stream
alkaline
hydrocarbon
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PCT/US2015/034805
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English (en)
Inventor
Jonathan Andrew Tertel
Ronald GATAN
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Uop Llc
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Publication of WO2015195402A1 publication Critical patent/WO2015195402A1/fr

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Classifications

    • 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
    • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C10G19/02—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions
    • 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/08—Inorganic compounds only
    • 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
    • C10G53/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step
    • 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
    • C10G53/12—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one alkaline treatment step
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

Definitions

  • the technical field generally relates to methods and apparatuses for processing hydrocarbons, and more particularly relates to methods and apparatuses for removing contaminants from a hydrocarbon stream with alkaline and amine and for removing the alkaline and amine from the hydrocarbon stream.
  • Sour hydrocarbon streams are typically treated to remove mercaptans, such as by extraction processes. Mercaptans have traditionally been removed from hydrocarbon streams because of their malodorous scent. Sour hydrocarbon streams may also include acid gases such as carbon dioxide. Attempts have been made to remove acid gases from hydrocarbon streams through the absorption of acid gases with amines.
  • caustic is used to convert mercaptans to mercaptides.
  • Hydrogen sulfide must be removed in a prewash vessel before extraction or the caustic will preferably react with the hydrogen sulfide in the extractor vessel and leave mercaptans in the hydrocarbon stream.
  • a liquid hydrocarbon stream is fed to an amine absorber column to be contacted with an amine, such as diethanolamine, to absorb acid gases such as hydrogen sulfide and carbon dioxide from the hydrocarbon stream.
  • the hydrocarbon stream lean of hydrogen sulfide and other acid gases is then prewashed in a prewash vessel containing liquid caustic to convert the remaining hydrogen sulfide to sodium sulfide which is soluble in caustic.
  • a product hydrocarbon stream lean in mercaptans may pass overhead from the extraction column. The mercaptide rich caustic exits the bottom of the extraction column.
  • the amine used to absorb acid gases may be soluble in the hydrocarbon stream.
  • the product formed from the extraction process may be required to be amine - free. Therefore, an amine removal process must be performed.
  • addition of a water wash to remove amine from the hydrocarbon product stream can add 10% or more to the installation cost of an extraction process unit.
  • a method for processing a hydrocarbon stream includes feeding a hydrocarbon stream including amine and mercaptan to an extraction zone. The method includes contacting the hydrocarbon stream with an alkaline stream in the extraction zone to convert the mercaptan to a mercaptide. Further, the method includes contacting the hydrocarbon stream with water in the extraction zone to remove the amine from the hydrocarbon stream.
  • a method for processing hydrocarbons including feeding a hydrocarbon stream containing sulfur compounds and acid gases to a prewash zone containing amine to remove the acid gases.
  • the method includes withdrawing a prewashed hydrocarbon stream from the prewash zone and feeding the prewashed hydrocarbon stream to an extraction zone.
  • the method contacts the prewashed hydrocarbon stream with an alkaline stream in the extraction zone to convert mercaptans to mercaptides.
  • the method contacts the hydrocarbon stream with water in the extraction zone, wherein the water removes amine entrained in the hydrocarbon stream.
  • the method includes withdrawing an extracted hydrocarbon stream from the extraction zone.
  • the apparatus comprises an extraction vessel including an extraction section positioned below a wash section.
  • the apparatus also includes a hydrocarbon conduit connected to the extraction vessel for delivering a hydrocarbon stream including a mercaptan and an amine for upward flow through the extraction section and through the wash section.
  • An alkaline conduit is connected to the extraction vessel for delivering an alkaline stream for downward flow through the extraction section.
  • a water conduit is connected to the extraction vessel for delivering water for downward flow through the wash section and through the extraction section.
  • the apparatus further includes an effluent outlet for removing the alkaline stream and the water from the extraction vessel.
  • FIG. 1 is a schematic diagram of an apparatus for extracting contaminants from a hydrocarbon stream with alkali and amine in accordance with an embodiment
  • FIG. 2 is a schematic diagram of an apparatus for removing alkali and amine from the extracted hydrocarbon stream in accordance with an embodiment.
  • amine and alkaline are contacted with the hydrocarbon stream in an extraction zone to facilitate removal of mercaptans and acid gases from the hydrocarbon stream. Then, the hydrocarbon stream passes through a wash section of the extraction zone where the hydrocarbon stream is contacted with water. The water removes amine other aqueous soluble impurities in the hydrocarbon stream. The hydrocarbon stream also passes through a coalescer that removes any entrained alkaline in the hydrocarbon stream. Thereafter, the hydrocarbon stream exits the extraction zone, substantially free of amine and alkaline.
  • FIGS. 1 and 2 have been simplified by the deletion of a large number of apparatuses customarily employed in a process of this nature such as vessel internals, temperature and pressure controls systems, flow control valves, recycle pumps, and the like that are not specifically required to illustrate the performance of the method and apparatus.
  • aqueous caustic is mentioned as the exemplary reagent for converting sulfur compounds, other aqueous alkaline solutions are contemplated.
  • an apparatus 8 is provided for removal of contaminants from a hydrocarbon stream 10.
  • the hydrocarbon stream 10 may be liquefied petroleum gas (LPG) or naphtha containing mercaptan sulfur and hydrogen sulfide.
  • LPG liquefied petroleum gas
  • the hydrocarbon stream 10 is fed to an amine absorber vessel 12.
  • Amines 14 such as diethanolamine or monoethanolamine are fed to the amine absorber vessel 12.
  • the amine absorber vessel 12 contains a series of trays.
  • the hydrocarbon stream 10 is introduced proximate the bottom of the amine absorber vessel 12 and the amines 14 are introduced proximate the top of the amine absorber vessel 12 to allow counter-current contact of the amines 14 descending in the amine absorber vessel 12 and the hydrocarbon stream 10 ascending through the amine absorber vessel 12.
  • the amines 14 in the amine absorber vessel 12 react with hydrogen sulfide to yield thiolamides.
  • a hydrocarbon stream 10 containing 100 to 100,000 weight parts per million (wppm) of hydrogen sulfide is reduced down to 15 to 50 wppm of hydrogen sulfide concentration in the amine absorber vessel 12.
  • An amine effluent stream 16 rich in thiolamides exits the bottom of the amine absorber vessel 12 while the hydrocarbon effluent stream 18 exits the top of the amine absorber vessel 12 with a substantially reduced concentration of hydrogen sulfide. Additionally, carbon dioxide or other acid gases that are possibly present in the hydrocarbon stream 10 also react with the amines 14 and are absorbed into the amine effluent stream 16 leaving the amine absorber vessel 12. [0017]
  • a caustic recirculation conduit 20 joins the hydrocarbon effluent stream 18 to allow an aqueous alkaline solution such as aqueous caustic and the hydrocarbon effluent stream 18 from the amine absorber vessel 12 to mix in combined stream 22 before entering an extraction vessel 24.
  • a pressure differential indicator controller (PDIC) 26 maintains a pressure drop across a control valve 28 such as 7 to 103 kilopascals (kPa) and preferably 28 to 55 kPa to ensure adequate mixing between the liquid caustic and the liquid hydrocarbon in the combined stream 22.
  • a static mixer can be used for adequate mixing.
  • the premixed hydrocarbon and aqueous caustic combined stream 22 enters the extraction vessel 24.
  • the extraction vessel 24 comprises a lower prewash zone 30 and an upper extraction zone 32 separated by an imperforate, downwardly convexed baffle 34.
  • the term "zone" can refer to an area including one or more equipment items and/or one or more sub-zones.
  • Equipment items can include one or more reactors or reactor vessels, heaters, exchangers, pipes, pumps, compressors, and controllers. Additionally, an equipment item, such as a reactor, dryer, or vessel, can further include one or more zones or sub-zones.
  • the extraction zone 32 is directly above the prewash zone 30 and both zones 30 and 32 preferably share at least one common wall 33.
  • the prewash zone 30 includes a coalescer 36 proximate a top of the prewash zone 30.
  • the combined stream 22 is fed into the prewash zone 30 proximate a bottom of the prewash zone 30.
  • an aqueous alkaline solution such as caustic of from 2 to 15 weight percent (wt%), such as from 3 to 12 wt%, for example from 6 to 12 wt%, reacts with any remaining hydrogen sulfide to yield a sulfide salt such as sodium sulfide.
  • wt% weight percent
  • sulfide salt such as sodium sulfide
  • a coalescer 36 serves to gather together smaller droplets of caustic that rise in the prewash zone 30 to give them sufficient weight to begin descending through the prewash zone 30 with the rest of the caustic.
  • the prewash zone 30 can also be used to remove COS from the hydrocarbon by reacting it with a solvent composed of a mixture of amine and alkaline.
  • the amine is from 5 to 20 wt% of the solution and the caustic is from 6 to 12 wt%.
  • a transfer conduit 38 has an inlet in communication with the prewash zone 30 proximate a top of the prewash zone 30 above the coalescer 36 and an outlet in communication with the extraction zone 32 proximate a bottom of the extraction zone 32.
  • the higher density caustic pushes the lower density hydrocarbon up through the transfer conduit 38 without the need for a pump.
  • a pump 42 pumps spent caustic out of the bottom of the prewash zone 30 through the recirculation conduit 20.
  • Spent caustic is withdrawn from the recirculation conduit 20 through a line 44 regulated by a control valve 46.
  • the flow rate of caustic through the control valve 46 is automatically controlled by a level indicator controller (LIC) 48 which monitors the level of caustic in the prewash zone 30 at the hydrocarbon-caustic interface.
  • the LIC 48 sensing the level of caustic in the prewash zone 30 signals a setting for the control valve 46 relative to fully open to bring the level of the caustic in the prewash zone 30 to a desired, preset level.
  • spent caustic is continuously withdrawn from the prewash zone 30 through the line 44 via the recirculation conduit 20.
  • the spent caustic withdrawn through the line 44 may be sent to a spent caustic degassing drum (not shown) which allows volatile hydrocarbons to evaporate off of the top of the drum before the spent caustic descends out of the drum to treatment.
  • Regenerated caustic in a line 50 is continuously fed to the caustic recirculation conduit 20 and hence to the prewash zone 30 at a flow rate regulated by a control valve 52 governed by a flow rate controller (FRC) 98.
  • FRC flow rate controller
  • water 54 is added to the caustic recirculation conduit 20.
  • An aqueous alkaline solution such as aqueous caustic in the extraction zone 32 has a concentration of from 12 to 19 wt%), such as from 13 to 16 wt%.
  • a hydrocarbon stream substantially devoid of hydrogen sulfide exits the outlet of the transfer conduit 38 into the extraction zone 32.
  • Mercaptans in the extraction zone 32 react with the caustic to yield sodium mercaptides and water.
  • the lower density hydrocarbons rise to the top of the extraction zone 32 while the aqueous caustic and mercaptides dissolved in the aqueous caustic sink to the bottom of the extraction zone 32 where it collects at the imperforate, downwardly convexed baffle 34.
  • the coalescer 58 coalesces smaller droplets of caustic together to form larger droplets that will tend to sink back to the bottom of the extraction zone 32.
  • Spent caustic rich in mercaptides is withdrawn through a drain at the lowermost portion of the downwardly convexed baffle 34 through a line 62.
  • the line 62 actually extends through the prewash zone 30 above the coalescer 36 and through the common wall 33 thereof.
  • a line 64 adds oxidation catalyst to the line 62.
  • a specific mercaptan oxidation catalyst is not required.
  • Many suitable catalysts are known in the art.
  • One preferred class of catalyst comprises sulfonated metal phthalocyanine.
  • a particularly preferred sulfonated metal phthalocyanine is highly monosulfonated cobalt phthalocyanine or other phthalocyanine catalysts.
  • Additional dipolar type catalysts are suitable for use in an alkaline contacting solution.
  • the oxidation catalyst in the aqueous alkaline solution will have a concentration of from 10 to 500 wppm, such as a concentration of 200 wppm.
  • the spent caustic stream with added catalyst may be heated in an indirect heat exchanger with low pressure stream as a heat exchange fluid in a heater 66.
  • the heater 66 may heat the spent aqueous caustic from 38°C to 43°C.
  • Air sufficient to oxidize the mercaptides is added to the spent caustic stream in the line 62 through a line 68 to form an oxidizer feed line 70.
  • the spent aqueous caustic and air mixture is distributed into an oxidation vessel 72.
  • the sodium mercaptides catalytically react with oxygen and water to yield caustic and organic disulfides.
  • Rashig rings or other particulate packing in the oxidation vessel 72 may increase the surface area therein to improve contact with the catalyst.
  • An exit conduit 74 withdraws effluent from a top of the oxidation vessel 72.
  • the effluent from the oxidation vessel 72 comprises three phases including an air phase, a liquid disulfide phase and a liquid aqueous caustic phase.
  • the exit conduit 74 carries the effluent from the oxidation vessel 72 to a disulfide separator 76 comprising a vertical section 78 and a horizontal section 80. Once settled in the separator, the air phase exits the top of the vertical section 78 through a line 82. The two liquid phases settle in the horizontal section 80 of the disulfide separator 76. The lighter disulfide phase exits the top of the horizontal section 80 through a line 84. The disulfide effluent from the disulfide separator 76 is carried by the line 84 to a sand filter 86 to coalesce and separate any traces of caustic and is removed from the process through a line 88.
  • the vertical section 78 of the disulfide separator 76 includes carbon Rashig rings or other particulate packing to increase the surface area such that liquid entrained in the air is knocked out of entrainment and prevented from exiting through the line 82.
  • a portion of the horizontal section 80 of the disulfide separator 76 includes anthracite coal or other material to serve as a coalescer.
  • Caustic droplets contained in the disulfide phase will be coalesced into larger, heavier droplets that will fall down to the heavier aqueous caustic phase to exit the inlet to the line 90 instead of the inlet to the line 84.
  • the line 90 carrying regenerated caustic splits into two lines 92 and 50.
  • the line 92 carries regenerated caustic to the extraction zone 32 at a rate regulated by a control valve 94 governed by a flow rate controller (FRC) 96.
  • the line 50 carries regenerated caustic to the caustic recirculation conduit 20 at a flow rate regulated by the control valve 52 governed by the FRC 98.
  • FRC 96 and FRC 98 measure the flow rate of caustic in their respective lines 92 and 50 and signal the control valves 52 and 94, a setting relative to fully open to obtain a desired input flow rate.
  • the desired input flow rate is determined to obtain a desired caustic concentration in the respective section of the extraction vessel 24.
  • the pressure in the amine absorber vessel 12 and in the extraction vessel 24 is maintained by regulating the flow of hydrocarbon from the extraction zone 32 in the product conduit 60 by a control valve 61 governed by a pressure indicator controller (PIC) 63 that monitors the pressure in the product conduit 60.
  • PIC pressure indicator controller
  • the pressure should preferably be kept at a level to ensure that the hydrocarbon remains in a liquefied state. This pressure typically ranges from 517 to 2758 kPa.
  • the temperature of the hydrocarbon streams may be maintained at a temperature of 35°C to 40°C.
  • the heater 66 raises the temperature of the spent caustic to from 40°C to 45°C before it enters the oxidation vessel 72 in the line 70.
  • FIG. 1 illustrates an embodiment in which alkali and amines are used to remove contaminants such as mercaptans and acid gases from a hydrocarbon stream 10.
  • FIG. 2 illustrates an apparatus 100 including additional components that may be used with the apparatus 8 of FIG. 1 or with other apparatuses to remove the alkali and amines from the extracted hydrocarbon stream.
  • the apparatus 100 receives a hydrocarbon stream 102.
  • the hydrocarbon stream 102 may be the hydrocarbon stream substantially devoid of hydrogen sulfide that exits the outlet of the transfer conduit 38 in FIG. 1. More generally, the hydrocarbon stream 102 is a hydrocarbon stream that includes amine and mercaptans. For example, the hydrocarbon stream 102 may include 10 wppm to 50 wppm of amine.
  • An exemplary hydrocarbon stream 102 is prewashed LPG. As shown, the hydrocarbon stream 102 is introduced into a lower section 104 of an extraction zone 106.
  • the extraction zone 106 is contained by a column 108 such as extraction vessel 24 of FIG. 1. Further, the extraction zone 106 may be similar or the same as extraction zone 32 of FIG. 1 and positioned over a prewash zone, such as prewash zone 30.
  • the hydrocarbon stream 102 moves upward through contact trays 110 in the lower section 104 of the extraction zone 106.
  • An exemplary lower section 104 of the extraction zone 106 includes from 7 to 12 trays 110.
  • the hydrocarbon stream 102 contacts an alkaline stream 112 that is introduced to the extraction zone 106 proximate the top of the lower section 104 of the extraction zone 106, such as above the uppermost tray 110 in the lower section 104 of the extraction zone 106.
  • mercaptans react with the alkaline stream 112 to yield sodium mercaptides and water.
  • the lower density hydrocarbon stream 102 rises to the top of the lower section 104 of the extraction zone 106 while the alkaline stream 112 and mercaptides dissolved in the alkaline stream 112 sink to the bottom of the lower section 104 of the extraction zone 106.
  • the hydrocarbon stream 102 passes from the lower section 104 of the extraction zone 106 to an upper section 114 of the extraction zone 106. Specifically, the hydrocarbon stream 102 moves above the entry point of the alkaline stream 112. A stream of water 116 is fed into the upper section extraction zone 106. Specifically, the water 116 is introduced above the uppermost tray 110 in the upper section 114 of the extraction zone 106.
  • the upper section 114 of the extraction zone 106 includes from 2 to 4 trays 110.
  • the water 116 move downward through the upper section 114 of the extraction zone 106. As the water 116 contacts the hydrocarbon stream 102 in the upper section 114 of the extraction zone 106, it absorbs amine from the hydrocarbon stream 102. As a result, the hydrocarbon stream 102 exiting the upper section 114 of the extraction zone 106 is substantially devoid of amine.
  • the hydrocarbon stream 102 may include less than 5 wppm amine, such as less than 2 wppm amine, for example less than 1 wppm amine or no amine
  • the hydrocarbon stream 102 passes through a coalescer 120.
  • the coalescer 120 may be the same or similar to the coalescer 58 of FIG. 1.
  • the coalescer 120 may include a mesh blanket having a thickness of 61 cm that coalesces smaller alkaline droplets carried to the top of the extraction zone 106 with the hydrocarbon stream 102 because of their smaller size.
  • the water 116 may be introduced below the coalescer 120 in the extraction zone 106.
  • the coalescer 120 coalesces smaller droplets of alkaline together to form larger droplets that will tend to sink back to the bottom of the extraction zone 106.
  • a treated hydrocarbon stream 122 such as treated LPG, substantially devoid of mercaptans, mercaptides, alkali, and amine exits the extraction zone 106.
  • the exemplary extraction zone 106 is operated at a temperature of from 26°C to 49°C, such as from 32°C to 43°C. Further, the exemplary extraction zone 106 is operated at a pressure of from 517 kPa to 2758 kPa, such as from 690 kPa to 2070 kPa.
  • an effluent stream 124 of alkaline solution rich in mercaptides exits the bottom of the extraction column 108.
  • the effluent stream 124 may exit through a side outlet above an integral prewash zone as in FIG. 1.
  • Air 126 sufficient to oxidize the mercaptides is added to the effluent stream 124 before the effluent stream 124 is heated by heater 128 to a temperature of 38°C to 49°C,. Then, the effluent stream 124 is fed to an oxidation unit 130, similar to or the same as oxidation vessel 72 of FIG. 1.
  • oxidation unit 130 sodium mercaptides catalytically react with oxygen and water to yield caustic and organic disulfides.
  • the oxidized effluent 132 then passes from the top of the oxidation unit 130 to a disulfide separator 134, similar to or the same as disulfide separator 76 of FIG. 1.
  • spent air 136 exist the top of a vertical section of the disulfide separator 134.
  • a lighter liquid phase of disulfide 138 exits the top of a horizontal section of the disulfide separator 134.
  • a heavier liquid phase of alkali forming a recovered alkaline stream 140 exits the bottom of the horizontal section of the disulfide separator 134.
  • the recovered alkaline stream 140 is pumped by pump 142 to a dehydration unit 144.
  • the dehydration unit 144 may be positioned upstream of pump 142 to allow dehydration at lower pressure.
  • the water content of the recovered alkaline stream 140 is reduced.
  • the recovered alkaline stream 140 may include water introduced into the extraction zone 106 at water stream 116 and have a reduced alkaline content.
  • the dehydration unit 144 includes a water balance column operated at 60°C to 70°C.
  • the alkaline stream 112 is formed with a selected water content and alkali content.
  • the alkaline stream 112 may have a water content of 85 wt% to 89 wt% and an alkaline concentration of 11 wt% to 15 wt%.
  • the circulating alkaline stream may be bled or purged and fresh alkaline solution may be added.
  • the alkaline stream may be bled or purged when the amine concentration reaches 5 wt%.
  • the apparatuses and methods described herein provide for the removal of mercaptans and acid gases from hydrocarbon streams. Such removal is performed with alkali and amine.
  • the apparatuses and methods described herein further provide for the removal of the alkaline and amine from the product stream formed by extraction. Further, the apparatuses and methods described herein remove alkaline and amine within an extraction zone, and more specifically, within an extraction vessel without requiring use of additional vessels. As a result, unit costs are reduced.
  • a first embodiment of the invention is a method for processing a hydrocarbon stream, the method comprising feeding a hydrocarbon stream including amine and mercaptan to an extraction zone; contacting the hydrocarbon stream with an alkaline stream in the extraction zone to convert the mercaptan to a mercaptide; and contacting the hydrocarbon stream with water in the extraction zone to remove the amine from the hydrocarbon stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising removing an effluent from the extraction zone; separating a recovered alkaline stream from the effluent; and dehydrating the recovered alkaline stream to form the alkaline stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising withdrawing the hydrocarbon stream from the extraction zone; and passing the hydrocarbon stream through a coalescer to remove alkaline components from the hydrocarbon stream before withdrawing the hydrocarbon stream from the extraction zone.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the extraction zone includes an extraction section positioned below a wash section, wherein contacting the hydrocarbon stream with the alkaline stream comprises contacting the hydrocarbon stream with the alkaline stream in the extraction section, and wherein contacting the hydrocarbon stream with water comprises contacting the hydrocarbon stream with water in the wash section.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the hydrocarbon stream flows upward through the extraction section and through the wash section, and wherein the method further comprises feeding the water to the wash section, wherein the water flows downward through the wash section and through the extraction section; and feeding the alkaline stream to the extraction section, wherein the alkaline stream flows downward through the extraction section.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising removing an effluent including the alkaline stream, the mercaptide, the water, and the amine from the extraction zone.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising oxidizing the effluent and converting the mercaptide to disulfide; and separating the effluent to remove the disulfide from a recovered alkaline stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising dehydrating the recovered alkaline stream to form the alkaline stream; and feeding the alkaline stream to the extraction zone to contact the hydrocarbon stream therein.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein feeding the hydrocarbon stream including amine and mercaptan to the extraction zone comprises feeding the hydrocarbon stream to the extraction zone in an extraction vessel; contacting the hydrocarbon stream with the alkaline stream in the extraction zone comprises contacting the hydrocarbon stream with the alkaline stream in the extraction vessel; and contacting the hydrocarbon stream with water in the extraction zone comprises contacting the hydrocarbon stream with water in the extraction vessel.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein feeding a hydrocarbon stream including amine and mercaptan to the extraction zone comprises feeding a stream of liquefied petroleum gas to the extraction zone.
  • a second embodiment of the invention is a method for processing a hydrocarbon stream, the method comprising feeding a hydrocarbon stream containing sulfur compounds and acid gases to a prewash zone containing amine to remove the acid gases; withdrawing a prewashed hydrocarbon stream from the prewash zone; feeding the prewashed hydrocarbon stream to an extraction zone; contacting the prewashed hydrocarbon stream with an alkaline stream in the extraction zone to convert mercaptans to mercaptides; contacting the hydrocarbon stream with water in the extraction zone, wherein the water removes amine entrained in the hydrocarbon stream; and withdrawing an extracted hydrocarbon stream from the extraction zone.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising removing an effluent from the lower section of the extraction zone; separating the effluent to form a recovered alkaline stream; dehydrating the recovered alkaline stream to form the alkaline stream; and feeding the alkaline stream to the lower section of the extraction zone to contact the prewashed hydrocarbon stream therein.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the prewashed hydrocarbon stream flows upward through the extraction zone, wherein contacting the prewashed hydrocarbon stream with the alkaline stream comprises contacting the prewashed hydrocarbon stream with the alkaline stream in a lower section of the extraction zone, and wherein contacting the prewashed hydrocarbon stream with water comprises contacting the hydrocarbon stream with water in an upper section of the extraction zone.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising feeding water to the upper section of the extraction zone, wherein the water flows downward through the extraction zone; feeding the alkaline stream to the lower section of the extraction zone, wherein the alkaline stream flows downward through the extraction zone; and removing an effluent comprising the water, the alkaline stream, the mercaptides, and the amine from an outlet adjacent the lower section of the extraction zone.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising passing the extracted hydrocarbon stream through a coalescer above the upper section of the extraction zone to remove alkaline components from the extracted hydrocarbon stream before withdrawing the extracted hydrocarbon stream from the extraction zone.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising adding air to the effluent; oxidizing the effluent and converting the mercaptides to disulfides; and separating the effluent to form a stream of air, a stream of disulfides and a recovered alkaline stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising dehydrating the recovered alkaline stream to form the alkaline stream with a higher alkali concentration than the prewash zone; and feeding the alkaline stream to the lower section of the extraction zone to contact the prewashed hydrocarbon stream therein.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the extraction zone is directly above the prewash zone and wherein withdrawing the prewashed hydrocarbon stream from the prewash zone and feeding the prewashed hydrocarbon stream to the extraction zone comprises passing the prewashed hydrocarbon stream from the prewash zone to extraction zone via a conduit.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein feeding the hydrocarbon stream comprises feeding the hydrocarbon stream at a location proximate a bottom of the prewash zone; withdrawing the prewashed hydrocarbon stream from the prewash zone comprises withdrawing the prewashed hydrocarbon stream at a location proximate a top of the prewash zone; feeding the prewashed hydrocarbon stream to the extraction zone comprises feeding the prewashed hydrocarbon stream to a lower section of the extraction zone; and the method further comprises feeding the water to an upper section of the extraction zone.
  • a third embodiment of the invention is an apparatus for processing a hydrocarbon stream, the apparatus comprising an extraction vessel including an extraction section positioned below a wash section; a hydrocarbon conduit connected to the extraction vessel for delivering a hydrocarbon stream including a mercaptan and an amine for upward flow through the extraction section and through the wash section; an alkaline conduit connected to the extraction vessel for delivering an alkaline stream for downward flow through the extraction section; a water conduit connected to the extraction vessel for delivering water for downward flow through the wash section and through the extraction section; and an effluent outlet for removing the alkaline stream and the water from the extraction vessel.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne des procédés et des appareils pour le traitement d'hydrocarbures. Dans un mode de réalisation, un procédé de traitement d'un courant d'hydrocarbures comprend l'alimentation par un courant d'hydrocarbure comprenant une amine et un mercaptan d'une zone d'extraction. Le procédé comprend la mise en contact du courant d'hydrocarbures avec un courant alcalin dans la zone d'extraction pour convertir le mercaptan en un mercaptide. En outre, le procédé comprend la mise en contact du courant d'hydrocarbures avec de l'eau dans la zone d'extraction pour retirer l'amine du courant d'hydrocarbure.
PCT/US2015/034805 2014-06-20 2015-06-09 Procédés et appareils pour le retrait d'amines dans des courants d'hydrocarbures extraits WO2015195402A1 (fr)

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US14/310,192 US20150368568A1 (en) 2014-06-20 2014-06-20 Methods and apparatuses for removing amines from extracted hydrocarbon streams
US14/310,192 2014-06-20

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6749741B1 (en) * 2001-12-20 2004-06-15 Uop Llc Apparatus and process for prewashing a hydrocarbon stream containing hydrogen sulfide
US20040175307A1 (en) * 2001-12-20 2004-09-09 Luigi Laricchia Apparatus and process for extracting sulfur compounds from a hydrocarbon stream

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2596175A (en) * 1948-10-28 1952-05-13 Texaco Development Corp Treating hydrocarbons with alkali metal hydroxides
US20110142738A1 (en) * 2009-12-16 2011-06-16 Uop Llc Method for treating spent regeneration gas

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6749741B1 (en) * 2001-12-20 2004-06-15 Uop Llc Apparatus and process for prewashing a hydrocarbon stream containing hydrogen sulfide
US20040175307A1 (en) * 2001-12-20 2004-09-09 Luigi Laricchia Apparatus and process for extracting sulfur compounds from a hydrocarbon stream
US7381309B1 (en) * 2001-12-20 2008-06-03 Uop Llc Apparatus for prewashing a hydrocarbon stream containing hydrogen sulfide

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