WO2017027554A1 - Gestion de mercaptans au cours d'une hydrodésulfuration sélective de naphta de craquage catalytique fluide - Google Patents

Gestion de mercaptans au cours d'une hydrodésulfuration sélective de naphta de craquage catalytique fluide Download PDF

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WO2017027554A1
WO2017027554A1 PCT/US2016/046281 US2016046281W WO2017027554A1 WO 2017027554 A1 WO2017027554 A1 WO 2017027554A1 US 2016046281 W US2016046281 W US 2016046281W WO 2017027554 A1 WO2017027554 A1 WO 2017027554A1
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stream
mercaptan
boiling point
range
lean
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PCT/US2016/046281
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English (en)
Inventor
Vikrant Vilasrao DALAL
Krishna Mani
Krishan PRATAP
Steven F. Zink
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Uop Llc
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Priority to RU2018104363A priority Critical patent/RU2698100C2/ru
Publication of WO2017027554A1 publication Critical patent/WO2017027554A1/fr
Priority to US15/885,643 priority patent/US20180155640A1/en

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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
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen
    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/10—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including alkaline treatment as the refining step in the absence of hydrogen
    • 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
    • C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
    • 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
    • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
    • 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
    • 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
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/301—Boiling range

Definitions

  • Tier 2 Vehicle and Gasoline Sulfur Program of the US Environmental Protection Agency requires new passenger vehicles to meet stringent emissions standards including a limit of 30 wt ppm sulfur.
  • the Tier 3 Vehicle Emission and Fuel Standards Program will establish even stricter standards with a limit of 10 wt ppm sulfur. Special processing is needed to obtain these sulfur levels.
  • Gasoline from fluid catalytic cracking (FCC) processes comprises up to 50 vol% of a refinery's motor gasoline pool, and up to 90% of the motor gasoline pool's sulfur content. Consequently, it is important that the treatment of this stream not significantly reduce its octane contribution to the pool.
  • Typical processing conditions for hydrodesulfunzation include a temperature of 250°C to 315°C and a pressure of 1.7 MPa (g) to 17-26 bar (g) with a supported CoMo catalyst.
  • the polishing reactor uses a Ni based catalyst with LHSV of lhr "1 and a temperature of 280°C to 380°C.
  • the polishing reactor reduces the mercaptans especially by saturating the olefins and thereby reducing the equilibrium mercaptans in the reactor effluent along with hydrodesulfurization of the recombinant mercaptans.
  • saturating the olefins reduces the octane content.
  • One aspect of the invention is a process for reducing the sulfur content of full range fluidized catalytic cracker (FCC) naphtha.
  • the process includes introducing a FCC naphtha feed to a selective hydrogenation zone in the presence of hydrogen and a hydrogenation catalyst under selective hydrogenation conditions to form a hydrogenated feed.
  • the hydrogenated feed is separated into at least two fractions, a light fraction and a heavy fraction.
  • the heavy fraction is introduced into a selective hydrodesulfurization zone in the presence of hydrogen and a hydrodesulfurization catalyst under selective hydrodesulfurization conditions to form a desulfurized stream, the desulfurized stream containing mercaptans.
  • At least a portion of the desulfurized stream is separated into at least two streams, a mercaptan rich stream and a first mercaptan lean stream. At least a portion of the mercaptan rich stream is treated to remove at least a portion of the mercaptan compounds to form a second mercaptan lean stream.
  • a variety of processes can be used to treat the mercaptan rich stream including, but not limited to, a caustic extraction process, a hydrodesulfurization reaction zone, a selective hydrogenation process, an adsorption process, and an ionic liquid extraction process.
  • FIG. 1 is an illustration of one embodiment of the process of the present invention.
  • Fig. 2 is an illustration of another embodiment of the process of the present invention.
  • Fig. 3 is an illustration of still another embodiment of the process of the present invention.
  • Fig, 4 is an illustration of yet another embodiment of the process of the present invention.
  • Fig. 5 is an illustration of another embodiment of the process of the present invention.
  • the sulfur characterization of the selective hydrodesulfurization (HDS) reactor effluent points to the presence of an abundance of butyl mercaptans.
  • thiophene desulfurization proceeds along two parallel pathways.
  • the thiophene hvdrogenation and hvdrogenolysis reactions occur simultaneously to generate cyclic sulfide and cis and trans-2-butene and then proceed further to 1-butene and butane.
  • This reaction network also includes olefin saturation reactions. Hydrogenolysis and hvdrogenation reactions take place on different sites of the catalyst simultaneously.
  • the hydrogenolysis reaction is represented as occurring at the sigma site, and hydrogenation at the pi site. All the above postulates are reflected in experimental selective HDS runs where equilibrium mercaptans are present due to the recombination of butenes with the H 2 S.
  • All of the processes begin with the treatment of the FCC naphtha feed in a selective hvdrogenation zone to hvdrogenate the diolefms in the feed.
  • the hvdrogenated feed is then separated in a splitter column into at least two fractions, a light fraction and a heavy fraction.
  • the light traction has a boiling point in the range of less than 60°C
  • the heavy fraction has a boiling point in the range of greater than 60°C.
  • the light fraction has a boiling point in the range of less than 65°C
  • the heavy fraction typically has a boiling point in the range of greater than 65°C
  • the heavy fraction is sent to the selective hydrodesulfurization zone where the sulfur in the feed is converted to hydrogen sulfide, and some of the hydrogen sulfide further reacts with olefins in the feed to form mercaptides.
  • the effluent from the selective hydrodesulfurization zone is separated into a least two streams, a mercaptan rich stream and a mercaptan lean stream.
  • a mercaptan rich stream and a mercaptan lean stream.
  • there are two mercaptan lean streams a low boiling mercaptan lean stream with a boiling point range lower than that of the mercaptan rich stream and a high boiling lean mercaptan stream with a boiling point range greater than that of the mercaptan rich stream.
  • the mercaptan rich stream is then treated to remove the mercaptans.
  • a mercaptan rich stream is sent to a caustic extraction zone to remove the mercaptans.
  • the mercaptan free effluent stream from the caustic extraction zone can be sent to the gasoline pool.
  • the mercaptan rich stream is treated in a polishing reactor to reduce the level of mercaptans. By sending a concentrated mercaptan rich feed to the polishing reactor, the size of the polishing reactor can be reduced by a significant amount, in some cases as much as 75-80%.
  • Another embodiment involves sending the mercaptan rich stream to the upstream selective hydrogenation reactor which converts the mercaptans into heavy disulfides.
  • the mercaptan rich stream is treated in an adsorbent zone to reduce the mercaptans.
  • Another possibility is to treat the mercaptan rich streamin an ionic liquid extraction zone. The ionic liquid can be regenerated as needed and recycled to the extraction zone.
  • the light fraction from the selective hydrodesulfurization zone can have a boiling point of less than 60°C, or less than 65°C.
  • the light fraction 140 typically has a T5 boiling point of 0°C to 25°C, a T95 boiling point of 50°C to 80°C, and a final boiling point of 85°C to 100°C.
  • the heavy fraction from the selective hydrodesulfurization zone can have a boiling point in the range of 60°C to 220°C, 65°C to 220°C, 60°C to 200°C, or 65°C to 200°C, for example.
  • the heavy fraction typically has a T5 boiling point of 50°C to 80°C, a T95 boiling point of 160°C to 220°C, and a final boiling point of greater than 220°C to 220°C
  • This heavy fraction could be fractionated into a mercaptan rich stream with a boiling point in the range of 60°C to 120°C, or 60°C to 100°C, or 65°C to 120°C, or 65°C to 100°C, and a mercaptan lean stream with a boiling point in the range of 100°C to 220°C, 120°C to 220°C, or 100°C to 200°C, or 120°C to 200°C.
  • the mercaptan rich stream has a T5 boiling point of 60°C to 70°C, a T95 boiling point of 90°C to 100°C, and a final boiling point of 100°C to 120°C.
  • the mercaptan lean stream has a T5 boiling point of 120°C to 140°C, a T95 boiling point of 190°C to 210°C, and a final boiling point of 200°C to 220°C.
  • the mercaptan rich stream has a T5 boiling point of 60°C to 70°C, a T95 boiling point of 90°C to 100°C, and a final boiling point of 100°C.
  • the desulfurized stream could be divided into a low boiling mercaptan lean stream with a boiling point in the range of 60°C to 85°C, or 65°C to 85°C, a mercaptan rich stream with a boiling point in the range of 85°C to 120°C, or 85°C to 100°C, and a high boiling mercaptan lean stream with a boiling point in the range of 100°C to 220°C, or 120°C to 220°C, or 100°C to 200°C, or 120°C to 200°C.
  • the low boiling mercaptan lean stream has a T5 boiling point of 60°C to 65°C, a T95 boiling point of 75°C to 85 C 'C, and a final boiling point of 80 C 'C to 90°C.
  • the mercaptan rich stream has a T5 boiling point of 80°C to 90°C, a T95 boiling point of 90°C to 100°C, and a final boiling point of 100°C to 120°C.
  • the high boiling mercaptan lean stream has a T5 boiling point of 100°C to 120°C, a T95 boiling point of 180°C to 200°C, and a final boiling point of 200°C to 220°C.
  • the mercaptan rich stream has a T5 boiling point of 80°C to 90°C, a T95 boiling point of 90°C to 100°C, and a final boiling point of 100°C.
  • FIG. 1 One embodiment of the process 100 is illustrated in Fig. 1.
  • the full range fluidized catalytic cracker (FCC) naphtha feed 105 and hydrogen stream 1 10 are introduced into a selective hydrogenation zone 115.
  • the hydrogen 110 can be a recycle hydrogen stream 125,
  • the selective hydrogenation zone 115 is normally operated at relatively mild hydrogenation conditions. These conditions will normally result in the hydrocarbons being present as liquid phase materials.
  • the reactants will normally be maintained under the minimum pressure sufficient to maintain the reactants as liquid phase hydrocarbons.
  • a broad range of suitable operating pressures therefore extends from 276 kPa (g) to 5516 kPa (g) (40 psig to 800 psig), or 345 kPa (g) to 2069 kPa (g) (50 and 300 psig).
  • a relatively moderate temperature between 25°C and 350°C (77°F to 662°F), or 50°C and 200°C (122°F to 392°F)is typically employed.
  • the liquid hourly space velocity of the reactants through the selective hydrogenati on catalyst should be above 1.0 hr "1 , or above 5.0 hr "1 , or between 5.01 hr '1 and 35.0 hr "1 .
  • Another variable operating condition is the ratio of hydrogen to diolefmic hydrocarbons maintained within the selective hydrogenati on zone 115. The amount of hydrogen required to achieve a certain conversion is believed dependent upon both reactor temperature and the molecular weight of the feed hydrocarbons.
  • the mole ratio of hydrogen to diolefmic hydrocarbons in the material entering the bed of selective hydrogenati on catalyst is maintained between 1 : 1 and 1.8: 1.
  • the optimum set of conditions will of course vary depending on such factors as the composition of the feed stream and the degree of saturation of diolefmic hydrocarbons which it is desired to perform ,
  • Suitable catalyst which is capable of selectively hydrogenating dioiefms in a naphtha stream may be used.
  • Suitable catalysts include, but are not limited to, a catalyst comprising copper and at least one other metal such as titanium, vanadium, chrome, manganese, cobalt, nickel, zinc, molybdenum, and cadmium or mixtures thereof.
  • the metals are preferably supported on inorganic oxide supports such as silica and alumina, for example.
  • the catalyst is employed in a fixed bed reactor containing a cylindrical bed of catalyst through which the reactants move in a vertical direction.
  • Other embodiments use trickle bed reactors.
  • the reactants flow upward through the reactor, while other embodiments use a downflow arrangement.
  • the subject catalyst may be present within the reactor as pellets, spheres, extrudates, irregular shaped granules, etc.
  • the reactants would be preferably brought up to the desired inlet temperature of the reaction zone, admixed with hydrogen and then passed into and through the reactor. Alternatively, the reactants may be admixed with the desired amount of hydrogen and then heated to the desired inlet temperature.
  • the effluent of the reaction zone may be passed into a product recovery facility for the removal of residual hydrogen or may be passed directly into downstream product utilization zones if the presence of the residual hydrogen is acceptable.
  • Hydrogen may be removed by flashing the effluent stream to a lower pressure or by passing the effluent stream into a stripping column.
  • the hydrogenated effluent 130 is sent to a splitter column 135 where it is separated into a light fraction 140 and a heavy fraction 145.
  • the light fraction 140 typically has a boiling point in the range of less than 65°C
  • the heavy fraction 145 typically has a boiling point in the range of greater than 65°C.
  • the heavy fraction 145 is combined with a hydrogen-rich stream 150 and introduced into a selective hydrodesulfurization zone 155 to selectively remove sulfur.
  • the selective hydrodesulfurization zone 1 55 contains a hydrotreating catalyst (or a combination of hydrotreating catalysis) and operated at selected hydrotreating conditions effective to convert a majority of the sulfur in the feed to hydrogen sulfide and minimize saturation of olefins at the same time.
  • Such selective conditions include a temperature from 260 o C(500°F) to 315°C (600°F), a pressure from 0.69 MPa (100 psig) to 3,45 MPa (500 psig), a liquid hourly space velocity of the fresh hydrocarbonaceous feedstock from 0.5 hr " 1 to 10 hr '1 .
  • Other hydrotreating conditions are also possible depending on the particular feed stocks being treated.
  • the selective hydrodesulfurization zone 155 may contain a single reactor or multiple reactors and each reactor may contain one or more reaction zones with the same or different catalysts to convert sulfur and nitrogen to hydrogen sulfide and ammonia.
  • Suitable hydrodesulfurization catalysts are any known conventional hydrotreating catalysts and include those which are comprised of at least one Group VIII metal (preferably iron, cobalt and nickel, more preferably cobalt and/or nickel) and at least one Group VI metal (preferably molybdenum and tungsten) on a high surface area support material, preferably alumina.
  • Other suitable hydrotreating catalysts include zeolitic catalysts, as well as noble metal catalysts where the noble metal is selected from palladium and platinum. It is within the scope of the processes herein that more than one type of hydrotreating catalyst be used in the same reaction vessel.
  • the Group VIII metal is typically present in an amount ranging from 0.5 to 20 weight percent, preferably from 0.5 to 0 weight percent.
  • the Group VI metal will typically be present in an amount ranging from I to 25 weight percent, and preferably from 1 to 12 weight percent. While the above describes some exemplar ⁇ ' catalysts for hydrotreating, other hydrotreating and/or hydrodesulfurization catalysts may also be used depending on the particular feedstock and the desired effluent quality.
  • the conditions in the selective hydrodesulfurization zone 155 are effective to convert greater than 50 percent of the sulfur in the heavy fraction 145 to hydrogen sulfide and, preferably, 60 to 80 percent of the sulfur to hydrogen sulfide. At the same time, the selected conditions disfavor olefin saturation to generally maintain the octane level. However, at these conditions, some of the hydrogen sulfide produced reacts to form mercaptans. These reactions are often called reversion or recombination reactions.
  • the effluent 160 from the selective hydrodesulfurization zone 155 can have a boiling point in the range of 60°C to 220°C, or 65°C to 220°C, or 60°C to 200°C, or 65°C to 200°C, for example.
  • the effluent 160 can have a T5 boiling point of 60°C to 70°C, a T95 boiling point of 160°C to 200°C, and a final boiling point of 200°C to 220°C or greater.
  • the effluent 160 from the selective hydrodesulfurization zone 155 is sent to a separator 165 where it is separated into the hydrogen rich stream 170 and a liquid stream 175,
  • one portion of hydrogen rich stream 170 comprises hydrogen-rich stream 150 and the remainder comprises recycle hydrogen stream 125, Makeup hydrogen 120 can be added to hydrogen rich stream 170 as needed.
  • Liquid stream 175 is sent to a fractionation zone 180 where it is separated into at least two streams. As illustrated in Fig. 1, liquid stream 175 is separated into a mercaptan rich stream 185 taken as a side cut stream and a first mercaptan lean stream 190 taken from a bottoms of the fractionation zone 180.
  • the mercaptan rich stream 185 has a boiling point in the range of 60°C to 120°C, or 60°C to 100°C, or 65°C to 120°C, or 65°C to 100°C.
  • the first mercaptan lean stream 190 has a boiling point in the range of I 00°C to 220°C, or 120°C to 220°C, or 100°C to 200°C, or 120°C to 200°C.
  • the mercaptan rich stream 185 has a T5 boiling point of 60°C to 70°C, a T95 boiling point of 90 C 'C to 100°C, and a final boiling point of 100°C to 120°C.
  • the mercaptan lean stream 190 has a T5 boiling point of 120°C to 140°C, a T95 boiling point of 190°C to 210°C, and a final boiling point of 200°C to 220°C.
  • the mercaptan rich stream 185 is sent to a caustic extraction zone 195 to remove the mercaptans.
  • a sulfur lean caustic stream 200 enters the caustic extraction zone 195 and contacts the mercaptan rich stream 185.
  • the caustic extraction process may utilize any alkaline reagent which is capable of extracting mercaptans from the feed stream at practical operating conditions and which may be regenerated in the manner described.
  • a preferred alkaline reagent comprises an aqueous solution of an alkaline metal hydroxide, such as sodium hydroxide or potassium hydroxide.
  • Sodium hydroxide commonly referred to as caustic
  • caustic may be used in concentrations of from 1 to 50 wt.%, with a preferred concentration range being from 5 to 25 wt.%.
  • an agent to increase the solubility of the mercaptans in the solution typically methanol or ethanol although others such as a phenol, cresol or butyric acid may be used.
  • the conditions employed in the caustic extraction zone 195 may vary greatly depending on such factors as the nature of the hydrocarbon stream being treated and its mercaptan content, etc.
  • the extraction may be performed at an ambient temperature above 15.6°C(60°F) and at a pressure sufficient to ensure liquid state operation.
  • the pressure may range from atmospheric up to 6.9 MPa (g) (1000 psig) or more, but a pressure in the range of from 345 kPa(g) to 1034 kPa(g) (50 psig to 150 psig) is preferred.
  • a second consideration is that the pressure chosen should ensure an adequate amount of oxygen is dissolved in the alkaline stream in the downstream oxidation step (not shown), which if practical is preferably operated at substantially the same pressure as the caustic extraction zone 195 after normal process flow pressure drops are taken into consideration.
  • the temperature in the caustic extraction zone 195 is desirably in the range of 10°C to 12PC (50°F to 250°F), or 26.7°C to 48.9°C (80°F to 120°F).
  • the ratio of the volume of the alkaline solution required per volume of the feed stream will vary depending on the mercaptan content of the feed stream. Normally this ratio will be between 0.01 : 1 and 1 : 1, although other ratios may be desirable.
  • Optimum extraction in this liquid system is obtained with a velocity through the perforations of from 5 to 10 feet per second.
  • Essentially all of the extractable mercaptans should be transferred to the alkaline solution from the feed stream.
  • the term "essentially all” is intended to refer to at least 95% and preferably 98% of all the material referred to.
  • the mercaptans are transferred from the mercaptan rich stream 185 to the sulfur lean caustic stream 200, resulting in a second mercaptan lean stream 205 and a sulfur rich caustic stream 210.
  • the sulfur rich caustic stream 210 can be sent for treatment to remove the sulfur (not shown) and recycled to the caustic extraction zone 195, if desired.
  • the second mercaptan lean stream 205 can be combined with the first mercaptan lean stream 190 to form a combined mercaptan lean stream 215.
  • light fraction 140 can be combined with the first mercaptan lean stream 190, the second mercaptan lean stream 205, or both.
  • the combined mercapta lea stream 215 can be sent to the gasoline pool. There is also an overhead stream 220, which is condensed and separated in a separator 225 into a gas stream 230 and a liquid stream 235 which is refluxed to the fractionation zone 180.
  • the olefins present in the naphtha fraction having a boiling point in the range of 60°C to 120°C in the mercaptan rich stream 185 taken from the side of the fractionation zone 180 are retained.
  • liquid stream 175 from the separator 165 could be separated into a mercaptan rich stream and a low boiling first mercaptan lean stream, and a high boiling first mercaptan lean stream, as discussed below in regard to Fig. 2.
  • the mercaptan rich stream is treated in a polishing reactor to reduce the mercaptans.
  • the FCC naphtha feed 105 is hydrogenated in the selective hydrogenation zone 1 15, separated into a light fraction 140 and a heavy fraction 145 in splitter column 135, and desulfurized in selective hydrodesulfurization zone 155 in the same way as described above with respect to Fig. 1.
  • the effluent 160 from the selective hydrodesulfurization zone 155 is sent to separator 165, which is a divided wail separator.
  • the divided wall separator 165 has a wall 305 dividing it in two sections 310, 315.
  • the effluent 160 enters section 310 where it is separated into hydrogen-rich stream 170 and liquid stream 175,
  • Liquid stream 175 is sent to fractionation zone 180 where it is separated into a low boiling first mercaptan lean stream 320, a mercaptan rich stream 325, and a high boiling first mercaptan lean stream 330.
  • the low boiling first mercaptan lean stream 320 has a boiling point range lower than the boiling point range of the mercaptan rich stream 325, while the high boiling first mercaptan lean stream 330 has a boiling point range greater than the mercaptan rich stream 325.
  • the low boiling mercaptan lean stream 320 could have a boiling point in the range of 60°C to 85°C, or 65°C to 85°C
  • the mercaptan rich stream 325 could have a boiling point in the range of 85°C to 120°C, or 85°C to 100°C
  • the high boiling mercaptan lean stream 330 could have a boiling point in the range of 100°C to 220°C, or 120°C to 220°C, or 100°C to 200°C, or 120°C to 200°C.
  • the low boiling mercaptan lean stream 320 has a T5 boiling point of 60°C to 65°C, a T95 boiling point of 75°C to 85°C, and a final boiling point of 80°C to 90°C).
  • the mercaptan rich stream 325 has a T5 boiling point of 80°C to 90°C, a T95 boiling point of 90°C to 100°C, and a final boiling point of 100°C to 120°C.
  • the high boiling mercaptan lean stream 330 has a T5 boiling point of 100°C to 120°C, a T95 boiling point of 180°C to 200°C, and a final boiling point of 200°C to 220°C.
  • the mercaptan rich stream 325 and a hydrogen rich stream 335 are sent to a polishing reactor (e.g., a hydrodesulfurization reactor) 340.
  • the hydrogen rich stream 335 can be a portion of the hydrogen rich stream 170 from the divided wall separator 165.
  • the polishing reactor 340 contains a desulfurization catalyst. Suitable catalysts include, but are not limited to nickel, nickel and molybdenum, zeolitic catalysts, and noble metal catalysts, e.g. platinum or palladium. In general, the polishing reactor 340 is operated at a temperature in the range of 280°C to 380°C, and a pressure in the range of 350 kPa(g) to 3450 kPa(g).
  • the desulfurized effluent 345 from the polishing reactor 340 is sent to section
  • Liquid stream 350 is sent to a stripping zone 355 to remove gases 360 forming a third mercaptan lean stream 365.
  • the third mercaptan lean stream 365 can be combined with one or more of the low boiling first mercaptan lean stream 320, the high boiling mercaptan lean stream 330, and the light fraction 140 from the splitter column 135 to form a combined mercaptan lean stream 370.
  • the size of the polishing reactor340 can be reduced by a significant amount, in some cases as much as 75-80%.
  • the low boiling mercaptan lean stream 320 which has a boiling point range of 60°C to 85°C is not sent to polishing reactor 340which results in the olefins present in this fraction being retained.
  • the liquid stream 175 can be separated into a mercaptan rich stream and a mercaptan lean stream as described above in Fig. 1, rather than a mercaptan rich stream and at least two mercaptan lean streams.
  • the mercaptan rich stream is treated by recycling it to the selective hydrogenation zone 115 which converts the mercaptans into heavy disulfides. In this way, a separate polishing zone is avoided.
  • the FCC naphtha feed 105 is hydrogenated in the selective hydrogenation zone 1 15, separated into a light fraction 140 and a heavy fraction 145 in splitter column 135, desulfurized in selective hydrodesulfurization zone 155, separated into hydrogen-rich stream 170 and liquid stream 175 in the same way as described above with respect to Fig. 1.
  • the liquid stream 175 is sent to the fractionation zone 180 where it is separated into a low boiling first mercaptan lean stream 405, a mercaptan rich stream 410, and a high boiling first mercaptan lean stream 415.
  • the mercaptan rich stream 410 is sent to the selective hydrogenation zone 15 to be reprocessed.
  • the flow rates of the mercaptan rich stream 410 and the high boiling first mercaptan lean stream 415 can be controlled with a ratio controller 420.
  • the low boiling first mercaptan lean stream 405 can be combined with one or more of the high boiling first mercaptan lean stream 415 and the light fraction 140 from the splitter column 135 to form a combined mercaptan lean stream 425.
  • the liquid stream 175 can be separated into a mercaptan rich stream and a mercaptan lean stream as described above in Fig, I, rather than a mercaptan rich stream and at least two mercaptan lean streams.
  • the mercaptan rich stream is treated by passing it on the adsorption zone 520,
  • the FCC naphtha feed 105 is hydrogenated in the selective hydrogenation zone 1 15, separated into a light fraction 140 and a heavy fraction 145 in splitter column 135, desulfurized in selective hydrodesulfurization zone 155, separated into hydrogen-rich stream 170 and liquid stream 175 in the same way as described above with respect to Fig. 1.
  • the liquid stream 175 is sent to the fractionation zone 180 where it is separated into a low boiling first mercaptan lean stream 505, a mercaptan rich stream 510, and a high boiling first mercaptan lean stream 515.
  • the mercaptan rich stream 510 is sent to an adsorption zone520.
  • the adsorption zone 520 contains one or more adsorbent beds containing an adsorbent.
  • the adsorbent can be regenerable or non-regenerable.
  • Suitable adsorbents include, but are not limited to nickel zeolite Y, nickel exchanged zeolite X, molybdenum exchanged zeolite X, a smectite clay having a surface area of at least 150 m 2 /g, and mixtures thereof.
  • Zeolite X belongs to the faujasite family of zeolites. Its synthesis was first reported in U.S. Pat. No. 2,882,244 which is incorporated by reference. Zeolite X has the empirical formula:
  • zeolite X is prepared by forming a reaction mixture containing reactive sources of the components, reacting the mixture at a temperature of 21°C to 120°C for a time of 1 hours to 100 hours. Zeolite X is usually synthesized in the sodium form. That is, sodium is the counter ion present in the pores of the zeolite.
  • Zeolite Y has an empirical formula expressed in terms of moles of oxides of:
  • the nickel or molybdenum forms of zeolites X and Y can be prepared by ion exchange methods well known in the art. Ion exchange can be carried out in a batch or continuous process with a continuous process preferred.
  • the metal salts which can be used to carry out the exchange include nickel chloride, nickel nitrate, and sodium moiybdate.
  • Yet another set of adsorbents is the group of clays which make up the smectite family of clays and which have a surface area of at least 150 m " Vg.
  • Clays are composed of infinite layers (lamellae) of metal oxides and hydroxides stacked one on top of the other.
  • These layers or sheets are composed of tetrahedrally coordinated cations which are linked through shared oxygens to sheets of cations octahedrally coordinated to oxygens and hydroxyls.
  • a 1 : 1 layered structure is formed as in kaolinite
  • a 2: 1 layered structure is produced as in beidellite.
  • Anionic charges on the tetrahedral layers are neutralized by cations such as Na ⁇ or Ca ⁇ 2 in the interiamellar spaces. These cations can be exchanged with other cations.
  • the smectite clays are 2: 1 layered swellable clays.
  • swellable is meant that the clays swell or expand when placed in water or other solvents.
  • Specific smectite clays are montmorillonite, beidellite, ontronite, hectorite, saponite and sauconite.
  • the contacting can be carried out in a batch mode or in a continuous mode.
  • the stream to be treated is mixed with a sufficient amount of adsorbent in an appropriate size reaction vessel.
  • the resultant mixture can be stirred or agitated to ensure complete contact of the stream with the adsorbent.
  • the adsorbent i placed in a vertical column and the stream to be treated is upflowed through the column.
  • the stream is flowed at a liquid hourly space velocity of 0.1 hr 'to 10 hr '1 .
  • the adsorbent can be used in the form of extrudates, pills, beads, spheres, etc.
  • the adsorbent is mixed with a binder such as at tapulgite clay, minugel clay and bentonite clay and then formed into the desired shape.
  • the amount of binder which is used varies from 8 to 20 wt. %. Processes for forming the various shapes are well known in the art.
  • the contacting can be carried out over a broad temperature range. Generally the temperature range is from 10°C to 100°C, or 20°C to 70 C' C.
  • the process is conducted at atmospheric pressure or pressures up to 1379 kPa (g) (200 psig).
  • the second mercaptan lean stream 525 from the adsorption zone 520 can be combined with the low boiling fixst mercaptan lean stream 505, and/or the high boiling first mercaptan lean stream 515 to form a combined mercaptan lean stream 530.
  • the light fraction 140 can be combined with one or more of these streams as well.
  • the liquid stream 175 can be separated into a mercaptan rich stream and a mercaptan lean stream as described above in Fig. 1 , rather than a mercaptan rich stream and at least two mercaptan lean streams.
  • the mercaptan rich stream is treated using an ionic liquid.
  • the FCC naphtha feed 105 is hydrogenated in the selective hydrogenation zone 115, separated into a light fraction 140 and a heavy fraction 145 in splitter column 135, desulfurized in selective hydrodesulfurization zone 155, separated into hydrogen-rich stream 170 and liquid stream 175 in the same way as described above with respect to Fig. 1 ,
  • the liquid stream 175 is sent to the fractionation zone 180 where it is separated into a low boiling first mercaptan lean stream 605, a mercaptan rich stream 610, and a high boiling first mercaptan lean stream 615.
  • the mercaptan rich stream 610 is sent to an ionic liquid extraction zone 620along with lean ionic liquid stream 625.
  • the lean ionic liquid stream 625 can include fresh ionic liquid and/or regenerated ionic liquid.
  • Ionic liquids suitable for use in the instant invention are naphtha-immiscible ionic liquids.
  • naphtha-immiscible ionic liquid means the ionic liquid is capable of forming a separate phase from naphtha under the operating conditions of the process. Ionic liquids that are miscible with naphtha at the process conditions will be completely soluble with the naphtha; therefore, no phase separation will be feasible. Thus, naphtha-immiscible ionic liquids may be insoluble with or partially soluble with the hydrocarbon feed under the operating conditions.
  • An ionic liquid capable of forming a separate phase from the naphtha under the operating conditions is considered to be naphtha- immiscible.
  • Ionic liquids according to the invention may be insoluble, partially soluble, or completely soluble (miscible) with water.
  • the ionic liquid can be any acidic ionic liquid. There can be one or more ionic liquids.
  • the ionic liquid comprises an organic cation and an anion. Suitable cations include, but are not limited to, nitrogen-containing cations and phosphorus-containing cations. Suitable organic cations include, but are not limited to:
  • R'-R 21 are independently selected from C1-C20 hydrocarbons, C-.-Czo hydrocarbon derivatives, halogens, and H.
  • Suitable hydrocarbons and hydrocarbon derivatives include saturated and unsaturated hydrocarbons, halogen substituted and partially substituted hydrocarbons and mixtures thereof.
  • Ci-Cg hydrocarbons are particularly suitable.
  • the anion can be derived from halides, typically halometallates, and combinations thereof.
  • the anion is typically derived from metal and nonmetal halides, such as metal and nonmetal chlorides, bromides, iodides, fluorides, or combinations thereof.
  • Combinations of halides include, but are not limited to, mixtures of two or more metal or nonmetal halides (e.g., AICI4 " and BF 4 " ), and mixtures of two or more halides with a single metal or nonmetal (e.g., AlCl 3 Br " ).
  • the metal is aluminum, with the mole fraction of aluminum ranging from 0 ⁇ Al ⁇ 0.25 in the anion.
  • Suitable anions include, but are not limited to, A1C1 4 " , A1 2 C1 7 “ , A1 3 C1 10 “ , AlCl 3 Br “ , Al 2 Cl 6 Br “ , Al 3 Cl 9 Br “ , AlBr “ , Al 2 Br 7 “ , Al 3 Brio “ , GaCl 4 “ , Ga 2 Cl “ , Ga 3 Cl 10 " , GaCl 3 Br “ , Ga 2 Cl 6 Br “ , Ga-jCUjBr “ , CuCl? “ , CU2CI3 “ , CU3CI4 “ , ZnCl 3 “ , FeCl 3 “ , FeCl 4 “ , Fe 3 Cl 7 “ , PF 6 ⁇ , and BF 4 " .
  • the mercaptan removal step may be conducted under mercaptan removal conditions including temperatures and pressures sufficient to keep the ionic liquid and naphtha feeds and effluents as liquids.
  • the mercaptan removal step temperature may range between 10°C and less than the decomposition temperature of the ionic liquid, and the pressure may range between atmospheric pressure and 700 kPa (g).
  • the decomposition temperature of the ionic liquid is the lowest temperature at which any of the ionic liquid components decompose.
  • the mercaptan removal step may be conducted at a uniform temperature and pressure or the contacting and separating steps of the mercaptan removal step may be operated at different temperatures and/or pressures.
  • the contacting step is conducted at a first temperature
  • the separating step is conducted at a temperature at least 5°C lower than the first temperature. Such temperature differences may facilitate separation of the naphtha and ionic liquid phases.
  • the mercaptan removal step conditions such as the contacting or mixing time, the separation or settling time, and the ratio of the mercaptan rich stream 610 to the lean ionic liquid stream 625 may vary greatly based, for example, on the specific ionic liquid or liquids employed, the nature of the naphtha feed (straight run or previously processed), the sulfur content of the naphtha feed, the degree of sulfur removal required, the number of sulfur removal steps employed, and the specific equipment used.
  • contacting time may range from less than one minute to two hours; settling time may range from one minute to eight hours: and the weight ratio of naphtha feed to lean ionic liquid introduced to the sulfur removal step may range from 1 : 10,000 to 10,000: 1 , In an embodiment, the weight ratio of naphtha feed to lean ionic liquid may range from 1 : 1,000 to 1,000: 1; and the weight ratio of naphtha feed to lean ionic liquid may range from 1 : 100 to 100: 1. In an embodiment the weight of naphtha feed is greater than the weight of ionic liquid introduced to the sulfur removal step.
  • the mercaptan rich stream 610 and the lean ionic liquid stream 625 are contacted forming the second mercaptan lean stream 630, and amercaptan rich ionic liquid stream 635 containing mercaptan compounds.
  • the ionic liquid extraction zone 620 includes a contacting zone with a mixer/settler in which the mercaptan rich stream 610 and the lean ionic liquid stream 625 are mixed and then allowed settle, forming two phases: an ionic liquid phase and a naphtha phase.
  • the ionic liquid extraction zone 620 includes a countercurrent extraction column.
  • the mercaptan rich stream 610and the lean ionic liquid stream 625 flow counter currently and the mercaptan compounds are transferred from the mercaptan rich stream to the ionic liquid.
  • the ionic liquid extraction zone 620 can include an optional water washing zone to recover ionic liquid that is entrained or otherwise remains in the naphtha.
  • the water washing step can be performed using any suitable equipment and conditions used to conduct other liquid-liquid wash and extraction operations.
  • the mercaptan rich ionic liquid stream 635 can be sent to an optional regeneration zone to regenerate the rich ionic liquid by removing the mercaptan compounds from the ionic liquid.
  • the rich ionic liquid can be regenerated in any suitable manner. A variety of methods for regenerating ionic liquids have been developed.
  • US 7,651,970; US 7,825,055; US 7,956,002; US 7,732,363, each of which is incorporated herein by reference, describe contacting ionic liquid containing the conjunct polymer with a reducing metal (e.g., Al), an inert hydrocarbon (e.g., hexane), and hydrogen and heating to 100°C to transfer the conjunct polymer to the hydrocarbon phase, allowing for the conjunct polymer to be removed from the ionic liquid phase.
  • a reducing metal e.g., Al
  • an inert hydrocarbon e.g.
  • Still another method of regenerating the ionic liquid involves contacting the ionic liquid containing the conjunct polymer with a reducing metal (e.g., Al), HC1, and an inert hydrocarbon (e.g. hexane), and heating to 100°C to transfer the conjunct polymer to the hydrocarbon phase.
  • a reducing metal e.g., Al
  • HC1 e.g., HC1
  • an inert hydrocarbon e.g. hexane
  • the ionic liquid can be regenerated by adding a homogeneous metal hydrogenation catalyst (e.g., (PPh 3 ) 3 RhCl) to ionic liquid containing conjunct polymer and an inert hydrocarbon (e.g. hexane), and introducing hydrogen.
  • a homogeneous metal hydrogenation catalyst e.g., (PPh 3 ) 3 RhCl
  • a homogeneous metal hydrogenation catalyst e.g., (PPh 3 ) 3 RhCl
  • an inert hydrocarbon e.g. hexane
  • Another method for regenerating the ionic- liquid involves adding HC1, isobutane, and an inert hydrocarbon to the ionic liquid containing the conjunct polymer and heating to 100°C.
  • the conjunct polymer reacts to form an uncharged complex, which transfers to the hydrocarbon phase.
  • the ionic liquid could also be regenerated by adding a supported metal hydrogenation catalyst (e.g. Pd/C) to the ionic liquid containing the conjunct polymer and an inert hydrocarbon (e.g. hexane). Hydrogen is introduced and the conjunct polymer is reduced and transferred to the hydrocarbon layer.
  • a supported metal hydrogenation catalyst e.g. Pd/C
  • an inert hydrocarbon e.g. hexane
  • Hydrogen is introduced and the conjunct polymer is reduced and transferred to the hydrocarbon layer.
  • Still another method involves adding a suitable substrate (e.g. pyridine) to the ionic liquid containing the conjunct polymer. After a period of time, an inert hydrocarbon is added to wash away the liberated conjunct polymer.
  • the ionic liquid precursor [hutyipyridinium] [CI] is added to the ionic liquid (e.g. [butylpyridinium] [AUG?]) containing the conjunct polymer followed by an inert hydrocarbon. After mixing, the hydrocarbon layer is separated, resulting in a regenerated ionic liquid. See, e.g., US 7,737,067, which is incorporated herein by reference.
  • Another method involves adding ionic liquid containing conjunct polymer to a suitable substrate (e.g. pyridine) and an electrochemical cell containing two aluminum electrodes and an inert hydrocarbon. A voltage is applied, and the current measured to determine the extent of reduction.
  • Ionic liquids can also be regenerated by contacting with silane compounds (U.S. Application Serial No. 14/269,943), borane compounds (US. Application Serial No. 14/269,978), Bransted acids, (US Application Serial No. 14/229,329), or Ci to C i0 Paraffins (US Application Serial No. 14/229,403), each of which is incorporated herein by reference.
  • the second mercaptan lean stream 630 can be combined with the low boiling first mercaptan lean stream 605, and/or the high boiling first mercaptan lean stream 615 to form a combined mercaptan lean stream 640.
  • the light fraction 140 can be combined with one or more of these streams as well.
  • the liquid stream 175 can be separated into a mercaptan rich stream and a mercaptan lean stream as described above in Fig. 1, rather than a mercaptan rich stream and at least two mercaptan lean streams.
  • a first embodiment of the invention is a process for reducing the sulfur content of full range naphtha comprising introducing a naphtha feed into a selective hydrogenation zone in the presence of hydrogen and a hydrogenation catalyst under selective hydrogenation conditions to form a hydrogenated feed; separating the hydrogen ated feed into at least two fractions, a light fraction and a heavy fraction; introducing the heavy fraction to a selective hydrodesulfurization zone in the presence of hydrogen and a hydrodesulfurization catalyst under selective hydrodesulfurization conditions to form a desulfurized stream, the desulfurized stream containing mercaptans; separating at least a portion of the desulfurized stream into at least two streams, a mercaptan rich stream and a first mercaptan lean stream; and treating at least a portion of the mercaptan rich stream to remove at least a portion of the mercaptan compounds to form a second mercaptan lean stream.
  • An embodiment of the invention is one, any or ail of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein treating the at least the portion of the mercaptan rich stream comprises introducing the mercaptan rich stream into at least one of a caustic
  • 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 combining the first mercaptan lean stream with the second mercaptan lean stream.
  • An embodiment of the invention is one, any or ail of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising combining the light fraction with at least one of the first mercaptan lean stream and the second mercaptan lean 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 wherein separating the at least the portion of the desulfunzed stream into at least two streams comprises separating the at least the portion of the desulfurized stream into the mercaptan rich stream and the first mercaptan lean 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 wherein the mercaptan rich stream has a boiling point in a range of 60 C 'C to 100°C, and the first mercaptan lean stream has a boiling point in a range of 100°C to 220°C.
  • An embodiment of the invention is one, any or ail of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein separating the at least the portion of the desulfurized stream into at least two streams comprises separating the at least the portion of the desulfurized stream into the mercaptan rich stream and at least two first mercaptan lean streams, a low boiling first mercaptan lean stream having a boiling point range lower than a boiling point range of the mercaptan rich stream and a high boiling first mercaptan stream having a boiling point range greater than the boiling point range of the mercaptan rich 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 wherein the mercaptan rich stream has a boiling point in a range of 85 C 'C to 100°C, and the low boiling first mercaptan lean stream has a boiling point in a range of 60°C to 85°C, and the high boiling first mercaptan lean stream has a boiling point in a range of 100°C to 220°C.
  • 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 mercaptan rich stream has a boiling point in a range of 60°C to 100°C and the first mercaptan lean stream has a boiling point in a range of 100°C to 220°C, and wherein treating the mercaptan rich stream comprises introducing the mercaptan rich stream into a caustic 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 and further comprising separating the desulfurized stream into a gas stream and a liquid stream in a first side of a divided wall separator and wherein separating the at least the portion of the desulfurized stream into the at least two streams comprises separating the liquid stream into at least the mercaptan rich stream and at least two first mercaptan lean streams, wherein the mercaptan rich stream has a boiling point in a range of 85°C to 100°C, and the at least two first mercaptan lean streams comprise a low boiling first mercaptan lean stream having a boiling point in a range of 60°C to 85°C, and a high boiling mercaptan lean stream having a boiling point in a range of 100°C to 220°C, and wherein treating the at least the portion of the mercaptan rich stream comprises introducing at least the portion of the mercaptan rich 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 wherein separating the at least the portion of the desulfurized stream into at least two streams comprises separating the at least the portion of the desulfurized stream into at least the mercaptan rich stream and at least two mercaptan lean streams, wherein the mercaptan rich stream has a boiling point in a range of 85°C to 100°C, and the at least two first mercaptan lean streams comprise a low boiling first mercaptan lean stream having a boiling point in a range of 60°C to 85°C, and a high boiling mercaptan lean stream having a boiling point in a range of 100°C to 220°C, and wherein treating the at least the portion of the mercaptan rich stream comprises introducing the at least the portion of the mercaptan rich stream into the selective hydrogenation zone.
  • An embodiment of the invention is one, any or ail of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein separating at least the portion of the desulfurized stream into at least two streams comprises separating at least the portion of the desulfurized stream into at least the mercaptan rich stream and at least two mercaptan lean streams, wherein the mercaptan rich stream has a boiling point in a range of 85°C to 100°C, and the at least two first mercaptan lean streams comprise a low boiling first mercaptan lean stream having a boiling point in a range of 60°C to 85°C, and a high boiling mercaptan lean stream having a boiling point in a range of 100°C to 220°C, and wherein treating the at least the portion of the mercaptan rich stream comprises introducing the at least the portion of the mercaptan rich stream into an adsorption 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 separating at least the portion of the desulfunzed stream into at least two streams comprises separating at least the portion of the desulfurized stream into at least the mercaptan rich stream and at least two mercaptan lean streams, wherein the mercaptan rich stream has a boiling point in a range of 85°C to 100°C, and the at least two first mercaptan lean streams comprise a low boiling first mercaptan lean stream having a boiling point in a range of 60°C to 85°C, and a high boiling mercaptan lean stream having a boiling point in a range of 100°C to 220°C, and wherein treating the at least the portion of the mercaptan rich stream comprising introducing the at least the portion of the mercaptan rich stream into an ionic liquid extraction zone.
  • a second embodiment of the invention is a process for reducing the sulfur content of full range FCC naphtha comprising introducing a FCC naphtha feed into a selective hydrogenation zone in the presence of hydrogen and a hydrogenation catalyst under selective hydrogenation conditions to form a hydrogenated feed; separating the hydrogenated feed into at least two fractions, a lighter fraction and a heavier fraction; introducing the heavier fraction to a selective hydrodesulfurization zone in the presence of hydrogen and a hydrodesulfurization catalyst under selective hydrodesulfurization conditions to form a desulfurized stream, the desulfurized stream containing mercaptans; separating at least a portion of the desulfurized stream into at least two streams, a mercaptan rich stream and a first mercaptan lean stream; and treating at least a portion of the mercaptan rich stream to remove at least a portion of the mercaptan compounds to form a second mercaptan lean stream, wherein treating the at least the portion of the mercapt
  • 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 at least one of combining the first mercaptan lean stream with the second mercaptan lean stream; and combining the lighter fraction with at least one of the first mercaptan lean stream and the second mercaptan lean stream.
  • An embodiment of the invention is one, any or ail of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein separating the at least the portion of the desulfurized stream into at least two streams comprises separating the at least the portion of the desulfurized stream into the mercaptan rich stream and the first mercaptan lean stream.
  • separating the at least the portion of the desulfurized stream into at least two streams comprises separating the at least the portion of the desulfurized stream into the mercaptan rich stream and at least two first mercaptan lean streams, a low boiling first mercaptan lean stream having a boiling point range lower than a boiling point range of the mercaptan rich stream and a high boiling first mercaptan stream having a boiling point range greater than the boiling range of the mercaptan rich 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 wherein the boiling point range of the mercaptan rich stream is 85°C to 100°C, and the boiling point range of the low boiling first mercaptan lean stream is 60°C to 85°C, and the boiling point range of the high boiling first mercaptan lean stream is 100°C to 220°C.
  • a third embodiment of the invention is a process for reducing the sulfur content of full range FCC naphtha comprising introducing a FCC naphtha feed into a selective hydrogenation zone in the presence of hydrogen and a hydrogenation catalyst under selective hydrogenation conditions to form a hydrogenated feed; separating the hydrogenated feed into at least two fractions, a lighter fraction and a heavier fraction; introducing the heavier fraction to a selective hydrodesuifurization zone in the presence of hydrogen and a hydrodesulfurization catalyst under selective hydrodesuifurization conditions to form a desulfurized stream, the desulfurized stream containing mercaptans; separating at least a portion of the desulfurized stream into at least a mercaptan rich stream, a low boiling mercaptan lean stream having a boiling point range lower than a boiling point range of the mercaptan rich stream, and a high boiling first mercaptan stream having a boiling point range greater than the boiling range of the mercaptan rich stream; and treating at least

Abstract

La présente invention concerne un procédé permettant de réduire la teneur en soufre d'un naphta de craquage catalytique fluide (FCC). Le procédé consiste à introduire une charge de naphta de FCC dans une zone d'hydrogénation sélective pour former une charge hydrogénée. La charge hydrogénée est séparée en une fraction légère et une fraction lourde. La fraction lourde est introduite dans une zone d'hydrodésulfuration sélective pour former un flux désulfuré qui contient des mercaptans. Le flux désulfuré est séparé en un flux riche en mercaptans et un flux pauvre en mercaptans. Le flux riche en mercaptans est traité avec un procédé d'extraction alcaline, une zone de réaction d'hydrodésulfuration, un procédé d'hydrogénation sélective, un procédé d'adsorption, ou un procédé d'extraction avec un liquide ionique pour éliminer au moins une partie des composés mercaptans pour former un second flux pauvre en mercaptans.
PCT/US2016/046281 2015-08-13 2016-08-10 Gestion de mercaptans au cours d'une hydrodésulfuration sélective de naphta de craquage catalytique fluide WO2017027554A1 (fr)

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RU2018104363A RU2698100C2 (ru) 2015-08-13 2016-08-10 Регулирование содержания меркаптанов при селективном гидрообессеривании нафты fcc
US15/885,643 US20180155640A1 (en) 2015-08-13 2018-01-31 Mercaptan management in selective hydrodesulfurization of fcc naphtha

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US11084990B2 (en) * 2018-12-17 2021-08-10 Phillips 66 Company Maximizing octane savings in a catalytic distillation unit via a dual reactor polishing system
US11041130B2 (en) 2019-09-10 2021-06-22 Saudi Arabian Oil Company Two-stage hydrotreating process employing mercaptanization and hydrodesulfurization
US11898103B2 (en) 2021-10-29 2024-02-13 Uop Llc Systems and process for controlling a sulfur extraction from a hydrocarbon stream

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US7951290B2 (en) * 2006-12-29 2011-05-31 Uop Llc Hydrocarbon conversion process
US20150090639A1 (en) * 2008-08-29 2015-04-02 Instituto Mexicano Del Petroleo Halogen-free ionic liquids in naphtha desulfurization and their recovery

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