US3308059A - Sulfolane solvent recovery from water wash - Google Patents

Sulfolane solvent recovery from water wash Download PDF

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Publication number
US3308059A
US3308059A US444366A US44436665A US3308059A US 3308059 A US3308059 A US 3308059A US 444366 A US444366 A US 444366A US 44436665 A US44436665 A US 44436665A US 3308059 A US3308059 A US 3308059A
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United States
Prior art keywords
sulfolane
water
aromatic
wash
via line
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US444366A
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English (en)
Inventor
Jr Carl H Deal
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Shell USA Inc
Original Assignee
Shell Oil Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to GB13784/66A priority Critical patent/GB1082188A/en
Priority to US444366A priority patent/US3308059A/en
Application filed by Shell Oil Co filed Critical Shell Oil Co
Priority to BE678610D priority patent/BE678610A/xx
Priority to NL6604095A priority patent/NL6604095A/xx
Priority to DE19661545376 priority patent/DE1545376A1/de
Priority to ES0324828A priority patent/ES324828A1/es
Priority to AT298066A priority patent/AT275695B/de
Priority to DK161366AA priority patent/DK116017B/da
Priority to FR55316A priority patent/FR1473564A/fr
Application granted granted Critical
Publication of US3308059A publication Critical patent/US3308059A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0488—Flow sheets
    • 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
    • C10G21/28—Recovery of used solvent

Definitions

  • This invention relates to a process for the extraction and recovery or aromatic hydrocarbons from a liquid hydrocarbon mixture. More particularly, the invention relates to an improved process employing a sulfolane as an extractive solvent for separating kerosene-range aromatics.
  • an aqueous sulfolane solution can be treated to separate the sulfolane therefrom by passing the solution in countercurrent contact with a hydrocarbon, e.g., the incoming feed to a liquid-liquid extraction system.
  • a hydrocarbon e.g., the incoming feed to a liquid-liquid extraction system.
  • a kerosene range hydrocarbon mixture is introduced into one end of an extractor and passed in countercurrent contact with sulfolane introduced near the other end.
  • the rafiinate phase containing primarily the non-aromatic hydrocarbons is passed to a raffinate wash column wherein it is water-washed to separate any sulfolane removed from the primary extractor with the non-aromatic railinite.
  • the fat sulfolane solvent containing primarily the aromatics is passed from the extractor to an extractive stripping column wherein any light hydrocarbon removed with the sulfolane is overheaded and refluxed to the extractor for further separation.
  • the bottoms product from the extractive stripping column, containing sulfolane and aromatic hydrocarbons is passed to a stripping column from wherein the aromatic hydrocarbons are removed overhead while the sulfolane is removed as bottom product and returned to the extractor.
  • the aromatic hydrocarbons, containing a portion of the sulfolane, which increases as the voltatilities of the aromatics approach that of the sulfolane, is waterwashed to remove the sulfolane before it is recovered as product.
  • This aqueous extract containing the solvent is distilled to separate sulfolane and water for recycle.
  • the sulfolane containing water wash (1) of the non-aromatic ratfinate separated in the extractor and/ or (2) of the aromatics obtained overhead from the stripping column are passed to a pre-wash column wherein these aqueous solutions flow in countercurrent contact with hydrocarbon feed.
  • the feed which selectively extracts the sulfolane is then introduced into the main extractor while the stripped aqueous phase can be passed as washing liquid to the raffinate washing zone and/or the aromatic washing zone. A portion of this feed washed water phase may, however, be distilled and used in a final wash of the product hydrocarbons.
  • the sulfolane solvents of the invention may be made by condensing a conjugated diolefin with sulfur dioxide and then subjecting the resulting product to hydrogenation, alkylation, hydration and/or other substitution or addition reactions.
  • a 2-sulfolene may be made similarly by isomerizing instead of by hydrogenating the product resulting from condensing a conjugated diolefin with sulfur dioxide.
  • Unsubstituted sulfolane, the preferred sulfolane solvent in the process of the invention has the formula:
  • solvents which have high selectivity for separating aromatics from non-aromatic hydrocarbons are: Z-methylsulfolane, 2,4-dirnethylsulfolane, 2,4-dimethyl-4-sulfolane, methyl 3-sulfolanyl ether, ethyl-3-sulfolanyl sulfide, methyl-aryl-3-sulfolany1 ether, n-aryl-3-sulfolanyl amine, 3-sulfolanyl acetate, and others.
  • sulfolane solvents is a preferred embodiment of the invention
  • suitable solvents such as diethylene glycol, various polyethylene glycols and mixtures thereof can be employed.
  • R can be a hydrogen atom, an alkyl group having up to 8 carbon atoms, an aryl rtdical having up to 8 carbon atoms, an allroxy radical having up to 8 carbon atoms, an arylalkyl radical having up to 8 carbon atoms, an ralkhydroxy having up to 8 carbon atoms or mixtures thereof.
  • all Rs are hydrogen.
  • the present process can be applied to feed stocks having a wide or a narrow boiling range. It is especially suitable for separating aromatics from catalytically reformed gasolines, such as hydroformates and platformates or from fractions thereof.
  • the volumetric ratio of sulfolane to hydrocarbon feed should be between 3:1 and 821, preferably between 4:1 and 6:1, whereas the ratio of the amount of top product returned from the stripping zone to the extraction system to the amount of hydrocarbon feed should be between 0.211 to 0.7:1, preferably between 03:1 and 05:1.
  • the feed to the aromatic extractor may be introduced at an intermediate point, but it is generally preferred to introduce it at or at least near that end of the extraction system at which the aromatic-rich extract phase is withdrawn, because in that case the best compromise between product purity and recovery is usually realized.
  • Suitable inlet points are at the ends of the extractor or at the second theoretical stage, the latter embodiment being preferred because in that case the purity is distinctly higher whereas the recovery is only slightly decreased.
  • the shown embodiment is a preferred system for the continuous separation of non-aromatics from aromatics employing sulfolane as the selective solvent.
  • a hydrocarbon feed mixture is introduced via line 1 into pre wash column 3 from which a substantially pure water stream is removed via line 5.
  • the water was introduced via line 7 as part of an aqueous sulfolane-containing stream to column 3, wherein it passes in countercurrent contact with the hydrocarbon feed which selectively extracts sulfolane from the aqueous sulfolane-containing stream.
  • a feed/sulfolane mixture is removed overhead via line 8 and is passed to the lower end of extractor 9 wherein it flows in countercurrent contact with the sulfolane solvent introduced into the upper end of extractor 9 via line 11.
  • the hydrocarbon feed stream, stripped of its aromatic portion is removed overhead via line 13.
  • a fat solvent stream containing an aromatic portion of the feed and a minor amount of the non-aromatic hydrocarbons is removed via line 15 and passes to a middle portion of extractor stripper '17 from which a raffinate containing the non-aromatic hydrocarbons is returned via line 19 to the bottom of extractor 9'.
  • the bottoms portion containing sulfolane and aromatic hydrocarbons is passed via line 21 to stripping column 2'3 from which an overhead fraction containing aromatic hydrocarbon and a minor portion of sulfolane is removed via line 25.
  • the sulfolane bottoms are recycled via line ill to the upper portion of extractor 5.
  • the non-aromatic hydrocarbon ralfinate removed via line M from extractor 9 passes to the lower portion of ralfinate wash zone 27 wherein it is countercurrently treated with :Water introduced near the top of zone 27 through line 28.
  • the stripped non-aromatics are recovered via line 29 while the sulfolane/water solution is removed via line 3 1 and returned via line 7 to pre-wash column 3.
  • the aromatic stream, containing a minor portion of sulfolane, is removed overhead from 23 and is passed via line 25 into extract wash zone 32 where it is countercurrently contacted with water introduced via line 33.
  • the water Washed aromatics are recovered via line 35 while the sulfolane-containing water wash is removed via line 7 and returned to pre-wash column 3.
  • a still further modification would involve distilling a portion of the water removed via line 5 and returning only the distillation product via line 28 and/ or line 33.
  • the remainder of the solvent-containing wash stream of line .5 would be introduced at some intermediate point in column 27 and/ or 32 via lines 36 and 37, respectively.
  • the drawing is merely diagrammatic and is not intended to fully show all the component parts of the equipment which one skilled in the art will routinely design for the operation. Indeed, the showing of an element or piece of equipment does not mean that all such or similar pieces of equipment which may or can be designed by one skilled in the art in possession of this disclosure cannot be utilized as substitution therefore. Likewise, the omission of an element which one skilled in the art may include in an actual unit does not mean that such a piece of equipment is intended to be omitted simply because it does not appear in the drawing. Sufiice to say, the drawing is for illustrative purposes, as in the description thereof.
  • step (d) separately Water-Washing the sulfolane-non-aromatic mixture removed overhead from step (b) and the sulfolane-aromatic mixture removed overhead from step (c), thereby extracting sulfolane into aqueous wash streams, the improvement comprising recycling at least one of the sulfolane-containing water-wash streams in countercurrent contact with said hydrocarbon feed mixture in a pre-washzone, separating water as a separate phase from said prewash zone and returning the sulfolane-hydrocarbon mixture to the extraction zone.
  • suifolane-containing water-Wash stream obtained by treatment of the sulfolane-nonnromatic mixture is recycled and passed in countercurrent contact with said hydrocarbon feed.
  • suifolane solvent is sulfolane.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Extraction Or Liquid Replacement (AREA)
US444366A 1965-03-31 1965-03-31 Sulfolane solvent recovery from water wash Expired - Lifetime US3308059A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
GB13784/66A GB1082188A (en) 1965-03-31 1965-03-29 Process for the separation of a mixture containing hydrocarbons
US444366A US3308059A (en) 1965-03-31 1965-03-31 Sulfolane solvent recovery from water wash
NL6604095A NL6604095A (en:Method) 1965-03-31 1966-03-29
DE19661545376 DE1545376A1 (de) 1965-03-31 1966-03-29 Verfahren zur Auftrennung eines Kohlenwasserstoffe enthaltenden Gemisches mittels einer Fluessig-Fluessig-Extraktion
BE678610D BE678610A (en:Method) 1965-03-31 1966-03-29
ES0324828A ES324828A1 (es) 1965-03-31 1966-03-29 Un procedimiento para la separacion de una mezcla que contiene hidrocarburos.
AT298066A AT275695B (de) 1965-03-31 1966-03-29 Verfahren zur Trennung eines Kohlenwasserstoffe enthaltenden Gemisches
DK161366AA DK116017B (da) 1965-03-31 1966-03-29 Fremgangsmåde til adskillelse af en kulbrinteblanding ved ekstraktion.
FR55316A FR1473564A (fr) 1965-03-31 1966-03-29 Procédé de séparation d'un mélange contenant des hydrocarbures

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US444366A US3308059A (en) 1965-03-31 1965-03-31 Sulfolane solvent recovery from water wash

Publications (1)

Publication Number Publication Date
US3308059A true US3308059A (en) 1967-03-07

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US444366A Expired - Lifetime US3308059A (en) 1965-03-31 1965-03-31 Sulfolane solvent recovery from water wash

Country Status (8)

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US (1) US3308059A (en:Method)
AT (1) AT275695B (en:Method)
BE (1) BE678610A (en:Method)
DE (1) DE1545376A1 (en:Method)
DK (1) DK116017B (en:Method)
ES (1) ES324828A1 (en:Method)
GB (1) GB1082188A (en:Method)
NL (1) NL6604095A (en:Method)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3429802A (en) * 1966-12-16 1969-02-25 Universal Oil Prod Co Method for producing a solvent for edible oils
US3457166A (en) * 1966-12-16 1969-07-22 Universal Oil Prod Co Separation method for purifying an edible oil solvent
US3492222A (en) * 1967-11-14 1970-01-27 Universal Oil Prod Co Solvent recovery process
US4353794A (en) * 1980-11-26 1982-10-12 Uop Inc. Process for the solvent extraction of aromatics and the recovery of an aromatics-free non-aromatic product from a hydrocarbon feedstock
US20090101746A1 (en) * 2007-10-12 2009-04-23 Werner Lanz Winder for a meterial web of flexible material

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2207989A1 (de) * 1971-03-08 1972-10-12 VEB Petrolchemisches Kombinat Schwedt, χ 1330 Schwedt Verfahren zur Extraktion mittels Lo sungsmittelgemischen, insbesondere zur Gewinnung von Aromaten

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2999892A (en) * 1958-09-02 1961-09-12 Shell Oil Co Solvent extraction process
US3209047A (en) * 1961-09-21 1965-09-28 Shell Oil Co Recovery of aromatics

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2999892A (en) * 1958-09-02 1961-09-12 Shell Oil Co Solvent extraction process
US3209047A (en) * 1961-09-21 1965-09-28 Shell Oil Co Recovery of aromatics

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3429802A (en) * 1966-12-16 1969-02-25 Universal Oil Prod Co Method for producing a solvent for edible oils
US3457166A (en) * 1966-12-16 1969-07-22 Universal Oil Prod Co Separation method for purifying an edible oil solvent
US3492222A (en) * 1967-11-14 1970-01-27 Universal Oil Prod Co Solvent recovery process
US4353794A (en) * 1980-11-26 1982-10-12 Uop Inc. Process for the solvent extraction of aromatics and the recovery of an aromatics-free non-aromatic product from a hydrocarbon feedstock
US20090101746A1 (en) * 2007-10-12 2009-04-23 Werner Lanz Winder for a meterial web of flexible material

Also Published As

Publication number Publication date
NL6604095A (en:Method) 1966-10-03
ES324828A1 (es) 1967-02-16
BE678610A (en:Method) 1966-09-29
GB1082188A (en) 1967-09-06
DE1545376A1 (de) 1970-01-22
AT275695B (de) 1969-11-10
DK116017B (da) 1969-12-01

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