WO2006135460A2 - Procede d'elimination de composes de soufre oxygenes d'hydrocarbures - Google Patents

Procede d'elimination de composes de soufre oxygenes d'hydrocarbures Download PDF

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Publication number
WO2006135460A2
WO2006135460A2 PCT/US2006/005965 US2006005965W WO2006135460A2 WO 2006135460 A2 WO2006135460 A2 WO 2006135460A2 US 2006005965 W US2006005965 W US 2006005965W WO 2006135460 A2 WO2006135460 A2 WO 2006135460A2
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WO
WIPO (PCT)
Prior art keywords
process according
sulfur compounds
effluent
sulfuric acid
sorbent
Prior art date
Application number
PCT/US2006/005965
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English (en)
Other versions
WO2006135460A3 (fr
Inventor
Lawrence A. Smith, Jr.
Christopher C. Boyer
Frits Dautzenberg
Original Assignee
Catalytic Distillation Technologies
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
Application filed by Catalytic Distillation Technologies filed Critical Catalytic Distillation Technologies
Publication of WO2006135460A2 publication Critical patent/WO2006135460A2/fr
Publication of WO2006135460A3 publication Critical patent/WO2006135460A3/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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/56—Addition to acyclic hydrocarbons
    • C07C2/58—Catalytic processes
    • C07C2/62—Catalytic processes with acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
    • C07C2527/03—Acids of sulfur other than sulfhydric acid or sulfuric acid, e.g. halosulfonic acids

Definitions

  • the present invention relates to the treatment of alkylate product from a process wherein normal olefins are reacted with isoalkanes in the presence of sulfuric acid to produce alkylate product. More particularly the invention relates to a process wherein sulfuric acid is mechanically removed from the effluent from the alkylation reactor and subsequently treated to remove residual oxygenated sulfur compounds. More particularly the invention relates to a process wherein the oxygenated sulfur compounds are removed by sorption.
  • Alkylation is the reaction of a paraffin, usually isoparaffins, with an olefin in the presence of a strong acid which produces paraffins, e.g., of higher octane number than the starting materials and which boil in range of gasolines.
  • a strong acid which produces paraffins, e.g., of higher octane number than the starting materials and which boil in range of gasolines.
  • the reaction is generally the reaction of a C 2 to C 5 olefin with isobutane.
  • hydrofluoric or sulfuric acid catalysts are most widely used under low temperature conditions. Low temperature or cold acid processes are favored because side reactions are minimized.
  • U.S. Patent Nos. 5,420,093 and 5,444,175 sought to combine the particulate contact material and the catalyst by impregnating a mineral or organic support particulate with sulfuric acid.
  • oxygenated sulfur compounds are removed from a hydrocarbon stream comprising passing said hydrocarbon stream over a supported sorbent comprising a component selected from the group consisting of copper, zinc and mixtures thereof.
  • the oxygenated sulfur compounds are present as a residual amount in the hydrocarbon stream, such as that present in a hydrocarbon stream separated and recovered from a sulfuric acid catalyzed paraffin alkylation.
  • the residual amount is preferably less than 1000 wppm.
  • the sorbent is regenerable.
  • the invention comprises removing the sulfuric acid from the alkylate by mechanical means instead of water wash or caustic treatment product prior to treatment to remove oxygenated compounds by absorption.
  • the preferred mechanical means comprises a vessel containing a coalescer material upon which the sulfuric acid impinges.
  • the sulfuric acid being much heavier than the hydrocarbon, falls out and may be removed by gravity.
  • the alkylate product may then be treated to remove the oxygenated sulfur compounds by adsorption in any of several points in the process after the mechanical deentrainment.
  • the adsorber may contain regenerable or nonregenerable sorbents and may be located directly after the coalescer to treat the entire stream or downstream on any of the other product streams.
  • the sorbents may remove the oxygenated sulfur compounds from light (C 4 and lighter) and heavier (C 5 and heavier) components separately if desired.
  • FIG. 1 is a simplified flow diagram of one embodiment of the invention.
  • FIG. 2 is a simplified flow diagram of the invention showing various placements of the sorber.
  • the alkylate product to be treated may come from any cold acid alkylation process which uses sulfuric acid as the catalyst.
  • the fluid system comprises a liquid and is maintained at about its boiling point in the reaction zone.
  • the coalescer is a conventional liquid-liquid coalescer of a type which is operative for coalescing vaporized liquids and comprises demisters and co-knit structures which are catalytically inert or active. Demisters and co-knit structures are typically used for liquid-liquid coalescers and coalescing of mists. They are known as "mist eliminators" or demisters and are composed of one or more materials which are knit together to form a mesh.
  • a suitable coalescer comprises a mesh such as a co-knit wire and fiberglass mesh.
  • the alkylate from the alkylation process contains some sulfuric acid as well as sulfonates and sulfonic esters which must be removed.
  • FIG. 1 a simplified flow diagram of one embodiment is shown.
  • the alkylate is taken from alkylation reactor 10 via flow line 101 and fed to deentrainment vessel 20.
  • Deentrainment vessel 20 contains a coalescer material upon which the sulfuric acid droplets impinge and fall out.
  • the sulfuric acid and hydrocarbons in the alkylate product are practically insoluble in one another.
  • the sulfuric acid droplets are collected and recycled to the alkylation reactor 10 via flow line 104.
  • the liquid from the deentrainment vessel is passed via flow line 102 to absorption vessel 50 containing a bed 52 of sorbent material. Any material that will sorb the oxygenated sulfur compounds will suffice.
  • One typical sorbent is Engelhard Cu-0226 14x28, 10%Cu on alumina.
  • Another is BASF R3-12, 40%Cu/ 40% Zn on alumina.
  • Substantially all of the oxygenated sulfur compounds are sorbed by the sorbent.
  • Hydrogen is fed to the sorber as required via flow line 108 during the regeneration step.
  • the liquid from the sorber is then fed via flow line 110 to a deisobutanizer 30 containing standard distillation structure 32 such as sieve trays, bubble cap trays and the like, where iC 4 and C 3 1 S and lighter are taken as overheads via flow line 109.
  • the overheads containing the iC 4 and lighter material is then fed via flow line 109 to depropanizer 60 containing standard distillation structure 62 where C 3 and lighter is removed as overheads via flow line 111.
  • the iC 4 is recycled to the alkylation reactor via flow line 104.
  • FIG. 2 shows alternate placements of the sorber 50 as indicated by the dashed lines and the reference numerals 50A-50G. The remaining vessels are numbered as in Figure 1.
  • the sorber may be placed to remove the oxygenated sulfur compounds from any of the streams downstream of the deentrainment vessel such as the nC 4 stream, the feed to the depropanizer, the C 3 product, the feed to the deisobutanizer, the feed to the debutanizer or the alkylate product stream.
  • the sorber may be placed to remove the oxygenated sulfur compounds from any of the streams downstream of the deentrainment vessel such as the nC 4 stream, the feed to the depropanizer, the C 3 product, the feed to the deisobutanizer, the feed to the debutanizer or the alkylate product stream.
  • the sorber may be placed to remove the oxygenated sulfur compounds from any of the streams downstream of the deentrainment vessel such as the nC 4 stream, the feed to the depropanizer, the C 3 product, the feed to the deisobutanizer, the feed to the debutanizer or the alkylate product stream.
  • sorbers in parallel use. One sorber would be in use, a second would
  • the sorbent unit was 3/8" OD tubing containing 10 grams (11 ml) of the sorbent. The sorption took place at 125 psig and 150 0 F to simulate conditions of the hydrocarbon stream entering a debutinizer column. The length of each run was determined by time to break through (Time to BT). Break through was defined as when the effluent from the sorber contained 15 % of the sulfur of the feed stream.
  • the adsorption procedure was carried by the following procedure: 1 . Purged with nitrogen (or He) - flowed 40 ccm for 30 min at 125 psig and kept temperature at 150 0 F. Shut off gas flow before starting hydrocarbons.
  • Engelhard Cu-0226 S 14x28, 10%Cu on alumina was used as sorbent to treat sulfur ester containing hydrocarbon feeds as described.
  • the conditions, residual sulfur compound content (wppm), and results are shown in TABLE I.
  • BASF R3-12, 40%Cu/40 Zn on alumina was used as sorbent to treat sulfur ester containing hydrocarbon feeds as described.
  • the conditions, residual sulfur compound content (wppm), and results are shown in TABLE II.
  • Catalyst BASF R3-12, 40%Cu ,40%Zn/alumina grams 10 ml 10.5

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé d'élimination de composés de soufre oxygénés d'un courant d'hydrocarbures, notamment de l'effluent d'un réacteur d'alkylation d'acide sulfurique. Dans ledit procédé, le courant d'hydrocarbures est d'abord soumis à un désentraînement de tout acide sulfurique liquide d'entraînement et est ensuite passé sur un sorbant qui supprime les composés de soufre oxygénés.
PCT/US2006/005965 2005-06-08 2006-02-21 Procede d'elimination de composes de soufre oxygenes d'hydrocarbures WO2006135460A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11/147,963 US20060278568A1 (en) 2005-06-08 2005-06-08 Method of removing oxygenated sulfur compounds from hydrocarbons
US11/147,963 2005-06-08

Publications (2)

Publication Number Publication Date
WO2006135460A2 true WO2006135460A2 (fr) 2006-12-21
WO2006135460A3 WO2006135460A3 (fr) 2007-09-20

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PCT/US2006/005965 WO2006135460A2 (fr) 2005-06-08 2006-02-21 Procede d'elimination de composes de soufre oxygenes d'hydrocarbures

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US (1) US20060278568A1 (fr)
WO (1) WO2006135460A2 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104927907B (zh) * 2015-07-01 2017-02-01 华东理工大学 烷基化产物脱硫脱酸的方法与装置

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6313362B1 (en) * 1998-12-17 2001-11-06 Exxonmobil Corporation Aromatic alkylation process
US20030163013A1 (en) * 2001-09-04 2003-08-28 Yang Ralph T. Selective sorbents for purification of hydrocarbons

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US2091917A (en) * 1933-09-06 1937-08-31 Pennsylvania Petroleum Res Cor Apparatus for treating mineral oils
US2364430A (en) * 1940-07-16 1944-12-05 Standard Oil Dev Co Alkylation process employing hydrogen
US2316108A (en) * 1941-03-17 1943-04-06 Robert F Ruthruff Alkylation process and catalyst therefor
US2472578A (en) * 1946-03-21 1949-06-07 Atlantic Refining Co Method of contacting fluids
US2756247A (en) * 1949-01-21 1956-07-24 Union Oil Co Process for chemical reaction in the adsorbed phase of solid adsorbents
US2981771A (en) * 1955-12-22 1961-04-25 D X Sunray Oil Company Regeneration of spent adsorbent
US3248343A (en) * 1964-04-07 1966-04-26 Standard Oil Co Hydrocarbon conversion catalyst
IL28565A (en) * 1967-08-25 1971-12-29 Hydro Chem & Mineral Corp Apparatus and process for providing direct contact between a liquid and one or more other fluids
US3839487A (en) * 1971-07-09 1974-10-01 Merichem Co Alkylation utilizing fibers in a conduit reactor
US3759318A (en) * 1972-03-15 1973-09-18 Stratford Eng Corp Contactor improvements
US4075528A (en) * 1977-03-15 1978-02-21 Shigeru Suga Xenon lamp with magnets on the electrodes
US4209656A (en) * 1978-10-23 1980-06-24 Texaco Inc. Sulfuric acid catalyzed alkylation process
DK168520B1 (da) * 1989-12-18 1994-04-11 Topsoe Haldor As Fremgangsmåde til væskefase-alkylering af et carbonhydrid med et olefinalkyleringsmiddel
US5420093A (en) * 1991-10-25 1995-05-30 Institut Francais Du Petrole Catalyst based on silica and sulfuric acid and its use for the alkylation of paraffins
DE69302973T2 (de) * 1992-08-20 1996-10-10 Inst Francais Du Petrol Verfahren zur Alkylierung von Paraffinen
US5785933A (en) * 1997-01-21 1998-07-28 Mobil Oil Corporation Sulfuric acid alkylation reactor system with static mixers
US6558533B2 (en) * 2001-04-13 2003-05-06 W.R. Grace & Co.-Conn Process for sulfur removal from hydrocarbon liquids

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6313362B1 (en) * 1998-12-17 2001-11-06 Exxonmobil Corporation Aromatic alkylation process
US20030163013A1 (en) * 2001-09-04 2003-08-28 Yang Ralph T. Selective sorbents for purification of hydrocarbons

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WO2006135460A3 (fr) 2007-09-20
US20060278568A1 (en) 2006-12-14

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