WO2010039716A1 - Procédé d’élimination de mercure - Google Patents

Procédé d’élimination de mercure Download PDF

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Publication number
WO2010039716A1
WO2010039716A1 PCT/US2009/058799 US2009058799W WO2010039716A1 WO 2010039716 A1 WO2010039716 A1 WO 2010039716A1 US 2009058799 W US2009058799 W US 2009058799W WO 2010039716 A1 WO2010039716 A1 WO 2010039716A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquid hydrocarbon
stream
hydrocarbon stream
water
accordance
Prior art date
Application number
PCT/US2009/058799
Other languages
English (en)
Inventor
Erin E. Tullos
Mark A. Hughes
John Michael Hays
Joseph B. Cross
Original Assignee
Conocophillips Company
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 Conocophillips Company filed Critical Conocophillips Company
Priority to EP09793119A priority Critical patent/EP2352567A1/fr
Priority to AU2009298710A priority patent/AU2009298710B2/en
Publication of WO2010039716A1 publication Critical patent/WO2010039716A1/fr

Links

Classifications

    • 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
    • B01D11/0492—Applications, solvents used
    • 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
    • C10G17/00—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge
    • C10G17/02—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge with acids or acid-containing liquids, e.g. acid sludge
    • C10G17/04—Liquid-liquid treatment forming two immiscible phases
    • C10G17/07—Liquid-liquid treatment forming two immiscible phases using halogen acids or oxyacids of halogen
    • 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
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • 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
    • C10G2300/1033—Oil well production fluids
    • 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
    • C10G2300/205—Metal content

Definitions

  • the present invention relates to a process for the removal of mercury from crude oil.
  • this invention relates to a process for the removal of mercury from crude oil using water and an oxidizing agent.
  • a process including the following: a) contacting a liquid hydrocarbon stream comprising liquid hydrocarbons and Hg(O) with a water stream consisting essentially of water and an oxidizing agent for conversion of at least a portion of the Hg(O) to Hg(II); b) extracting at least a portion of the Hg(II) from the liquid hydrocarbon stream into the water stream, thereby forming a treated liquid hydrocarbon stream containing less total Hg than the liquid hydrocarbon stream and a waste water stream comprising water and Hg(II); and c) separating the treated liquid hydrocarbon stream from the waste water stream.
  • FIGURE 1 is a bar graph showing the mass balance of Hg between the hydrocarbon and aqueous phases for variously treated samples of a crude oil.
  • FIGURE 2 is a bar graph showing the mass balance of Hg between the hydrocarbon and aqueous phases for variously treated samples of a crude oil.
  • FIGURE 3 is a bar graph showing the mass balance of Hg between the hydrocarbon and aqueous phases for variously treated samples of a crude oil.
  • the liquid hydrocarbon stream of this invention can be any liquid hydrocarbon stream which comprises liquid hydrocarbons and mercury in the 0 valence state (Hg (O)).
  • the liquid hydrocarbon stream will be a crude oil stream or a condensate stream from a natural gas well.
  • the liquid hydrocarbon stream comprises, consists of, or consists essentially of a crude oil containing Hg(O).
  • the liquid hydrocarbon stream typically comprises at least about 10 ppb (parts per billion) Hg(O), and more particularly comprises at least about 200 ppb Hg (0).
  • the liquid hydrocarbon stream is contacted with a water stream consisting essentially of water and an oxidizing agent for conversion of at least a portion of the Hg(O) to mercury in a +2 valence state (Hg(II)).
  • the oxidizing agent can be any chemical or chemical compound capable of oxidizing Hg(O) to Hg(II).
  • the oxidizing agent can be sodium hypochlorite.
  • the water stream preferably does not contain any component(s) in sufficient quantities such that such component(s) materially affect the ability of the oxidizing agent to oxidize the Hg(O) to Hg(II) or materially affect the ability of the water to extract the Hg(II) from the liquid hydrocarbon stream.
  • the oxidizing agent is present in the water stream preferably in an amount such that the molar ratio of the oxidizing agent to the Hg(O) present in liquid hydrocarbon stream is at least about 1 :1, more preferably at least about 7:1, and most preferably at least about 143 : 1.
  • the contacting of the liquid hydrocarbon stream with the water stream is preferably at a temperature at least above the freezing points of the liquid hydrocarbon stream and the water stream, more preferably at a temperature at least above the freezing points of the liquid hydrocarbon stream and the water stream and below about 100 0 C, and most preferably at a temperature at least above about 2O 0 C and below about 7O 0 C.
  • At least a portion of the Hg(II) is then extracted from the liquid hydrocarbon stream into the water stream, thereby forming a treated liquid hydrocarbon stream containing less Hg than the liquid hydrocarbon stream and a waste water stream comprising water and Hg(II).
  • the treated liquid hydrocarbon stream is then separated from the waste water stream by any suitable means.
  • the treated liquid hydrocarbon stream preferably contains less than about 50 wt. %, more preferably less than about 20 wt. %, and most preferably less than about 1 wt. %, of the Hg contained in the liquid hydrocarbon stream.
  • Table 1 shows that compared to the first bottle with no aqueous wash, there was substantially more mercury removed from the hydrocarbon phase upon the addition of an oxidizing agent (bleach) to the aqueous wash.
  • Example 2 Reagent grade decane, in the amounts shown in Table 2, was spiked with approximately
  • the optimal mole ratio of mercury to NaOCl in the decane/Bleach solution mix is at least about 1:7.
  • Figures 1 - 3 are plots of the mass balance of mercury for samples 1-4 for crude oils A, B and C.
  • the black bars in the graph represent the total mercury in ng of the analyzed hydrocarbon phase (or crude oil sample) and the grey bars (to the right of the black bars, if visible) represent the total mercury in ng of the analyzed aqueous phase. Errors due to loss of mass to a rag layer or dilution during centrifuge balancing were small and did not influence the conclusions drawn from the data.
  • Example 4 A sample of a crude oil was heated beyond the wax point to obtain a representative sample. To four glass bottles, the following was added: 1) 40 g crude oil only, 2) 40 g crude oil and 4 g deionized water, 3) 40 g crude oil and 4 g 5.6-6.0% sodium hypochlorite (bleach) solution, and 4) 40 g crude oil and 4 g 50% ethylene glycol in water solution. The four samples were shaken for 2 minutes.

Landscapes

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

Abstract

La présente invention concerne un procédé permettant de réduire le niveau de mercure élémentaire contenu dans un flux d’hydrocarbures liquides par a) la mise en contact du flux d’hydrocarbures liquides avec un flux d’eau contenant un agent oxydant pour la conversion d’au moins une partie de Hg(0) en Hg(II); b) l’extraction d’au moins une partie du Hg(II) depuis le flux d’hydrocarbures liquides vers le flux d’eau, formant ainsi un flux d’hydrocarbures liquides traité et un flux d’eaux usées contenant de l’eau et du Hg(II); et c) la séparation du flux d’hydrocarbures liquides du flux d’eaux usées.
PCT/US2009/058799 2008-09-30 2009-09-29 Procédé d’élimination de mercure WO2010039716A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP09793119A EP2352567A1 (fr) 2008-09-30 2009-09-29 Procédé d'élimination de mercure
AU2009298710A AU2009298710B2 (en) 2008-09-30 2009-09-29 Mercury removal process

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US12/241,126 2008-09-30
US12/241,126 US20100078358A1 (en) 2008-09-30 2008-09-30 Mercury removal process

Publications (1)

Publication Number Publication Date
WO2010039716A1 true WO2010039716A1 (fr) 2010-04-08

Family

ID=41259675

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2009/058799 WO2010039716A1 (fr) 2008-09-30 2009-09-29 Procédé d’élimination de mercure

Country Status (4)

Country Link
US (1) US20100078358A1 (fr)
EP (1) EP2352567A1 (fr)
AU (1) AU2009298710B2 (fr)
WO (1) WO2010039716A1 (fr)

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US8489231B2 (en) * 2009-09-18 2013-07-16 Raf Technology, Inc. Loop mail processing
US8673133B2 (en) * 2010-09-16 2014-03-18 Chevron U.S.A. Inc. Process, method, and system for removing heavy metals from fluids
WO2012036986A2 (fr) * 2010-09-16 2012-03-22 Chevron U.S.A. Inc. Procédé, méthode et système pour retirer des métaux lourds de liquides
US8702975B2 (en) 2010-09-16 2014-04-22 Chevron U.S.A. Inc. Process, method, and system for removing heavy metals from fluids
US8663460B2 (en) 2010-09-16 2014-03-04 Chevron U.S.A. Inc. Process, method, and system for removing heavy metals from fluids
US8728304B2 (en) 2010-09-16 2014-05-20 Chevron U.S.A. Inc. Process, method, and system for removing heavy metals from fluids
US9296956B2 (en) 2010-10-28 2016-03-29 Chevron U.S.A. Inc. Method for reducing mercaptans in hydrocarbons
US8728303B2 (en) * 2010-11-19 2014-05-20 Chevron U.S.A. Inc. Process, method, and system for removing heavy metals from fluids
US8721873B2 (en) * 2010-11-19 2014-05-13 Chevron U.S.A. Inc. Process, method, and system for removing heavy metals from fluids
SG190775A1 (en) * 2010-11-19 2013-07-31 Chevron Usa Inc Process, method, and system for removing heavy metals from fluids
US8721874B2 (en) * 2010-11-19 2014-05-13 Chevron U.S.A. Inc. Process, method, and system for removing heavy metals from fluids
US9140679B2 (en) 2010-12-28 2015-09-22 Chevron U.S.A. Inc. Process for characterizing corrosivity of refinery feedstocks
US9103813B2 (en) 2010-12-28 2015-08-11 Chevron U.S.A. Inc. Processes and systems for characterizing and blending refinery feedstocks
CA2818679A1 (fr) 2010-12-28 2012-07-05 Chevron U.S.A. Inc. Processus et systemes de caracterisation et de melange de charges de raffinerie
US9464242B2 (en) 2010-12-28 2016-10-11 Chevron U.S.A. Inc. Processes and systems for characterizing and blending refinery feedstocks
WO2013173586A1 (fr) 2012-05-16 2013-11-21 Chevron U.S.A. Inc. Traitement, procédé et système pour éliminer le mercure de fluides
CA2872804A1 (fr) * 2012-05-16 2013-11-21 Chevron U.S.A. Inc. Reaction en canalisation pour l'elimination de metaux lourds a partir de fluides produits
US9447674B2 (en) 2012-05-16 2016-09-20 Chevron U.S.A. Inc. In-situ method and system for removing heavy metals from produced fluids
CN104334692A (zh) 2012-05-16 2015-02-04 雪佛龙美国公司 从流体中去除重金属的工艺、方法和系统
US9181497B2 (en) 2012-05-16 2015-11-10 Chevon U.S.A. Inc. Process, method, and system for removing mercury from fluids
US9023196B2 (en) 2013-03-14 2015-05-05 Chevron U.S.A. Inc. Process, method, and system for removing heavy metals from fluids
US9234141B2 (en) 2013-03-14 2016-01-12 Chevron U.S.A. Inc. Process, method, and system for removing heavy metals from oily solids
US9169445B2 (en) 2013-03-14 2015-10-27 Chevron U.S.A. Inc. Process, method, and system for removing heavy metals from oily solids

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US4915818A (en) 1988-02-25 1990-04-10 Mobil Oil Corporation Use of dilute aqueous solutions of alkali polysulfides to remove trace amounts of mercury from liquid hydrocarbons
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Also Published As

Publication number Publication date
EP2352567A1 (fr) 2011-08-10
US20100078358A1 (en) 2010-04-01
AU2009298710B2 (en) 2014-07-24
AU2009298710A1 (en) 2010-04-08

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