EP1789518A2 - Neutralisation d'emulsion de petrole brut a indice d'acidite (tan) eleve - Google Patents

Neutralisation d'emulsion de petrole brut a indice d'acidite (tan) eleve

Info

Publication number
EP1789518A2
EP1789518A2 EP05792553A EP05792553A EP1789518A2 EP 1789518 A2 EP1789518 A2 EP 1789518A2 EP 05792553 A EP05792553 A EP 05792553A EP 05792553 A EP05792553 A EP 05792553A EP 1789518 A2 EP1789518 A2 EP 1789518A2
Authority
EP
European Patent Office
Prior art keywords
crude
water
treated
fraction
oil emulsion
Prior art date
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.)
Withdrawn
Application number
EP05792553A
Other languages
German (de)
English (en)
Other versions
EP1789518A4 (fr
Inventor
Edward Ching-Shen Hsu
Rutton Dinshaw Patel
Leo Dale Brown
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Technology and Engineering Co
Original Assignee
ExxonMobil Research and Engineering 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
Application filed by ExxonMobil Research and Engineering Co filed Critical ExxonMobil Research and Engineering Co
Publication of EP1789518A2 publication Critical patent/EP1789518A2/fr
Publication of EP1789518A4 publication Critical patent/EP1789518A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C10G19/02—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C10G19/073—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with solid alkaline material
    • 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
    • C10G33/00—Dewatering or demulsification of hydrocarbon oils
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities

Definitions

  • This invention relates to the neutralization of the organic acids contained in petroleum oils to reduce the acidity and corrosivity of such oils.
  • Examples of such technologies include treatment of metal surfaces with corrosion inhibitors such as poly sulfides (USP 5,182,013) or oil soluble reaction products of an alkynediol and a polyalkene polyamine (USP 4,647,366), and treatment of a liquid hydrocarbon with a dilute aqueous alkaline solution, specifically, dilute aqueous NaOH or KOH (USP 4,199,440).
  • corrosion inhibitors such as poly sulfides (USP 5,182,013) or oil soluble reaction products of an alkynediol and a polyalkene polyamine (USP 4,647,366)
  • USP 4,199,440 notes, however, that a problem arises with the use of aqueous solutions that contain higher concentrations of aqueous base. These solutions form emulsions with the oil, necessitating use of only dilute aqueous base solutions.
  • USP 4,300,995 discloses the treatment of carbonous materials particularly coal and its products such as heavy oils, vacuum gas oil, and petroleum residua, having acidic functionalities, with a quaternary base such as tetramethyl ammonium hydroxide in a liquid (alcohol or water). Additional processes using aqueous alkali hydroxide solutions include those disclosed in Kalichevsky and Kobe, Petroleum Refining With Chemicals, (1956) Ch. 4, as well as U.S. Pat. Nos.
  • U.S. Pat. Nos. 2,795,532 and 2,770,580 (Honeycutt) disclose processes in which "heavy mineral oil fractions" and "petroleum vapors", respectively are treated.
  • the '532 patent further discloses that "flashed vapors" are contacted with "liquid alkaline material” containing, inter alia, alkali metal hydroxides and "liquid oil”.
  • a mixture solely of NaOH and KOH in molten form is disclosed as the preferred treating agent, however, "other alkaline materials, e.g., lime, can also be employed in minor amounts”.
  • '532 does not disclose the treatment of whole crudes or fractions boiling at 105O +0 F (565 +O C). Rather '532 treats only vapors and condensed vapors of the
  • Amine naphthenates (Wasson et al, USP 2,401,993) and zinc naphthenates (Johnson et al, USP 2,415,353; Rouault, USP 2,430,951; and Zisman et al, USP 2,434,978) were also claimed as anticorrosive additives in various lubricating oil products.
  • Another use of calcium compounds with petroleum includes removal of naphthenic acids from hydrocarbon oils by limestone-on-glass abstraction (Elkin et al, Soviet Union 1,786,060) or by metal oxides related to hydrotalcites (Gillespie et al, USP 5,389,240).
  • calcium hydroxide (Kessick, Canadian Patent 1,249,760) aids in separation of water from heavy crude oil wastes.
  • USP 5,683,626 teaches treatments of acidic crudes with tetraalkyl- ammonium hydroxide and USP 5,643,439 uses trialkylsilanolates.
  • US/13689 and US/13690 Publications 97/08271 and 97/08275 dated March 6, 1997) teach the use of Group IA and Group HA oxides and hydroxides to treat whole crudes and crude fractions to decrease naphthenic acid content.
  • USP 3,847,774 teaches treatment of heavy petroleum distillates containing naphthenic acids by employing a caustic solution in the form of a fine droplet dispersion of an aqueous alkali metal hydroxide within an inert or non- reactive carrier hydrocarbon wherein the aqueous droplet size is about 1 to 10 ⁇ .
  • This dispersion is mixed with the heavy distillate in a common conduit by pass ⁇ ing through a mixing means for dispersing the aqueous alkali metal hydroxide in carrier hydrocarbon uniformly throughout the heavy petroleum distillate stream containing naphthenic acids and subjecting this mixture immediately after mixing and before any significant phase separation occurs to an electrical field to separate purified heavy hydrocarbon distillate phase from an aqueous mixture of excess alkali metal hydroxide and the alkali metal hydroxide salts of naphthenic acid.
  • USP 6,022,494 teaches a process for treating acidic crudes or fractions thereof to reduce or eliminate their acidity and corrosivity by, in one embodiment, the direct addition of metal carboxylates into the crude.
  • the metal carboxylates are prepared by adding an alkaline earth metal hydroxide to a small quantity of the crude to be treated or other hydrocarbon oil to produce a treating crude oil containing alkaline earth metal naphthanate which is then combined into the total quantity of the crude to be treated.
  • a naphthanate salt content in the range of 0.025: 1 to 1 : 1 moles of metal based on acid content of the acidic crude to be treated.
  • the acidic crude to be treated and the treating crude oil containing the metal naphthate salts should have comparable boiling points and characteristics.
  • the preferred hydrocarbon oil for the production of the treating crude oil is a small quantity of the same crude oil which is to be neutralized. If a different hydrocarbon oil is used, it must be compatible with the crude oil to be neutralized.
  • the patent goes on to expressly state that the formation of a crude oil-aqueous emulsion (i.e., either water-in-oil or oil-in- water) tends to interfere with the efficient separation of the crude oil and water phases and thus with recovery of the treated crude oil. Emulsion formation is undesirable and a particular problem that is encountered during treatment of naphthenic acid-containing crudes with aqueous bases.
  • wash water is mixed with crude usually through a mixing valve to produce an emulsion which is then sent to the desalter vessel where the wash water coalesces with brine droplets present in the crude.
  • An electrostatic field in the vessel serves to enhance coalescence and the large coalesced droplets settle by gravity and are withdrawn as waste water at the vessel bottom.
  • Desalted crude leaves from the vessel top.
  • Mixing valve pressure drop and hence mixing energy must be carefully controlled to avoid formation of too tight an emulsion which could then become difficult to separate electrostatically. This is especially important for certain crudes which contain naturally occurring surfactants or finely divided solids, both of which can stabilize emulsions.
  • USP 6,627,069 teaches a process for reducing the naphthenic acid content of crude oils and fractions thereof in the essential absence of oxygen in the presence of an aqueous base selected from Group IA and Group IIA hydroxides and ammonium hydroxide and mixtures thereof, a phase transfer agent that is a quaternary ammonium salt in amounts of from 10-5 to 10-1 at a temperature and pressure effective to produce a treated petroleum feed having a decreased naphthenic acid content and an aqueous phase containing naphthenate salts, phase transfer agent and base.
  • the feed is in the liquid state.
  • the oil On mixing the feed with the aqueous base-phase transfer agent mixture, the oil is in droplet form, the oil droplets being of sufficient size to enable the naphthenic acid containing component to achieve intimate contact with the aqueous phase.
  • Contact can be achieved by vigorous mixing of the components of the mixture. Thus it is seen that in this case an oil in water emulsion/mixture is created.
  • WO 00/75262 teaches deacidifying crude oil and/or fraction(s) thereof comprising contacting the crude oil and/or fraction(s) thereof with a Group HA metal hydroxide in the presence of water wherein water is present in a concentration of 0.01 to 100 wt% of the crude oil and/or fraction(s) thereof, introducing a demulsifier to the mixture of crude oil and/or fraction thereof, Group IIA metal hydroxide and water in an amount effective to cause the mixture to separate into in oil rich phase, an aqueous phase and an interface layer disposed between the oil rich phase and the aqueous phase.
  • the crude oil and/or fraction thereof and the Group HA metal hydroxide may be mixed by stirring or agitation using a mechanical stream an ultrasonic stirrer or by bubbling an inert gas through the reaction mixture.
  • the present invention is a method for decreasing the acidity and corrosivity of an acid containing corrosive crude comprising, securing an aqueous alkaline earth metal hydroxide solution or slurry, forming a water-in-oil emulsion of the aqueous alkaline earth metal hydroxide solution or slurry in a hydrocarbon carrier oil, preferably a small quantity of the same corrosive crude to be treated, the water-in-oil emulsion having an aqueous phase droplet size of between about 0.5 to 50 ⁇ , preferably between about 1 to 25 ⁇ , more preferably between about 1 to 10 ⁇ , mixing the water-in-oil emulsion with the crude to be treated in a ratio of about 0.2 to 10 volume of emulsion to 100 volumes of crude to be treated, preferably 0.5 to 5 volume of emulsion to 100 volumes of crude or fraction thereof to be treated, holding the crude or fraction thereof to which the water-in-oil emulsion has been
  • Naphthenic acid is a generic term used to identify a mixture of organic acids present in petroleum stocks. Naphthenic acids can cause corrosion at tempera ⁇ tures ranging from about 65°C (150 0 F) to 420°C (790 0 F). Naphthenic acids are distributed through a wide range of boiling points (i.e., fractions) in acid contain ⁇ ing crudes. The present invention provides a method for broadly removing such acids, and most desirably from heavier (higher boiling point) and liquid fractions in which these acids are often concentrated.
  • the naphthenic acids may be present either alone or in combination with other organic acids, such as phenols.
  • Corrosive, acidic crudes i.e., those containing naphthenic acids alone or in combination with other organic acids such as phenols may be treated according to the present invention.
  • the acidic crudes are preferably whole crudes.
  • acidic fractions of whole crudes such as topped crudes and other high boiling point fractions also may be treated.
  • 500 0 F (260 0 C) fractions, 650 +o F (343+ 0 C) fractions, vacuum gas oils, and most desirably 1050+°F (565+ 0 C) fractions and topped crudes may be treated.
  • the process of the present invention has utility in processes in which inhibiting or controlling or removing oil soluble contaminants present in crude oils or fractions thereof, is desired.
  • the reactive contacting method exploits the very large interfacial area characteristic of the fine water-in-oil emulsion and the long time available before the fine aqueous droplets will coalesce and settle. This permits sufficient mass transfer between the two phases and reactions to occur at the interface.
  • the method has application in the removal of acidic compounds from crude oil and/or fractions thereof by use of water-in-oil emulsions of alkaline earth metal hydrocarbons in carrier oil, in the removal of nitrogen compounds from oil by sulfuric acid treatment, in the removal of elemental sulfur and sulfur compounds from pipelined products, e.g., motor gasoline, diesel, crude, etc., using sodium hydroxide.
  • the present invention may be used in applications in which a reduction in the acidity, typically, as evidenced by a decrease in the neutralization number of an acidic crude or fraction thereof would be beneficial.
  • the concentration of acid in the crude oil is typically expressed as an acid neutralization number or acid number, which is the number of milligrams of KOH required to neutralize the acidity of one gram of oil. It may be determined according to ASTM D-664. Typically, the decrease in acid content may be determined by a decrease in the neutralization number or in the intensity of the carboxyl band in the infrared spectrum at about 1708 cm" 1 .
  • Crude oils with total acid numbers (TAN) of about 1.0 mg KOH/g and lower are considered to be of moderate to low corrosivity (crudes with a TAN of 0.2 or less generally are considered to be of low corrosivity). Crudes with total acid numbers greater than 1.5 are considered corrosive.
  • Acidic crudes having free carboxyl groups may be effectively treated using the process of the present invention.
  • the IR analysis is particularly useful in cases in which a decrease in neutralization number is not evident upon treatment with the base as has been found to occur upon treatment with bases weaker than KOH.
  • the crudes that may be used are any naphthenic acid-containing crude oils or fractions thereof that are liquid or liquefiable at the temperatures at which the present invention is carried out.
  • whole crudes means unrefined, undistilled crudes.
  • stoichiometric amount means a sufficient amount of alkaline earth metal hydroxide on a molar basis to neutralize a mole of acidic functionality in the crude oil. In moles, for Group HA hydroxides the stoichiometric ratio is 0.5:1 moles of metal to acid functionality.
  • the terms "above”, “greater than” or “in excess of stoichiometric are defined in relation to the foregoing, as is the term “substoichiometric”.
  • Substoichiometric ranges from 0.025:1 moles up to a stoichiometric amount, preferably 0.25:1 to less than 0.5:1 (i.e., a stoichiometric amount) for Group HA. Greater than stoichiometric can range up to 10:1 moles preferably up to 5:1. In the present process, however, preferably a stoichiometric to substoichiometric amount of alkaline earth metal hydroxide as metal to the acid to be treated in the crude is employed.
  • Preferred metals are calcium, magnesium, barium and strontium, with calcium and magnesium preferred, and calcium most preferred.
  • Contacting can be at any convenient temperature sufficient to facilitate reaction between the alkaline earth metal hydroxide and the acidic component in the crude or fraction thereof to be treated, typically about 20 0 C to 15O 0 C, preferably about 2O 0 C to 100 0 C, more preferably about 20 0 C to 60 0 C.
  • alkaline earth metal hydroxides in the form of a solid in water slurry.
  • aqueous slurry is then utilized as a water-in-oil emulsion which has an aqueous droplet size in the range of 0.5 to 50 ⁇ , preferably 1 to 25 ⁇ , more preferably about 1 to 10 ⁇
  • the alkaline earth metal hydroxide employed be in the form of a fine powder of a particle size in the range of and preferably smaller than the average aqueous droplet size in the water-in-oil emulsion.
  • the water-in-oil emulsion employed contains about 5 to 45 vol% of aqueous alkaline earth metal hydroxide solution or slurry to hydrocarbon carrier oil continuous phase, preferably 20 to 33 vol% of the aqueous alkaline earth metal hydroxide slurry to the hydrocarbon oil continuous phase.
  • the highest concentration is economically preferable while maintaining a water-in-oil emulsion to permit subsequent blending with a large volume of untreated crude.
  • the water-in-oil emulsion is formed by vigorously mixing the aqueous alkaline earth metal hydroxide slurry with the hydrocarbon phase to produce an emulsion wherein the aqueous droplet size is about 0.5 to 50 ⁇ , preferably 1 to 25 ⁇ , more preferably about 1 to 10 ⁇ .
  • This vigorous mixing can be accomplished by use of impellers, paddles, or other mechanical mixing means, sonic mixers, air-jet mixers, static mixers at high velocity, etc.
  • high shear high speed rotor-stator mixers are capable of producing the desired aqueous droplet size with low required residence times. Regardless of the technique employed, however, the aqueous droplet size is in the 0.5 to 50 ⁇ , preferably 1 to 25 ⁇ , more preferably 1 to 10 ⁇ range.
  • the hydrocarbon oil which is employed in the production of the water-in-oil emulsion can be any hydrocarbon or petroleum oil having a boiling point, viscosity, miscibility, etc., compatible with the crude oil or fraction thereof which is to be treated for acid removal. Most preferably it can be the same as the high TAN crude or fraction thereof to be treated.
  • the water-in-oil emulsion and the crude oil or fraction thereof which is to be treated are mixed at about 0.2 to 10 vol%, preferably about 1 to 5 vol% emulsion added to the crude oil or fraction thereof to be treated.
  • the amount added depends on the basicity of the emulsion and the acidity of the crude or fraction thereof to be treated.
  • the alkaline earth metal hydroxide content of the amount of emulsion added can range from substoichiometirc to super stoichiometric of the amount of metal needed to neutralize the total acid content of quantity of crude or fraction thereof to be treated. It is most desirable that the alkaline earth metal hydroxide content of the amount of emulsion added not be in excess of the stoichoimeter amount of metal needed to neutralize the total acid content of the crude or fraction thereof to be treated.
  • an amount of emulsion is used such that the alkaline earth metal hydroxide content is about 0.375 to 0.5 mole of metal per mole of acid to be neutralized. Operation at substoichometric concentration increases the likelihood if not ensuring the preferred condition that no unreacted alkaline earth metal hydroxide remains in the treated crude oil.
  • the mixture of the water-in-oil emulsion and the crude or fraction thereof to be treated is permitted to stand for a time sufficient to permit the desired partial or complete neutralization of the oil to be treated.
  • the holding time employed is typically that necessary for the complete consumption of the alkaline earth metal hydroxide. Holding times on the order of at least about 30 minutes, preferably at least about 1 hour, more preferably at least about 2 hours, and still more preferably at least about 4 hours are desirable, the upper limit to be set solely by practicality and storage issues.
  • Holding can be accomplished in crude storage tanks at the refinery if the neutralization step is practiced at the refinery or in the storage compartments of oil transport vessels, i.e., tankers, tank truck, barrels, etc., if the process is practiced at the well head or near the production facility. If the crude is to be pipelined over a distance even the holding time experienced in the pipeline during transit by the water-in-oil emulsion plus crude oil or fraction thereof to be treated may be sufficient to insure adequate reaction time and the desired level of neutralization.
  • oil transport vessels i.e., tankers, tank truck, barrels, etc.
  • a further advantage of treatment in crude storage tanks or upstream is that contaminants in the added alkaline earth metal hydroxide, which are inevitably present in commercial grades of such materials, or unreacted alkaline earth metal hydroxides can be effectively removed in the normal desalting operation in the refinery.
  • Modern desalters can efficiently remove undissolved, unreacted particulates into the desalter waste water thereby preventing potential downstream deposition and fouling in process equipment such as heat exchangers, furnaces, tower internals, etc.
  • Intense or extraneous mixing during the standing/holding stage is not needed. Because of the small aqueous droplet size, the aqueous phase remains distributed in the oil continuous phase for a long time.
  • TAN analysis next morning showed 75% and 76% TAN reduction respectively for two repeated experiments.
  • the calcium analysis of the crude showed 80% TAN neutralization for both, which checks the TAN reduction data.
  • An emulsion of aqueous calcium hydroxide in Gryphon crude was prepared using a high-speed (19000 rpm) shear mixer at room temperature. A mixing time as short as 20 seconds is very effective in preparing small drop size water-in-oil emulsions giving a water droplet size distribution of 1 to 10 microns with occasional droplets up to 25 microns. A measured amount of this emulsion equivalent to 100% TAN neutralization was dispersed in the crude oil (separately Gryphon and Chad) by moderate hand shaking for less than 15 seconds. The mixture was allowed to stand overnight in a tall vessel (H ⁇ V ⁇ 6) with periodic sampling of the crude mixture. Summarized below is the effective TAN reduction vs. time for both Gryphon and Chad crudes:

Abstract

L'invention concerne un procédé de réduction de l'indice d'acidité d'huiles de pétrole contenant des acides organiques. Ce procédé consiste: à former une émulsion d'eau dans l'huile contenant une solution ou une suspension épaisse d'hydroxyde métallique du Groupe IIA aqueuse dans une huile hydrocarbonée, ladite émulsion présentant un diamètre de particules de gouttelettes aqueuses compris entre 1 et 25 ν; à ajouter l'émulsion d'eau dans l'huile aux huiles de pétrole contenant des acides organiques; et à permettre le repos du mélange pendant une durée suffisante pour assurer la neutralisation des acides organiques dans les huiles de pétrole.
EP05792553A 2004-09-14 2005-08-30 Neutralisation d'emulsion de petrole brut a indice d'acidite (tan) eleve Withdrawn EP1789518A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US60962404P 2004-09-14 2004-09-14
US11/202,593 US20060054538A1 (en) 2004-09-14 2005-08-12 Emulsion neutralization of high total acid number (TAN) crude oil
PCT/US2005/030800 WO2006031432A2 (fr) 2004-09-14 2005-08-30 Neutralisation d'emulsion de petrole brut a indice d'acidite (tan) eleve

Publications (2)

Publication Number Publication Date
EP1789518A2 true EP1789518A2 (fr) 2007-05-30
EP1789518A4 EP1789518A4 (fr) 2011-09-21

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EP05792553A Withdrawn EP1789518A4 (fr) 2004-09-14 2005-08-30 Neutralisation d'emulsion de petrole brut a indice d'acidite (tan) eleve

Country Status (6)

Country Link
US (1) US20060054538A1 (fr)
EP (1) EP1789518A4 (fr)
JP (1) JP2008513551A (fr)
BR (1) BRPI0515296A (fr)
CA (1) CA2578589A1 (fr)
WO (1) WO2006031432A2 (fr)

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US9688920B2 (en) 2009-11-02 2017-06-27 Field Upgrading Limited Process to separate alkali metal salts from alkali metal reacted hydrocarbons
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CA2578589A1 (fr) 2006-03-23
WO2006031432A2 (fr) 2006-03-23
US20060054538A1 (en) 2006-03-16
WO2006031432A3 (fr) 2006-11-09
EP1789518A4 (fr) 2011-09-21
JP2008513551A (ja) 2008-05-01
BRPI0515296A (pt) 2008-07-15

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