EP2780434A1 - Dispositif et procédé pour valoriser des charges d'alimentation pétrolières à l'aide d'une membrane conductrice à base de métal alcalin - Google Patents

Dispositif et procédé pour valoriser des charges d'alimentation pétrolières à l'aide d'une membrane conductrice à base de métal alcalin

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Publication number
EP2780434A1
EP2780434A1 EP12849838.3A EP12849838A EP2780434A1 EP 2780434 A1 EP2780434 A1 EP 2780434A1 EP 12849838 A EP12849838 A EP 12849838A EP 2780434 A1 EP2780434 A1 EP 2780434A1
Authority
EP
European Patent Office
Prior art keywords
oil feedstock
alkali metal
chamber
feedstock
oil
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.)
Granted
Application number
EP12849838.3A
Other languages
German (de)
English (en)
Other versions
EP2780434B1 (fr
EP2780434A4 (fr
Inventor
John Howard Gordon
Javier Alvare
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.)
Enlighten Innovations Inc
Original Assignee
Ceramatec Inc
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Filing date
Publication date
Application filed by Ceramatec Inc filed Critical Ceramatec Inc
Publication of EP2780434A1 publication Critical patent/EP2780434A1/fr
Publication of EP2780434A4 publication Critical patent/EP2780434A4/fr
Application granted granted Critical
Publication of EP2780434B1 publication Critical patent/EP2780434B1/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
    • C10G32/00—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms
    • C10G32/02—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms by electric or magnetic means
    • 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/04—Metals, or metals deposited on a carrier
    • 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
    • C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
    • C10G75/02—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of corrosion inhibitors
    • 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
    • C10G2300/203—Naphthenic acids, TAN

Definitions

  • the present disclosure relates to a process for removing nitrogen, sulfur, heavy metals, and acid protons from sulfur-, nitrogen-, and metal-bearing shale oil, bitumen, heavy oil and petroleum refinery streams so that these materials may be used as a hydrocarbon fuel. More specifically, the present disclosure relates to removing nitrogen, sulfur, heavy metals and acid protons from shale oil, bitumen, heavy oil, or petroleum refinery streams while at the same time, upgrading these materials to have a higher hydrogen-to-carbon ratio.
  • hydrocarbon raw materials used to provide this energy often contain difficult-to-remove sulfur and metals.
  • sulfur can cause air pollution and can poison catalysts designed to remove hydrocarbons and nitrogen oxide from motor vehicle exhaust, necessitating the need for expensive processes used to remove the sulfur from the hydrocarbon raw materials before it is allowed to be used as a fuel.
  • metals such as heavy metals
  • These heavy metals can poison catalysts that are typically utilized to remove the sulfur from hydrocarbons. To remove these metals, further processing of the hydrocarbons is required, thereby further increasing expenses.
  • bitumen which exists in ample quantities in Alberta, Canada
  • heavy oils such as are found in Venezuela
  • oil feedstock The high level of nitrogen, sulfur, and heavy metals in shale oil, bitumen and heavy oil (which may collectively or individually be referred to as "oil feedstock") makes processing these materials difficult. Typically, these oil feedstock materials are refined to remove the sulfur, nitrogen and heavy metals through a process known as "hydro-treating.”
  • Hydro-treating may be performed by treating the material with hydrogen gas at an elevated temperature and an elevated pressure using catalysts such as C0-M0/AI2O3 or Ni-Mo/Al 2 0 3 .
  • the oil feedstock is mixed with an alkali metal (such as sodium) and hydrogen gas.
  • This mixture is reacted under modest pressure (and usually at an elevated temperature).
  • the sulfur and nitrogen atoms are chemically bonded to carbon atoms in the oil feedstocks.
  • the sulfur and nitrogen heteroatoms are reduced by the alkali metals to form ionic salts (such as Na 2 S, Na 3 N, Li 2 S, etc.).
  • ionic salts such as Na 2 S, Na 3 N, Li 2 S, etc.
  • the organic phase (oil feedstock) is less viscous and may be sent for further refining into a hydrocarbon fuel material.
  • the ionic salts formed in the hydro-treating process may be removed from the organic products by filtering, or first mixing the treated feedstock with hydrogen sulfide to form an alkali hydrosulfide, which forms a separate phase from the organic phase (oil feedstock). This reaction is shown below with sodium (Na) being the alkali metal, although other alkali metals may also be used:
  • the nitrogen product is removed in the form of ammonia gas (NH 3 ) which may be vented and recovered, whereas the sulfur product is removed in the form of an alkali hydro sulfide, NaHS, which is separated for further processing. Any heavy metals will also be separated out from the organic hydrocarbons by gravimetric separation techniques.
  • NH 3 ammonia gas
  • NaHS alkali hydro sulfide
  • alkali metals are used as part of the process.
  • An advantage of using alkali metals such as sodium or lithium instead of hydrogen to reduce the heteroatoms is alkali metals offer a greater reduction strength.
  • the alkali metals are better able to reduce the heteroatoms and form alkali metal nitrides or alkali metal sulfides.
  • a disadvantage of using the hydro-treating process is that hydrogen gas is a necessary reactant needed for the hydro-treating process.
  • hydrogen gas can be expensive.
  • hydrogen gas is formed by reacting hydrocarbon molecules with water.
  • 95% of the hydrogen is formed using the Steam-Methane Reforming Process from natural gas.
  • methane (CH 4 ) in natural gas is reacted with steam (H 2 0) at 750 °C - 800 °C to produce synthesis gas (syngas).
  • Syngas is a mixture primarily comprised of hydrogen gas (H 2 ) and carbon monoxide (CO).
  • the carbon monoxide produced in the first reaction is reacted with steam (H 2 O) over a catalyst to form hydrogen gas (H 2 ) and carbon dioxide (CO 2 ).
  • This second process e.g., the water gas shift reaction
  • Naphthenic acids are carboxylic acids present in petroleum crude or various refinery streams. These acids are responsible for corrosion in refineries.
  • a common measure of acidity of petroleum is called the Total Acid Number (“TAN") value and is defined as the milligrams (mg) of potassium hydroxide needed to neutralize the acid in one gram of the petroleum material. (Other acids found in the oil feedstock may also contribute to the TAN value). All petroleum streams with TAN >1 are called high TAN.
  • NAPs are a mixture of many different compounds and cannot be separated via distillation.
  • high TAN crudes are discounted over Brent Crude prices. For example, Doba crude with a TAN of 4.7 is discounted by $19 per barrel on a base price of $80 for Brent crude.
  • NAPs boil in the same range as that of kerosene/jet fuel. (However, kerosene/jet fuels have very stringent TAN specifications.) Attempting to neutralize these acids using aqueous caustic or other bases form salts. These salts in presence of water, lead to formation of stable emulsions. Additional methodologies of NAP reduction include hydrotreating or decarboxylation that are both destructive methodologies and the NAPs cannot be recovered using these methods. Solvent extraction or adsorption methodologies lead to high costs and energy usage for sorbent regeneration or solvent boiling. A new method for NAPs removal with lower energy consumption wherein NAPs can be recovered and processed as commercial products is required. Accordingly, a new method of neutralizing and/or removing NAPs is needed. Such a method and device is disclosed herein.
  • the present embodiments include a method of upgrading an oil feedstock with the benefit of a strong alkali metal agent without directly being required to handle, store, or transport the alkali metal.
  • the method comprises obtaining a quantity of an oil feedstock, the oil feedstock comprising at least one carbon atom and a heteroatom and/or one or more heavy metals.
  • the quantity of the oil feedstock is reacted with an alkali metal generated on an electrode within the reactor.
  • the reaction with the alkali metal may also include using an upgradant hydrocarbon such as hydrogen gas or a hydrocarbon.
  • a reactor may be utilized with at least two chambers separated in part by a membrane conductive to alkali metal ions.
  • This membrane conducts alkali metal ions from an alkali metal ion source material (such as a liquid comprised of sodium salts or sodium metal).
  • a positive charged electrode (anode) is in communication with the alkali metal ion source.
  • the opposite chamber of the reactor (called the feedstock chamber) includes a feedstock stream (comprised of the organic oil feedstock) and a negatively charged electrode (cathode).
  • the alkali metal enters the feedstock chamber and reacts with the heteroatom and/or the heavy metals in the feedstock to form one or more inorganic products, wherein the upgradant hydrocarbon reacts with the oil feedstock to produce an upgraded oil feedstock.
  • the reaction with the upgradent hydrocarbon operates such that the number of carbon atoms in the upgraded oil feedstock may be greater than the number of carbon atoms in the original oil feedstock.
  • the inorganic products are then separated from the upgraded oil feedstock.
  • the reaction of the oil feedstock, the alkali metal, and the upgradant hydrocarbon molecule may be implemented with or without using hydrogen gas. If hydrogen gas is utilized, the amount of hydrogen gas needed is much less than would be required using conventional hydrotreating.)
  • the alkali metal comprises sodium, lithium, or alloys of lithium and sodium.
  • the upgradant hydrogen source may comprise hydrogen, natural gas, shale gas and/or mixtures thereof.
  • the upgradant hydrocarbon comprises methane, ethane, propane, butane, pentane, their isomers, ethene, propene, butene, pentene, dienes, and/or mixtures thereof. (Oil retort gas, which is a mixture of gases that is produced in a refinery process may also be used as the upgradant hydrocarbon.)
  • the process of reacting the feedstock with the alkali metal may consist of two steps.
  • a first step involves having alkali metal ions be transferred across the membrane and reduced to metal at the membrane surface at a negatively charged electrode (which may be directly fixed to the membrane surface).
  • a second step involves having the formed alkali metal react directly with the constituents in the oil feedstock (or carried away with the oil to react downstream).
  • the electrode where the alkali metal is formed may be porous, or comprised of a mesh.
  • the electrode may be a film of metallic alkali metal connected to an electrical lead (or current collector).
  • a screen or mesh may provide a divider to separate a zone where the alkali metal is reduced from the oil feedstock. This screen allows the alkali metal to pass through as it is formed.
  • the reaction between the alkali metal and the oil feedstock may occur at a pressure that is between barometric and about 2500 psi and/or at a temperature that is between about 100 °C temperature and 450 °C. In other embodiments, the reaction between the alkali metal and the oil feedstock occurs at a temperature that is above the melting point of the alkali metal but is lower than 450 °C. Further embodiments may utilize a catalyst in the reaction.
  • the catalyst may comprise molybdenum, nickel, cobalt or alloys thereof, molybdenum oxide, nickel oxide or cobalt oxides and/or combinations thereof.
  • a separation step may be needed.
  • the separation used in the process may occur in a separator, wherein the inorganic products form a phase that is separable from an organic phase that comprises the upgraded oil feedstock and/or unreacted oil feedstock.
  • a flux may be added to the separator.
  • the alkali metal from the inorganic products may be regenerated and reused.
  • the upgraded oil feedstock produced in the reaction may have a greater hydrogen-to-carbon ratio than the oil feedstock.
  • the upgraded oil feedstock produced in the reaction may also have a greater energy value than the oil feedstock.
  • the heteroatom-to-carbon ratio of the upgraded oil feedstock may be less than the heteroatom-to-carbon ratio of the oil feedstock.
  • Additional embodiments may be designed in which an alkali metal is added to the oil feedstock in order to reduce the TAN value of the oil feedstock.
  • the alkali metal may react with the oil feedstock to remove the acidic components, thereby lowering the TAN value.
  • the original (unreacted) oil feedstock may have a TAN value of greater than or equal to 1 , but after reaction with the alkali metal, may have a TAN value of less than or equal to 1 .
  • Figure 1 shows a schematic drawing of a device that may be used to de- acidify a quantity of an oil feedstock
  • Figure 2 shows a schematic drawing of a device that may be used to upgrade a quantity of an oil feedstock
  • Figure 3 shows a schematic drawing of a device that may be used to de- acidify a quantity of an oil feedstock
  • Figure 4 shows a schematic drawing of another embodiment of a device that may be used to de-acidify a quantity of an oil feedstock
  • Figure 5 shows a schematic drawing of another embodiment of a device that may be used to upgrade a quantity of an oil feedstock
  • Figure 6 is a flow diagram of a method for upgrading a quantity of an oil feedstock.
  • Figure 7 a schematic drawing of another embodiment of a system that may be used to upgrade a quantity of an oil feedstock.
  • the present embodiments relate to a method to de-acidify feedstocks and refinery streams. Such de-acidification is beneficial as it may operate to reduce piping corrosion and may convert naphthenic acids to a salt form.
  • the present embodiments involve the addition of alkali metals (such as sodium or lithium metal) to the feedstocks as a means of reacting with the naphthenic acids, thereby de- acidifying these acids. When this reaction occurs, the naphthenic acids may be converted into the corresponding sodium or lithium salts (or other inorganic products). Hydrogen gas is also formed in this reaction. This reaction is summarized as follows:
  • the reaction with NAPs in this manner may be desirable and may result in a reduction of Total Acid Number ("TAN") associated with the oil feedstock.
  • TAN Total Acid Number
  • the alkali metal may be added to the feedstock.
  • the sodium or lithium metal is directly added to the stream. Once this occurs, the inorganic products may then be filtered from the oil stream.
  • Other embodiments may also be designed (as described herein) to provide other mechanisms for adding the alkali metal to the stream of oil feedstock (such as, for example, by forming the alkali metal in situ).
  • the alkali metals that are added to the feedstock may also react to remove sulfur, nitrogen, metals (such as heavy metals), etc. This process for removing these metals/heteroatoms is discussed in the '874 application.
  • the problems associated with metals/heteroatoms in the stream, as well as problems with acids in the stream may be overcome.
  • the present embodiments also provide methods and devices which operate to electrochemically produce alkali metals within an oil feedstock chamber (e.g., in situ), thereby bringing an alkali metal such as sodium in direct contact with the feedstock. Once this alkali metal is produced in the chamber, it is consumed by reacting with the heavy metals/heteroatoms and/or the acids in the feedstock.
  • inventions may be desirable in that they provide the strong reducing power and reactivity associated with alkali metals without ever having an appreciable amount of the metal present.
  • the present embodiments upgrade an oil feedstock using the alkali metal (e.g., a strong agent) without the practitioner being required to handle, store, or transport the alkali metal.
  • the alkali metal e.g., a strong agent
  • a device 2 that may be used to de- acidify a quantity of a first oil feedstock 9.
  • the oil feedstock 9 is a liquid that is placed within a chamber 3.
  • the chamber 3 may be a reaction vessel, a chamber of an electrolysis cell (as will be described herein), etc. Those skilled in the art will appreciate what vessels, containers, etc., may be used as the chamber 3.
  • the oil feedstock 9 comprises a quantity of naphthenic acids 8.
  • naphthenic acids 8 comprise carboxylic acids present in petroleum crude or various refinery streams. Naphthenic acids 8 are a mixture of many different compounds and cannot be separated out via distillation.
  • a quantity of an alkali metal 5 is added to the chamber 3.
  • the alkali metal is abbreviated as "AM."
  • the alkali metal may be sodium, lithium or alloys of sodium and lithium.
  • the chamber 3 may be kept at a temperature that is above the melting point of the alkali metal 5 such that the liquid alkali metal 5 may easily be added to the liquid oil feedstock.
  • the reaction occurs at a temperature that is above the melting point of the alkali metal (or above a temperature of about 100 °C). In other embodiments, the temperature of the reaction is less than about 450 °C.
  • the alkali metal 5 may react with the oil feedstock 9. More specifically, the alkali metal 5 reacts with the quantity of the naphthenic acids 8 to form a de-acidified feedstock 12.
  • a product separator 10 may be used to separate the de-acidified oil feedstock 1 2 from the inorganic acid products. Those skilled in the art will appreciate how this separation may occur. Moreover, those skilled in the art will appreciate the structures (such as a settling chamber, etc.) that may be used as the product separator 10.
  • the product separator 10 may be integral with the chamber 3 or may be a separate structure, as shown in Figure 1 .
  • the reaction between the alkali metal 5 and the naphthenic acids 8 operates to eliminate the naphthenic acids 8 from the oil feedstock 9.
  • the TAN value of the de-acidified oil feedstock 12 will be lower than the TAN value of the original (unreacted) first oil feedstock 9.
  • the TAN value of the original (unreacted) oil feedstock 9 may be greater than or equal to 1 (such as, for example, 3, 4, 5, etc.) whereas the TAN value of the de-acidified oil feedstock 12 is a lower value, such as less than or equal to 1 .
  • other acids in the oil feedstock 9 may contribute to the TAN value of the feedstock 9. These acids may also react with the alkali metal in a similar manner, further reducing the TAN value.
  • This reduction in TAN value may provide a significant financial benefit to the owner of the oil feedstock.
  • prices per barrel of oil products that are considered to be high TAN e.g., with a TAN value greater than 1
  • the value of the oil feedstock may be significantly increased.
  • the device 2a is similar to the device 2 shown in Figure 1 .
  • the device 2a may be designed to de-acidify the oil feedstock 9.
  • the device 2a may also be designed to further upgrade the first oil feedstock 9 by removing heavy metals 14 and/or one or more heteroatoms 1 1 that are present in the oil feedstock 9.
  • the device 2a may be designed such that the alkali metal 5 may react with the heavy metals 14 in the oil feedstock 9. More specifically, in addition to the alkali metal 5 reacting with the napthenic acids 8 to de-acidify the feedstock (as described above), the quantity of the alkali metal 5 may further react with the heavy metals 14, thereby reducing the heavy metals into their metallic states. This reaction may also occur in the chamber 3.
  • these heavy metals 1 6 may then be separated and recovered (using the product separator 10).
  • the heavy metals 16 in their metallic state, are inorganic materials and thus may separate out from the organic oil feedstock materials. Accordingly, the product separator 10 may use this property as a means of separating out the heavy metals 16.
  • the product separator 10 may use this property as a means of separating out the heavy metals 16.
  • other separation techniques may also be used to separate out the heavy metals 16.
  • Once the metals 16 have been separated they may be recovered, sold, used in further processing, etc. As these metals are generally expensive commodities, the fact that such metals may be collected (and used/sold) may provide a significant commercial advantage for the owner of the feedstock.
  • the alkali metal 5 may also react with one or more heteroatoms 1 1 (such as N, S) that are present in the oil feedstock 9. These N, S atoms may be bonded to the carbon/hydrogen atoms in the organic oil feedstock 9. However, as noted herein, the alkali metal 5 may react with these one or more heteroatoms 1 1 to form inorganic sulfur/nitrogen products 17. For example, if the alkali metal 5 is sodium, then the reaction with the heteroatoms 1 1 forms inorganic sulfur/nitrogen products 17 such as Na 2 S, Na 3 N and/or other inorganic products.
  • heteroatoms 1 1 such as N, S
  • a product separator 1 0 may be used to separate out the inorganic sulfur/nitrogen products 17 from the oil feedstock). Once the inorganic sulfur/nitrogen products 17 have been removed, the heteroatom to carbon ratio of the resulting oil feedstock is less than the heteroatom to carbon ratio of the original (unreacted) oil feedstock 9.
  • oil feedstock 9 has been de-acidified, demetalized, de-sulfurized and/or de-nitrogenized, then this oil feedstock is referred to as an "upgraded" oil feedstock 12a in that this material is better suited for further refining, commercialization, etc.
  • a single product separator 10 is shown as separating out the heavy metals 16, the inorganic acid products 13 and the inorganic sulfur/nitrogen products 17, thereby removing these materials from the upgraded oil feedstock 12a.
  • multiple product separators 10 and/or separation techniques may be used to accomplish such separations.
  • embodiments may be designed in which a first chamber is used to react the alkali metal 5 with the heavy metals 14 (and the heavy metals 14 are subsequently separated out), a second chamber is used to react the alkali metal 5 with the naphthenic acid 8 (and the acid products 1 3 are subsequently separated out) and then a third chamber used to react the alkali metal 5 with the heteroatoms 1 1 (and the sulfur/nitrogen products 17 are subsequently separated out).
  • the reaction conditions such as pressure, temperature, flow rates, etc., could be adjusted/tailored to optimize each specific reaction.
  • the alkali metal 5 is shown being added to the chamber 3.
  • the alkali metal 5 may be added in order to induce a reaction.
  • a sample of the alkali metal 5 may simply be added to the chamber 3.
  • many in the oil processing industry are uncomfortable handling metallic sodium (or other metallic alkali metals) because of their reactive nature.
  • other embodiments may be designed in which the alkali metal 5 is formed in situ within the chamber 3 from alkali metals ions. In other words, alkali metal ions are added to the chamber 3 (which are safe and easy to handle) and then such ions are reduced back to the metallic state via an electrochemical reduction reaction.
  • the device 100 consists of at least two chambers, namely a feedstock chamber 20 and an alkali metal source chamber 30.
  • the feedstock chamber 20 has an outer wall 21 and may have an inlet 22 and outlet 23.
  • the feedstock chamber 20 may be separated from the alkali metal source chamber 30 by an alkali metal ion conductive separator 25.
  • the ion separator 25 may be comprised of ceramic materials generally known as Nasicon, sodium beta alumina, sodium beta prime alumina or sodium ion conductive glass if the alkali metal is sodium; or Lisicon, lithium beta alumina, lithium beta prime alumina or lithium ion conductive glass if the alkali metal is lithium.
  • the materials used to construct the ion separator 25 are commercially available from Ceramatec, Inc., of Salt Lake City, Utah.
  • a cathode 26 which is negatively charged and connected to a power source 40 (via wires 42) may be, at least partially, housed within the feedstock chamber 20.
  • the cathode 26 is located in close proximity to the ion separator 25 to minimize ionic resistance.
  • the cathode 26 may be contacting the ion separator 25 (as shown in Figure 3) or screen printed on the ion separator 25.
  • the cathode 26 may be integrated with the ion separator 25 as disclosed in U.S.
  • Patent Publication 2010/0297537 entitled “ELECTROCHEMICAL CELL COMPRISING IONICALLY CONDUCTIVE MEMBRANE AND POROUS MULTIPHASE ELECTRODE” (which patent application is expressly incorporated herein by reference.)
  • the oil feedstock does not necessarily have to be ionically conducting in order to transfer ions/charges.
  • the alkali metal source chamber 30 has an outer wall 31 and may have an inlet 32 and outlet 33.
  • An anode 36 (which is positively charged) and connected to the power source 40 (via wires 42) may be, at least partially, housed within the source chamber 30.
  • Suitable materials for the cathode 26 include materials comprising, carbon, graphite, nickel, iron which are electronically conductive.
  • Suitable materials for the anode 36 include materials comprising titanium, platinized titanium, carbon, graphite.
  • the cathode 26 and the anode 36 are connected to the same power supply 40.
  • Figure 3 shows the wires 42 exiting the chambers 20, 30 via inlets 22, 32. Such depictions are made for clarity and are not limiting.
  • the power source 40/wires 42 may be otherwise arranged in order to connect to the cathode 26 and/or the anode 36.
  • the cathode 26 and the anode 36 may be connected to power supplies in various manners, etc.
  • a first oil feedstock 50 may enter the feedstock chamber 20 (such as, for example, by flowing through the inlet 22).
  • a dissolved solution of alkali metals 51 will flow through the alkali metal source chamber 30.
  • This solution of alkali metals may be, for example, a solution of sodium sulfide, lithium sulfide, sodium chloride, sodium hydroxide, etc.
  • a voltage is then applied to the anode 36 and cathode 26 from the source 40. This voltage causes chemical reactions to occur. These reactions cause alkali metal ions 52 (abbreviated "AM ions" 52") to pass through the ion separator 25. In other words, the alkali metal ions 52 flow from the alkali metal source chamber 30, through the ion separator 25, into the feedstock chamber 20.
  • AM ions alkali metal ions 52
  • the alkali metal ions 52 (such as, for example, sodium ions or lithium ions) pass through the ion separator 25, the ions 52 are reduced to the alkali metal state 55 (e.g., into sodium metal or lithium metal) at the cathode 26.
  • the alkali metal 55 intermixes with the feedstock 50 (as shown by arrow 58).
  • the reaction between the oil feedstock 50 and the alkali metal 55 may involve a reaction between the acids (such as naphthenic acid) in the oil feedstock 50.
  • the reaction with the alkali metal 55 which was formed in situ within the chamber 20, operates to reduce the acid content in the oil feedstock 50, thereby reducing the TAN value of the oil feedstock 50.
  • the reaction between the oil feedstock 50 and the alkali metal 55 formed within the chamber 20 may cause a reaction with the sulfur or nitrogen moieties within the oil feedstock 50. This reaction may also reduce heavy metals, such as vanadium and nickel in the feedstock 50. Further, as explained in the '874 application, at an elevated temperature and elevated pressure, the reaction between alkali metals 55 and the heteroatoms (S, N) forces the sulfur and nitrogen heteroatoms to be reduced by the alkali metals into ionic salts (such as Na 2 S, Na 3 N, Li 2 S, etc.). These ionic salts may then be removed from the oil feedstock 50.
  • ionic salts such as Na 2 S, Na 3 N, Li 2 S, etc.
  • the content of sulfur and nitrogen within the oil feedstock 50 may be significantly reduced by the reaction of the alkali metal 55 formed within the chamber 20.
  • the heteroatom-to-carbon ratio of the upgraded oil feedstock may be less than the heteroatom-to-carbon ratio of the original (unreacted) oil feedstock.
  • the amount of heavy metals in the feedstock may further be reduced.
  • the ratio of carbon to heavy metals in the upgraded (reacted) feedstock is less than the ratio of carbon to heavy metals in the original (unreacted) feedstock.
  • the chamber 20 may also include a quantity of an upgradant hydrocarbon 60 that reacts with the oil feedstock 50 (as shown by arrow 74).
  • an upgradant hydrocarbon 60 that reacts with the oil feedstock 50 (as shown by arrow 74).
  • the upgradant hydrocarbon 60 may be hydrogen gas, including the hydrogen gas formed by the reaction with naphthenic acid. (It should be noted that if hydrogen is used as the hydrocarbon 60, the amount of hydrogen needed is less than the amount of hydrogen that would be required if a typical hydrotreatment process were utilized).
  • the upgradant hydrocarbon 60 comprises natural gas, shale gas and/or mixtures thereof, methane, ethane, propane, butane, pentane, their isomers, ethene, propene, butene, pentene, dienes, and/or mixtures thereof.
  • this reaction with the upgradant hydrocarbon 60 may operate to produce an upgraded hydrocarbon that has a greater hydrogen-to-carbon ratio than the original oil feedstock 60.
  • the upgraded oil feedstock produced in the reaction may also have a greater energy value than the original oil feedstock 60.
  • the presence of upgradant hydrocarbon 60 may result in a reduction of formation of insoluble solids during the reaction.
  • these solids are large organic polymers that are formed as part of the radical reactions.
  • this hydrocarbon 60 acts as a "capping" species that prevents the formation of these solid, organic polymers.
  • the subsequent yield of the liquid oil feedstock e.g., the desired product
  • the reactions described in Figure 3 may be conducted at elevated temperatures.
  • the reactions may occur at temperatures above the melting temperature of sodium or at higher temperatures found effective for the particular feedstock.
  • the mode of operation of the device 1 00 may further consist of using molten sodium as the sodium source 51 in the alkali metal source chamber 30 or lithium metal as the lithium source.
  • the reactions may further be conducted at elevated pressure, for example in the 300 - 2000 pounds per square inch range.
  • the oil feedstock 50 may be passed through the device 100 (as the solution of sodium sulfide also passed through). Once passed through the device 1 00, the oil feedstock may flow into another vessel operated at a different temperature and pressure (e.g., temperatures and pressures more conducive to the reactions desired and where the residence time of the feedstock in the second vessel size is matched to the reaction kinetics and flow rates).
  • a different temperature and pressure e.g., temperatures and pressures more conducive to the reactions desired and where the residence time of the feedstock in the second vessel size is matched to the reaction kinetics and flow rates.
  • various solids, inorganic compounds, etc. may be formed when performing the reactions outlined herein.
  • These inorganic products may comprise Na 2 S, NaN 3 , heavy metals and solid organic polymers that are formed by the radical reactions.
  • the process used in conjunction with the device of Figure 3 may further involve filtering, or separating by centrifugal forces the feedstock after it has been exposed to the sodium for sufficient time to remove solids from the liquids. This separation may involve the use of a separator 80, as described below.
  • the oil feedstock 50, alkali metal solution 51 and other components of the device 100 may be dissolved in a polar solvent such as Formamide, Methyl formamide, Dimethyl formamide, Acetamide, Methyl acetamide, Dimethyl acetamide, Triethylamine, Diethyl acetamide, Ethylene glycol, Diethylene glycol, Triethylene glycol, Tetraethylene glycol, Ethylene Carbonate, Propylene Carbonate, Dimethylpropyleneurea, Butylene Carbonate, Cyclohexanol, 1 ,3-Cyclohexanediol, 1 ,2 Ethanediol, 1 ,2-Propanediol, Ethanolamine, Methyl sulfoxide, Dimethyl sulfoxide, Tetramethylene sulfoxide, Sulfolane, Gamma-butyrolactone, Nitrobenzene, Acetonitrile, Pyridine, quinoline, am
  • the alkali metal solution 51 may be dissolved in one or more of these solvents and then be allowed to flow into the alkali metal source chamber 30.
  • the salts that are used for the alkali metal solution 51 may be alkali metal chlorides, hydroxides, phosphates, carbonates, sulfides and the like.
  • such solvents may be used with the oil feedstock 50 and/or the hydrocarbon 60 and then the mixture may be allowed to flow into the chamber 20.
  • the anode reaction in the alkali metal source chamber 30 may vary.
  • sulfides may form polysulfides and or elemental sulfur
  • chlorides may form chlorine gas
  • hydroxides may form oxygen gas
  • carbonates may form oxygen gas and evolve carbon dioxide and the like.
  • alkali metal source is an alkali metal
  • metal ions will simply form.
  • the products formed in the oil feedstock chamber 20 may be sent to a product separator 80 (as shown by arrow 82).
  • the inorganic products may form a phase that is separable from an organic phase that comprises the upgraded oil feedstock and/or unreacted oil feedstock.
  • a flux may be added to the product separator.
  • the product separator 80 may be a settling chamber or other similar structure.
  • Figure 4 is a schematic that includes another embodiment of the device 100. Much of the structures/elements depicted in Figure 4 are similar to that which was described in Figure 3. Accordingly, for purposes of brevity, the discussion of many of these structures/elements is omitted.
  • FIG 4 depicts a schematic embodiment similar to the depiction in Figure 3 except a porous partition 101 resides between the ion separator 25 and the feedstock 50.
  • This partition 101 may be a metal mesh or perforated metal sheet, or glass fiber mesh, carbon fiber mesh or other material with holes or pores that will allow alkali metal to flow through.
  • Alkali metal 102 is formed at the ion separator 25 and may serve as the cathode with a negatively charged current collector 103 in contact with the alkali metal 1 02.
  • the porous partition 101 if electronically conductive, may be negatively charged and serve as the current collector.
  • the alkali metal 102 Once the alkali metal 102 is formed, it may flow through the porous partition 101 and may then react with the oil feedstock 50 in the manner described above.
  • the addition of the alkali metal 102 may not simply neutralize the acidic hydrogen in the napthenic acid.
  • naphthenic acid has the structure: R— COOH.
  • the alkali metal 102 may react with the oxygen atoms (in addition to the hydrogen atoms) such that the remaining hydrocarbon after the alkali metal addition has the structure R— CH 3 , R— H, etc. (The reason for this is that the alkali metal 102 may also reduce the oxygen moiety as well as the hydrogen moiety.)
  • the formed inorganic products may thus include NaOH, Na 2 0, etc.
  • the TAN value of the feedstock 50 is reduced.
  • the TAN value may not be increased (or returned to its original state) by simply reacting the de-acidified oil feedstock with base (such as NaOH). Rather, as described herein, the reduction of the TAN value may also operate to convert the napthenic or other acid groups into pure hydrocarbon functional groups (such as is R— CH 3 , R— H, etc.).
  • the device 1 00 may be used to upgrade an oil feedstock 50. More specifically, the feedstock 50 may be upgraded by having the feedstock 50 be de-acidified, desulfirized, demetalized and denitrogenized. In other words, the device 100 is operable to remove sulfur, heavy metals, acids (such as napthenic acid) and nitrogen from the oil feedstock 50.
  • FIG. 5 The embodiment of the device 100 that is shown in Figure 5 is similar to that which is shown and described in Figure 3. For purposes of brevity, much of this discussion will be omitted. However, for clarity, the wires 42 and the power source 40 are not shown in Figure 5. However, those skilled in the art will appreciate that such structures are indeed present and may be necessary in order to conduct the electrolytic reactions associated with the device 1 00.
  • the oil feedstock 50 shown in Figure 5 may include quantities of heavy metals, napthenic acid and at least one heteroatom (e.g., nitrogen and sulfur). Accordingly, such materials may be removed from the oil feedstock 50 using the methods outlined herein. Specifically, the oil feedstock 50 is contacted with quantities of alkali metals 55a, 55b, 55c. (The arrows 58 are designed to represent the reactions between the alkali metals 55a, 55b, 55c and the oil feedstock 50.) More specifically, the feedstock 50 may be contacted with a first quantity of an alkali metal 55a.
  • the reaction between the first quantity of the alkali metal 55a and the feedstock 50 is such that the alkali metal 55a reacts with the heavy metals that are in the feedstock 50.
  • This reacted feedstock may then exit the chamber 20 and may pass through a product separator 80.
  • the purpose of the product separator 80 is to remove the heavy metals from the oil feedstock. These heavy metals may then be recovered, sold, etc.
  • the feedstock 50 (minus the heavy metals which were previously removed) may be brought back into the chamber 20.
  • This chamber 20 may be the same chamber that was previously used to remove the heavy metals, or it may be a chamber 20 of a different device 100 that is positioned downstream from the product separator 80.
  • the oil feedstock 50 (which has had the heavy metals removed) may then be reacted with a second quantity of the alkali metal 55b.
  • the alkali metal 55b reacts with the napthenic acid to form a de-acidified oil feedstock, wherein a TAN value of the unreacted oil feedstock is less than a TAN value of the de-acidified oil feedstock.
  • the reacted oil feedstock 50 may be sent to the product separator 80 which may operate to remove the inorganic materials that were formed during the reaction with the second quantity of alkali metals 55b. This separation of inorganic materials may occur within the same product separator 80 that was used to remove the heavy metals or may be conducted in a different separator product 80.
  • the feedstock 50 (minus the heavy metals and the napthenic acids which were previously removed) may be brought back into the chamber 20.
  • This chamber 20 may be the same chamber that was previously used to remove the heavy metals/napthenic acids, or it may be a chamber 20 of a different device 100 that is positioned downstream from the product separator 80.
  • the oil feedstock 50 (which has had the heavy metals/napthenic acids removed) may then be reacted with a third quantity of the alkali metal 55c. This reaction with the third quantity of the alkali metal 55c removes at least one heteroatom (e.g., N, S) from the feedstock 50 to form an upgraded oil feedstock.
  • heteroatom e.g., N, S
  • the heteroatom to carbon ratio of the upgraded oil feedstock is less than a heteroatom to carbon ratio of the oil feedstock.
  • this product may then pass through a product separator 80 to remove the inorganic materials and/or N, S moieties from the oil feedstock, thereby resulting in an upgraded oil feedstock.
  • the alkali metal quantities 55a, 55b, 55c in Figure 5 were introduced using the method of the device 100-e.g., by having alkali metal ions pass through the ion separator 25 and then be reduced to the metallic state in situ within the chamber 20.
  • the alkali metal quantities 55a, 55b, 55c are introduced directly into the oil feedstock 50 (e.g., without having the metal be formed via a reduction reaction).
  • the different quantities of the alkali metals 55a, 55b, 55c may be the same alkali metal or may be different alkali metals.
  • FIG. 6 a flow diagram of a method 190 that may be used to upgrade a quantity of a first oil feedstock 50a is shown.
  • the quantity of the oil feedstock 50 may be obtained.
  • This oil feedstock 50 may include quantities of heavy metals, acids (such as napthenlic acid), and/or one or more heteroatoms (such as sulfur and nitrogen moieties).
  • these metals/heteroatoms/acids may be removed from the oil feedstock 50a.
  • the quantity of the oil feedstock 50a may be added to a chamber 1 1 0a.
  • This chamber 1 10a may be referred to as a "de-metalization" chamber in that the heavy metals are removed from the oil feedstock 50a in this chamber 1 10a.
  • the chamber 1 10a may be an oil feedstock chamber 20 of the type described above.
  • the chamber 1 10a may simply be another type of vessel that is designed to remove metals from the oil feedstock 50a.
  • a quantity of alkali metals (such as alkali metals 55a shown in Figure 5) may be added to the feedstock 50a. Once the reaction has occurred, the products may be placed within a product separator 80a.
  • This oil feedstock 50b may then be added to a chamber 1 10b.
  • the chamber 1 10b may be the same chamber as the chamber 1 10a (e.g., the oil feedstock material is re-inserted into the chamber 1 10a) or it may be a different vessel.
  • the chamber 1 10b may be referred to as a "de-acidification" chamber in that the oil feedstock 50b may be de-acidified in this chamber 1 10b.
  • the oil feedstock 50b is reacted with a quantity of an alkali metal (such as second quantity of the alkali metal 55b shown in Figure 5).
  • This reaction with the alkali metal 55b reacts with the napthenic acid in the feedstock 50b. More specifically, the alkali metal 55b eliminates the naphtenic acid such that the reacted oil feedstock has a TAN value that is less than the TAN value of the (unreacted) oil feedstock 50a.
  • the products may be placed within a product separator 80b.
  • a product separator 80b Those skilled in the art will appreciate the types of devices (such as a settling chamber) that may be used as the product separator 80b.
  • the product separator 80b may be the same structure as the product separator 80a or may be a different element. In this product separator 80b, inorganic acid products 127 are separated out, leaving only a quantity of "de-acidified" oil feedstock 50c.
  • This de-acidified oil feedstock 50c (which has also been de-metalized) may then be added to a chamber 1 10c.
  • This chamber 1 10c may be the same as either or both of the chambers 1 10a, 1 10b, or in other embodiments, the chamber 1 1 0c may be a different chamber than the chambers 1 10a, 1 1 0b.
  • This chamber 1 1 0c may be referred to as a "de-sulfurization" chamber in that sulfur moieties from the oil feedstock may be removed. More specifically, an alkali metal (such as a third quantity of the alkali metal 55c) may be added to react with the oil feedstock.
  • this reaction involves reacting the alkali metal with a heteroatom, such as sulfur. (This reaction is described above). Once reacted, the products may be added to a product separator 80c which operates to remove inorganic sulfur products 129 from the oil feedstock, thereby producing de-sulfurized feedstock 50d.
  • a heteroatom such as sulfur
  • This feedstock 50d may further be added to a chamber 1 10d.
  • This chamber 1 10d may be the same as or different than the chambers 1 10a, 1 10b, 1 10c.
  • heteroatoms such as nitrogen are removed from the oil feedstock by reacting the feedstock with an alkali metal quantity (such as, for example, alkali metal 55c of Figure 5).
  • an alkali metal quantity such as, for example, alkali metal 55c of Figure 5
  • the inorganic nitrogen products 131 may be removed via product separator 80d (which may be the same as, or a different structure than, the product separators 80a, 80b, 80c).
  • the resulting oil feedstock, after all of these products have been removed, may be classified as an "upgraded" oil feedstock 50e.
  • FIG 7 another embodiment of a system 200 for upgrading an oil feedstock is shown.
  • the system 200 includes many of the same features that are associated with the device 1 00 of Figure 3. For purposes of brevity, much of this discussion will be omitted. However, for clarity, the wires 42 and the power source 40 are not shown in Figure 7. However, those skilled in the art will appreciate that such structures are indeed present and may be necessary in order to conduct the electrolytic reactions associated with the system 200.
  • a quantity of a first oil feedstock 150a is added to a TAN reduction chamber 205.
  • This chamber 205 is a chamber into which an alkali metal (in its metallic form) may be added.
  • This addition of the alkali metal to the feedstock 150a operates to eliminate naphthenic acid in the feedstock 150a. Accordingly, the TAN value of the feedstock 150a after it has been reacted in the TAN reduction vessel 205 is significantly reduced.
  • a separator (which is not shown in Figure 7) may be used to remove the formed inorganic materials from the feedstock.
  • the feedstock leaving this chamber 205 may be referred to as de- acidified oil feedstock 150b.
  • the de-acidified feedstock 150b may be added to a chamber 20 so that it may be exposed to alkali metal 155b, thereby eliminating the heteroatoms and/or the heavy metals in the feedstock 150b.
  • Figure 7 shows an embodiment in which the chamber 205 used to reduce the TAN value is separate from the chamber 20 that is used to de-nitrogenize/de-sulfurize the feedstock.
  • the temperature and pressure and flow rate for optimal TAN reduction may be used in the TAN vessel 205, and then different temperatures/pressures/flow rates, etc. may be used in the chamber 20 for the other chemical reactions. These different temperatures/pressures/flow rates may be matched to the reaction kinetics of the specific reactions.
  • FIG. 7 illustrates that there is a significant amount of flexibility associated with the present embodiments.
  • a TAN reduction chamber 205 that is designed to reduce the TAN value of the oil feedstock.
  • this TAN value has been reduced (for example to a value that is less than or equal to 1 )
  • other processes may be used to eliminate the heteroatoms, heavy metals, etc. associated with the oil feedstock.
  • the owner of the oil feedstock can design a system that will be appropriate for processing their particular sample of hydrocarbon material.
  • the oil feedstock 1 50c may flow out of the chamber 20. This oil feedstock will be referred to as "upgraded” oil feedstock 150c.
  • alkali metal that is needed to reduce the TAN value below 1 , to remove the heteroatoms, to react with the heavy metals, etc., will depend upon the particular sample of oil feedstock/hydrocarbon material. Accordingly, by performing testing on the sample oil feedstock, a skilled artisan can determine how much alkali metal may be needed to upgrade the oil feedstock.

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

Abstract

L'invention concerne un réacteur qui possède deux chambres, à savoir une chambre de charge d'alimentation d'huile et une chambre de source. Un séparateur d'ions sépare la chambre de charge d'alimentation d'huile de la chambre de source, le séparateur d'ions permettant à des ions de métaux alcalins de passer de la chambre de source, à travers le séparateur d'ions, et dans la chambre de charge d'alimentation en huile. Une cathode est au moins partiellement reçue à l'intérieur de la chambre de charge d'alimentation d'huile et une anode est au moins partiellement reçue à l'intérieur de la chambre de source. Une quantité d'une charge d'alimentation d'huile se situe à l'intérieur de la chambre de charge d'alimentation d'huile, la charge d'alimentation d'huile comprenant au moins un atome de carbone et un hétéroatome et/ou un ou plusieurs métaux lourds, la charge d'alimentation d'huile comprenant en outre de l'acide naphténique. Lorsque l'ion de métal alcalin entre dans la chambre de charge d'alimentation en huile, le métal alcalin réagit avec l'hétéroatome, les métaux lourds et/ou l'acide naphténique, la réaction avec le métal alcalin ainsi formant des produits inorganiques.
EP12849838.3A 2011-11-16 2012-11-16 Procédé pour valoriser des charges d'alimentation pétrolières à l'aide d'une membrane conductrice à base de métal alcalin Active EP2780434B1 (fr)

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US201161560653P 2011-11-16 2011-11-16
PCT/US2012/065670 WO2013075021A1 (fr) 2011-11-16 2012-11-16 Dispositif et procédé pour valoriser des charges d'alimentation pétrolières à l'aide d'une membrane conductrice à base de métal alcalin

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GB9912842D0 (en) * 1999-06-02 1999-08-04 Bp Exploration Operating Process for reducing the acidity of oil
GB0113645D0 (en) * 2001-06-05 2001-07-25 Bp Exploration Operating Process
JP3516446B2 (ja) * 2002-04-26 2004-04-05 東京応化工業株式会社 ホトレジスト剥離方法
BRPI0405935A (pt) * 2003-12-19 2005-10-04 Shell Int Research Métodos de produzir um produto de petróleo bruto e combustìvel de transporte, combustìvel de aquecimento, lubrificantes ou substâncias quìmicas e produto de petróleo bruto
US7897028B2 (en) * 2004-01-26 2011-03-01 Ceramatec, Inc. Process for the recovery of materials from a desulfurization reaction
US20060054538A1 (en) * 2004-09-14 2006-03-16 Exxonmobil Research And Engineering Company Emulsion neutralization of high total acid number (TAN) crude oil
WO2009070593A1 (fr) * 2007-11-27 2009-06-04 Ceramatec, Inc. Procédé pour récupérer des métaux alcalins et du soufre à partir de sulfures et de polysulfures de métaux alcalins
US8486251B2 (en) * 2008-08-05 2013-07-16 Exxonmobil Research And Engineering Company Process for regenerating alkali metal hydroxides by electrochemical means
US8338038B2 (en) * 2008-09-12 2012-12-25 Ceramatec, Inc Electrochemical cell comprising ionically conductive membrane and porous multiphase electrode
US20100087124A1 (en) * 2008-10-07 2010-04-08 Farzad Saghian Cd repair apparatus
JP5720055B2 (ja) * 2009-11-02 2015-05-20 セラマテック・インク アルカリ金属および炭化水素を使用した石油原料の改質
US8608952B2 (en) * 2009-12-30 2013-12-17 Uop Llc Process for de-acidifying hydrocarbons

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EP2780434B1 (fr) 2021-03-03
SG11201402307SA (en) 2014-09-26
IN2014CN04302A (fr) 2015-09-04
ES2862578T3 (es) 2021-10-07
CA2997472C (fr) 2020-02-25
WO2013075021A1 (fr) 2013-05-23
JP2015501860A (ja) 2015-01-19
CA2997472A1 (fr) 2013-05-23
CA2855966C (fr) 2018-05-01
CA2855966A1 (fr) 2013-05-23
HK1202572A1 (en) 2015-10-02
ES2862578T8 (es) 2022-01-10
JP6162711B2 (ja) 2017-07-12
EP2780434A4 (fr) 2015-07-15
KR101909773B1 (ko) 2018-10-18
KR20140096119A (ko) 2014-08-04

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