EP2986691A1 - Procédé pour séparer des sels de métal alcalin d'hydrocarbures ayant réagi avec un métal alcalin - Google Patents

Procédé pour séparer des sels de métal alcalin d'hydrocarbures ayant réagi avec un métal alcalin

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Publication number
EP2986691A1
EP2986691A1 EP14786094.4A EP14786094A EP2986691A1 EP 2986691 A1 EP2986691 A1 EP 2986691A1 EP 14786094 A EP14786094 A EP 14786094A EP 2986691 A1 EP2986691 A1 EP 2986691A1
Authority
EP
European Patent Office
Prior art keywords
alkali metal
mixture
process according
hydrocarbon feedstock
hydrocarbon
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.)
Ceased
Application number
EP14786094.4A
Other languages
German (de)
English (en)
Other versions
EP2986691A4 (fr
Inventor
John Gordon
Javier Alvare
Dennis Leroy Larsen
Jeff Killpack
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.)
Field Upgrading Ltd
Original Assignee
Field Upgrading Ltd
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 Field Upgrading Ltd filed Critical Field Upgrading Ltd
Publication of EP2986691A1 publication Critical patent/EP2986691A1/fr
Publication of EP2986691A4 publication Critical patent/EP2986691A4/fr
Ceased legal-status Critical Current

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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
    • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C10G19/08—Recovery of used refining agents
    • 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
    • C10G19/067—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with molten 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
    • 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
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/12—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one alkaline treatment step
    • 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

Definitions

  • the present invention relates to a process for removing nitrogen, sulfur, and heavy metals from sulfur-, nitrogen-, and metal-bearing shale oil, bitumen, heavy oil, or refinery streams using an alkali metal. More particularly, the invention relates to a process to facilitate separation of alkali metal compounds and reduced heavy metals from alkali metal reacted hydrocarbons.
  • U.S. Patent Application Serial No. 12/916,984 (which has been incorporated herein by reference) has been published as United States Patent Application Publication No. 2011/0100874. The reader is presumed to be familiar with the disclosure of this published application. This published application will be referred to herein as the "'984 application.”
  • U.S. Patent No. 8,088,270 which is expressly incorporated herein by reference, relates to a "Process For Recovering Alkali Metals And Sulfur From Alkali Metal Sulfides And Poly Sulfides.” The reader is presumed to be familiar with the disclosure of this published patent. This published patent will be referred to herein as the "'270 patent.”
  • catalysts such as Co-Mo/ A1 2 0 3 or Ni-Mo/Al 2 0 3 .
  • catalysts are deactivated (poisoned) by the presence of heavy metals as the heavy metals operate to mask the catalysts.
  • M is an alkali metal such as sodium or lithium.
  • R, R', R" represent portions of organic molecules or organic rings.
  • a method of upgrading an oil feedstock (such as heavy oil, shale oil, bitumen, etc.) may be used by combining the oil feedstock with an alkali metal and an upgradant hydrocarbon material, as disclosed in the '984 Application. This reaction operates to remove the sulfur, nitrogen and/or heavy metals contained within the oil feedstock.
  • heavy metals contained in the oil feedstock may also be removed via the use of alkali metals such as sodium.
  • Heavy metals contained in organometallic molecules such as complex porphyrins are reduced to the metallic state by the alkali metal. Once the heavy metals have been reduced, they can be separated from the oil because they no longer are chemically bonded to the organic structure.
  • the nitrogen heteroatoms in the structure are exposed for further denitrogenation.
  • Liquid phase alkali metal is brought into contact with the organic molecules containing heteroatoms and metals in the presence of hydrogen, methane, and also gases such as nitrogen (or inert gases such as helium, neon, argon, krypton, xenon and radon).
  • gases such as nitrogen (or inert gases such as helium, neon, argon, krypton, xenon and radon).
  • nitrogen or inert gases such as helium, neon, argon, krypton, xenon and radon.
  • the present invention provides a process to facilitate separation of alkali metal compounds and reduced heavy metals from alkali metal reacted hydrocarbons.
  • the disclosed process facilitates gravimetric separation of alkali metal salts from alkali metal reacted hydrocarbons.
  • the process includes heating a mixture resulting from a reaction of an alkali metal and a quantity of a hydrocarbon feedstock having at least one heavy fraction and mechanically mixing the mixture during the heating step.
  • the mixture includes alkali metal salts and alkali metal reacted hydrocarbon feedstock.
  • the mixture is heated to a temperature in the range from about 350°C to 400°C.
  • the mixture may be heated to a temperature of about 375°C ⁇ 10°C.
  • the alkali metal may be sodium or lithium.
  • the alkali metal salts comprise sodium sulfide and/or sodium polysulfide.
  • the mixture is heated and mechanically mixed for a time period of over 15 minutes. In another embodiment, the mixture is heated and mechanically mixed for a time period of over 30 minutes. In yet another embodiment, the mixture is heated and mechanically mixed for a time period of at least 1 hour. In a further embodiment, the mixture is heated and mechanically mixed for a time period between about 1 and 2 hours.
  • the quantity of a hydrocarbon feedstock may be a sulfur-, nitrogen-, and metal- bearing shale oil, bitumen, heavy oil, or refinery stream that contains a heavy fraction.
  • the hydrocarbon feedstock comprises bitumen.
  • the process may further comprise the step of separating gravimetrically the alkali metal salts from the alkali metal reacted hydrocarbons.
  • the process includes the step of adding a portion of the separated alkali metal salts to the mixture of alkali metal salts and alkali metal reacted hydrocarbons prior to heating. In another embodiment, the process includes the step of adding a portion of the separated alkali metal salts to the hydrocarbon feedstock prior to reacting with the alkali metal.
  • the disclosed process may be part of a broader process of upgrading a hydrocarbon or oil feedstock.
  • the process is most useful with hydrocarbon feedstocks having at least one heavy fraction, such as bitumen.
  • the hydrocarbon feedstock typically includes at least one carbon atom and a sulfur heteroatom and/or one or more heavy metals.
  • the quantity of hydrocarbon feedstock is reacted with an alkali metal and an upgradant hydrocarbon, wherein the upgradant hydrocarbon includes at least one carbon atom and at least one hydrogen atom or with hydrogen gas or liquid with hydrogen dissolved within.
  • the alkali metal reacts with the sulfur heteroatom and/or the one or more heavy metals to form one or more inorganic products comprising alkali metal sulfide or alkali metal polysulfides.
  • the upgradant hydrocarbon or hydrogen reacts with the hydrocarbon feedstock to produce an upgraded hydrocarbon feedstock, wherein the number of carbon atoms in the upgraded hydrocarbon feedstock may be greater than the number of carbon atoms in the hydrocarbon feedstock.
  • the mixture of inorganic products and the upgradant hydrocarbon is heated to a temperature in the range from about 350°C to 400°C, while undergoing mechanical mixing of the mixture. Thereafter, the inorganic products are gravimetrically separated from the upgraded hydrocarbon feedstock.
  • the process may include the optional step of adding a portion of the separated inorganic products to the mixture of inorganic products the upgradant hydrocarbon prior to heating.
  • the process may optionally include the step of adding a portion of the separated inorganic products to the hydrocarbon feedstock prior to reacting with the alkali metal.
  • FIG. 1 is flow diagram showing one embodiment of a process of upgrading an oil feedstock.
  • FIG. 2 is a flow diagram showing one embodiment of a process of upgrading an oil feedstock with an alkali metal and for separating inorganic products from the upgraded oil feedstock.
  • the present embodiments relate to a method of upgrading a hydrocarbon or oil feedstock (such as heavy oil, shale oil, bitumen, etc.) by combining the oil feedstock with an alkali metal and an upgradant hydrocarbon material or hydrogen, as disclosed in the '984 Application, to cap broken bonds previously attached to heteroatoms and metals. This reaction operates to remove the sulfur, nitrogen and/or heavy metals contained within the oil feedstock.
  • a hydrocarbon or oil feedstock such as heavy oil, shale oil, bitumen, etc.
  • the upgradant hydrocarbon used in this process may be hydrogen gas (H 2 ), or may be a hydrocarbon.
  • hydrocarbons examples include methane, ethane, propane, butane, pentane, hexane, ethene, propene, butane, pentene, dienes, and their isomers. Other hydrocarbons (such as octane, or other carbon containing compounds containing one or more carbon atoms) may also be used.
  • the hydrocarbon gas may also be comprised of a mixture of hydrocarbon gases (such as natural gas, or shale gas - the gas produced by retorting oil shale). In many embodiments, the hydrocarbon gas may be methane from natural gas because this component is inexpensive and readily available.
  • the hydrocarbon has at least one carbon atom and at least one hydrogen atom.
  • the hydrogen atom should be such that it can be pulled off from the carbon atom to form a bond with the organic molecules of the feedstock.
  • the hydrocarbon atom may include hydrogen atoms bonded therein, but the hydrocarbon molecule must include at least one carbon atom (and thus cannot comprise H 2 gas).
  • the hydrocarbon may be selected such that it will increase the ratio of hydrogen to carbon in the organic product. This occurs by selecting the hydrocarbon such that the hydrocarbon has a greater hydrogen-to-carbon ratio than the starting feedstock. Of course, a lower hydrogen-to-carbon ratio in the hydrocarbon can still provide upgrading benefits if the heteroatom content is reduced.
  • hydrogen is utilized or a gas mixture comprising hydrogen.
  • the hydrocarbon or oil feedstock is combined with the hydrocarbon (such as methane) or hydrogen and the alkali metal (such as sodium) in a reactor vessel and allowed to react for a period of time.
  • the reaction may, in some embodiments, be conducted at a temperature less than about 450 °C. In one embodiment, the reaction is conducted at a temperature higher than 150 °C.
  • the reaction may be conducted at a pressure higher than about 250 psi. In one embodiment, the reaction is conducted at a pressure below about 2500. Other embodiments may be done at lower temperatures and/or lower pressures.
  • This process may, in some embodiments, occur in the presence of a catalyst to help promote the chemical reactions.
  • the catalysts may include by way of non-limiting example, molybdenum, nickel, cobalt or alloys of molybdenum, alloys of nickel, alloys of cobalt, alloys of molybdenum containing nickel and/or cobalt, alloys of nickel containing cobalt and/or molybdenum, molybdenum oxide, nickel oxide or cobalt oxides, iron or iron oxide and combinations thereof.
  • Any alkali metal could be used in the process including, but not limited to, mixtures and/or alloys of alkali metals.
  • potassium, sodium, lithium and/or alloys thereof may be used.
  • alkali metal sodium or lithium
  • sulfur and nitrogen atoms separate from the organic molecules in the oil feedstock and combine with the alkali metal (sodium or lithium) to form sulfides and nitrides.
  • These alkali metal sulfides/nitrides are inorganic compounds that separate into an inorganic phase that is distinct from the organic phase housing the organic compounds.
  • a portion of the heavy metals originally contained in the organic materials, such as iron, arsenic and vanadium, are reduced and can also be separated into the inorganic phase as well.
  • the resulting organic compounds are in the organic phase and react with the upgradant hydrocarbon, such as methane or with hydrogen. Because the heteroatoms react with the alkali metal, the resulting product has a lower heteroatom to carbon ratio than the original oil feedstock.
  • the alkali metal may be added to the reaction vessel because the free energy of formation of the alkali metal sulfide is greater than the free energy of formation of H 2 S.
  • the reaction proceeds more readily with the introduction of the alkali metal.
  • the alkali metal may include sodium, lithium, or the like.
  • a schematic method 100 of an embodiment for upgrading an oil feedstock is disclosed.
  • a quantity of oil feedstock 102 is obtained.
  • This oil feedstock 102 may comprise bitumen, shale oil, heavy oil, or other materials described herein.
  • the oil feedstock 102 may be obtained via mining or other processes.
  • the oil feedstock 102 is added to a reaction vessel 104 (which is referred to herein as reactor 104).
  • the reactor 104 may include a mixer 107 that is designed to mix (stir) the chemicals added therein in order to facilitate a reaction.
  • a catalyst 105 of the type described above may also be added to the reactor 104 to foster the reaction.
  • alkali metal 108 may be any alkali metal 108 and may include mixtures of alkali metals 108. In some embodiments, sodium or lithium may be used.
  • a quantity of an upgradant hydrocarbon 106 may also be used and added to the reactor 104 or in place of upgradant hydrocarbon hydrogen may be used.
  • this upgradant hydrocarbon 106 may be methane, ethane, propane, etc. or any other hydrocarbon (or even mixtures thereof).
  • natural gas or shale oil gas (which generally contains methane CH ) may be used.
  • the reactor 104 may cause the reaction to occur at a certain temperature or pressure.
  • the temperature used for the reaction may be elevated up to about 450 °C.
  • One exemplary temperature may be 350 °C.
  • the temperature may be such that the alkali metal 108 is in a molten state. It will be appreciated by those of skill in the art that sodium becomes molten at about 98 °C whereas lithium becomes molten at about 180 °C.
  • embodiments may be designed in which the temperature of the reactor 104 is at a temperature above the melting temperature of the alkali metal 108.
  • the pressure of the reaction may be anywhere from atmospheric pressure and above. Some exemplary embodiments are performed at a pressure that is above about 250 psi. Other embodiment may be performed at a pressure that is below about 2500 psi.
  • the alkali metal 108 may be molten to facilitate the mixing of this chemical with the other chemicals.
  • other embodiments may be designed in which a powdered or other solid quantity of the alkali metal 108 is blown into, or otherwise introduced, into the reactor 104 so that it reacts with the other chemicals.
  • the heteroatoms such as sulfur and nitrogen
  • other heavy metals are removed from the oil feedstock 102.
  • the products from the reactor 104 are then sent to a separator 112.
  • the separator 112 may include a variety of devices/processes that are designed to separate the upgraded oil feedstock 116 from the other reaction products.
  • the separator 112 may include filters, centrifuges and the like.
  • the separator 112 may also receive, depending upon the embodiment, an influx of a flux 119.
  • This flux material 119 may be hydrogen sulfide H 2 S or water or other chemical(s) that facilitate the separation.
  • 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 reduced heavy metals will also be separated out from the organic hydrocarbons by gravimetric separation techniques.
  • NH 3 ammonia gas
  • NaHS alkali hydro sulfide
  • the flux may be ammonia utilized to scavenge unreacted alkali metal. Then the alkali metal laden ammonia is separated from the oil, flashed off and the alkali metal may be sent back to the reactor for further processing.
  • Some heavy metals 118 which were reduced from the feedstock 102 may separate here and be extracted as heavy metals 118.
  • the separation also produces the organic product, which is the upgraded oil feedstock 116.
  • This upgraded oil feedstock 116 may be shipped to a refinery for further processing, as needed, to make this material a suitable hydrocarbon fuel.
  • Another output of the separator 112 is a mixture 114 (stream) of alkali metal sulfides, alkali metal nitrides, and heavy metals 118.
  • This mixture 114 may be further processed as described below.
  • any nitrogen containing products such as via ammonia gas (NH 3 ) that is vented off and collected) may also be removed from this stage depending on the type of the process employed.
  • the mixture 114 of alkali metal sulfides, alkali metal nitrides, and heavy metals 118 may be thermally processed as described in the 217 application where the mixture is heated to elevated temperature in a non-oxidizing and dry atmosphere then may be sent to a regenerator 120.
  • the purpose of the regenerator 120 is to regenerate the alkali metal 108 so that it may be reused in further processing at the reactor 104.
  • one of the outputs of the regenerator 120 is a quantity of the alkali metal 108.
  • the regeneration step involves an electrolytic reaction (electrolysis) of an alkali metal sulfide and/or polysulfide using an alkali metal ion conductive ceramic membrane (such as, for example, a NaSiCON or LiSiCON membrane that is commercially available from Ceramatec, Inc. of Salt Lake City, Utah).
  • an alkali metal ion conductive ceramic membrane such as, for example, a NaSiCON or LiSiCON membrane that is commercially available from Ceramatec, Inc. of Salt Lake City, Utah.
  • nitrogen compounds 128 may be ammonia gas that is vented off or collected.
  • nitrogen compound precursors 130 are added to the regenerator 120 to capture/react with the nitrogen containing compounds in the mixture 114 and produce the compounds 128.
  • Those skilled in the art will appreciate the various chemicals and processes that may be used to capture the nitrogen compounds 128 (or to otherwise process the nitrogen obtained from the reaction).
  • the method 100 of Fig. 1 may be run as a batch process or may be a continuous process, depending upon the embodiment. Specifically, if it is a continuous process, the reactants would be continuously added to the reactor 104 and the products continuously removed, separated, etc. Further, the reaction in the reactor 104 may be performed as a single step (e.g., placing all of the chemicals into a single reactor 104) or potentially done as a series of steps or reactions.
  • a schematic method 200 of an embodiment for upgrading an oil feedstock is disclosed. The disclosed method is based upon the method of Fig. 1. Even though some features shown in Fig. 1 are not reproduced in relation to Fig. 2, it is to be understood that Fig. 2 can include the features discussed above.
  • a quantity of oil feedstock 202 is obtained.
  • This oil feedstock 202 may comprise bitumen, shale oil, heavy oil, or other materials described herein that contains a heavy fraction.
  • the term "heavy fraction” refers to one or more fractions that have a boiling point above 524°C. Bitumen is known to contain a heavy fraction.
  • the oil feedstock 202 may be obtained via mining or other processes.
  • the oil feedstock 202 is added to a reaction vessel 204 (which is referred to herein as reactor 204).
  • the reactor 204 may include a mixer
  • the reactor 204 may also include a heater 209 to heat the reactants to a predetermined temperature.
  • alkali metal 208 Also added to the reactor 204 is a quantity of an alkali metal 208. This alkali metal
  • alkali metal 208 may be any alkali metal 208 and may include mixtures of alkali metals 208. In some embodiments, sodium or lithium may be used.
  • a quantity of an upgradant hydrocarbon 206 or hydrogen may also be used and added to the reactor 204.
  • this upgradant hydrocarbon 206 may be methane, ethane, propane, etc. or any other hydrocarbon (or even mixtures thereof).
  • natural gas or shale oil gas which generally contains methane CH
  • hydrogen may be used or a mixture thereof.
  • the reactor 204 may cause the reaction to occur at a certain temperature or pressure.
  • the temperature used for the reaction may be elevated up to about 450 °C.
  • One exemplary temperature may be 350 °C.
  • the temperature may be such that the alkali metal 208 is in a molten state. It will be appreciated by those of skill in the art that sodium becomes molten at about 98 °C whereas lithium becomes molten at about 180 °C.
  • embodiments may be designed in which the temperature of the reactor 204 is at a temperature above the melting temperature of the alkali metal 208.
  • the pressure of the reaction may be anywhere from atmospheric pressure and above. Some exemplary embodiments are performed at a pressure that is above about 250 psi. Other embodiment may be performed at a pressure that is below about 2500 psi.
  • the heteroatoms such as sulfur and nitrogen
  • other heavy metals are converted into a mixture of alkali metal sulfides or polysulfides, alkali metal nitrides, and heavy metals, collectively referred to as inorganic products and the upgraded oil feedstock. It has been observed that when the oil feedstock 202 contains a heavy fraction, the mixture of inorganic products and upgraded oil feedstock cannot be effectively separated without further processing.
  • the inorganic products and upgraded oil feedstock are introduced into a holding vessel 210 that also contains a mixer 207 and a heater 209.
  • the holding vessel 210 is shown in dashed lines because it can be a vessel separate from the reactor 204 or it can be the reactor 204 itself.
  • the mixture of inorganic products and upgraded oil feedstock are heated to a temperature in the range from about 350°C to 400°C, and the mixture is mechanically mixed during the heating step.
  • the mixture may be heated to a temperature of about 375°C ⁇ 10°C.
  • the mixture is heated and mechanically mixed for a time period of over 15 minutes. In another embodiment, the mixture is heated and mechanically mixed for a time period of over 30 minutes. In yet another embodiment, the mixture is heated and mechanically mixed for a time period of at least 1 hour. In a further embodiment, the mixture is heated and mechanically mixed for a time period between about 1 and 2 hours.
  • the mixture of alkali metal reaction products from the reactor 204 are then sent to a separator 212.
  • the separator 212 may include a variety of devices/processes that are designed to separate the upgraded oil feedstock 216 from the other reaction products.
  • the separator 212 may include filters, centrifuges and the like.
  • the organic product which is the upgraded oil feedstock 216.
  • This upgraded oil feedstock 216 may be shipped to a refinery for further processing, as needed, to make this material a suitable hydrocarbon fuel.
  • Another output of the separator 212 is a mixture 214 (stream) of alkali metal sulfides, alkali metal nitrides, and heavy metals.
  • This mixture 214 may be further processed as described below.
  • any nitrogen containing products (such as via ammonia gas (NH 3 ) that is vented off and collected) may also be removed from this stage depending on the type of the process employed.
  • the inorganic products 214 which contain a mixture of alkali metal salts, such as alkali metal sulfides, alkali metal nitrides, and/or heavy metals, may be thermally processed as described in the 217 application where the mixture is heated to elevated temperature in a non-oxidizing and dry atmosphere then may be sent to a regenerator 220.
  • the purpose of the regenerator 220 is to regenerate the alkali metal 208 so that it may be reused in further processing at the reactor 204.
  • one of the outputs of the regenerator 220 is a quantity of the alkali metal 208.
  • the process shown in Fig. 2 includes the ability to add a portion of the separated inorganic products, such as the alkali metal sulfides or polysulfides, to the mixture of inorganic products and upgraded oil feedstock prior to heating in the holding vessel 210.
  • the separated inorganic products may provide a "seed" to facilitate the agglomeration of fine alkali metal sulfide particles within the mixture, which ultimately facilitates the separation process.
  • a recycle stream 224 is provided in which a portion of the separated inorganic products may be fed to the holding vessel 210.
  • the process shown in Fig. 2 includes the ability to add a portion of the separated inorganic products to the oil feedstock prior to reacting with the alkali metal.
  • the separated inorganic products may provide a "seed" to facilitate the agglomeration of fine alkali metal sulfide particles within the mixture, which ultimately facilitates the separation process.
  • a recycle stream 226 is provided in which a portion of the separated inorganic products may be fed to the reactor 204.
  • the seeding process may occur before alkali metal addition or after alkali metal addition.
  • oil feedstock in this invention may originate from many sources such as petroleum, heavy oil, retorted oil shale, bitumen, and oil refinery streams where the oil originally comprised organic sulfur.
  • the disclosed process is most applicable to oil feedstocks that contain a heavy fraction.
  • a process to facilitate separation of alkali metal salts from alkali metal reacted hydrocarbons includes adding a portion of the separated alkali metal salts to the mixture of alkali metal hydrocarbon feedstock having at least one heavy fraction.
  • the mixture may include alkali metal salts and alkali metal reacted hydrocarbons.
  • the process may also include adding a portion of the separated alkali metals salts to the mixture of alkali metal hydrocarbon feedstock prior to addition of the alkali metal.
  • a flux is mixed with the hydrocarbon to dissolve the alkali metal.
  • the flux is ammonia. The ammonia with dissolved alkali metal may be flashed off to yield the alkali metal.

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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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un procédé destiné à faciliter la séparation gravimétrique de sels de métal alcalin, par exemple des sulfures et polysulfures de métal alcalin, d'hydrocarbures ayant réagi avec un métal alcalin. Le procédé divulgué fait partie d'un procédé de valorisation d'une charge d'hydrocarbures par suppression d'hétéroatomes et/ou d'un ou plusieurs métaux lourds de la composition de la charge d'hydrocarbures. Ce procédé consiste à faire réagir la charge d'huiles avec un métal alcalin et un hydrocarbure de valorisation. Le métal alcalin réagit avec une partie des hétéroatomes et/ou avec un ou plusieurs métaux lourds pour former une phase inorganique contenant des sels de métal alcalin et des métaux lourds réduits, et une charge d'hydrocarbures valorisée. La phase inorganique peut être séparée par gravimétrie de la charge d'hydrocarbures valorisée après mélangeage à une température comprise entre environ 350 °C et 400 °C pendant un laps de temps compris entre environ 15 minutes et 2 heures.
EP14786094.4A 2013-04-15 2014-04-15 Procédé pour séparer des sels de métal alcalin d'hydrocarbures ayant réagi avec un métal alcalin Ceased EP2986691A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201361812057P 2013-04-15 2013-04-15
PCT/US2014/034183 WO2014172361A1 (fr) 2013-04-15 2014-04-15 Procédé pour séparer des sels de métal alcalin d'hydrocarbures ayant réagi avec un métal alcalin

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EP2986691A1 true EP2986691A1 (fr) 2016-02-24
EP2986691A4 EP2986691A4 (fr) 2017-03-29

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EP (1) EP2986691A4 (fr)
JP (1) JP6480914B2 (fr)
KR (1) KR102090358B1 (fr)
CN (1) CN105229120B (fr)
CA (1) CA2909443C (fr)
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MX (1) MX2015014348A (fr)
MY (1) MY173980A (fr)
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US10113122B2 (en) 2015-08-31 2018-10-30 University Of New Brunswick Process for upgrading heavy hydrocarbon liquids
EP3523396B1 (fr) * 2016-10-04 2020-11-25 Enlighten Innovations Inc. Procédé de séparation de particules contenant des sels de métaux alcalins à partir d'hydrocarbures liquides
CN109803923A (zh) * 2016-10-19 2019-05-24 国立研究开发法人物质·材料研究机构 合成氨的方法及其装置
KR20230087600A (ko) * 2020-10-19 2023-06-16 차이나 페트로리움 앤드 케미컬 코포레이션 연료유 생산 방법, 시스템 및 그 응용, 연료유 및 그 응용

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EP2986691A4 (fr) 2017-03-29
KR102090358B1 (ko) 2020-03-17
MY173980A (en) 2020-03-02
SG11201508465WA (en) 2015-11-27
HK1224325A1 (zh) 2017-08-18
CA2909443C (fr) 2019-10-01
MX2015014348A (es) 2016-10-03
JP2016521303A (ja) 2016-07-21
KR20150143652A (ko) 2015-12-23
CN105229120A (zh) 2016-01-06
WO2014172361A1 (fr) 2014-10-23
JP6480914B2 (ja) 2019-03-13
CA2909443A1 (fr) 2014-10-23
CN105229120B (zh) 2018-09-21

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