WO2018067753A1 - Process for separating particles containing alkali metal salts from liquid hydrocarbons - Google Patents
Process for separating particles containing alkali metal salts from liquid hydrocarbons Download PDFInfo
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- WO2018067753A1 WO2018067753A1 PCT/US2017/055213 US2017055213W WO2018067753A1 WO 2018067753 A1 WO2018067753 A1 WO 2018067753A1 US 2017055213 W US2017055213 W US 2017055213W WO 2018067753 A1 WO2018067753 A1 WO 2018067753A1
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- alkali metal
- mixture
- sulfur
- liquid hydrocarbon
- liquid
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Classifications
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- 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
- C10G29/02—Non-metals
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
Definitions
- the present technology relates to a process for removing particles containing alkali metal salts, such as alkali metal sulfides, from liquid hydrocarbons. It further relates to processes for converting carbon-rich solids into fuels
- Liquid hydrocarbons including many oil feedstocks, often contain difficult to remove sulfur in the form of organosulfur compounds as well as metals and other heteroatom- containing compounds that hinder usage of the hydrocarbons.
- Sulfur can cause air pollution, and can poison catalysts used in petroleum processing or catalysts designed to remove hydrocarbons and nitrogen oxide from motor vehicle exhaust.
- hydrocarbon fuels such as gasoline, diesel, and fuel oils, including marine bunker fuels.
- Metals contained in the hydrocarbon stream can also poison catalysts typically utilized for removal of sulfur through standard and improved hydro- desulfurization processes whereby hydrogen reacts under extreme conditions to break down the sulfur bearing organosulfur molecules.
- Sodium is capable of reacting with the oil and its contaminants to dramatically reduce the sulfur, nitrogen, oxygen, and metal content through the formation of sodium sulfide compounds (sulfide, polysulfide and hydrosulfide) as well as other byproducts.
- sodium sulfide compounds sulfide, polysulfide and hydrosulfide
- removal of these byproducts from the treated feedstock can be challenging.
- the suspensions and/or emulsions the byproducts may form often cannot be completely removed using standard separation techniques, and can be difficult to carry out efficiently on an industrial scale. Indeed, no large scale desulfurization using sodium metal or other alkali metals is in regular commercial use due in part to this problem.
- the present technology provides a process for separating particles containing alkali metal salts from liquid hydrocarbons.
- Such mixtures result from the use of alkali metals (in their metallic state) to remove nitrogen, sulfur, oxygen and heavy metals from liquid hydrocarbons (e.g., oil feedstocks) contaminated with compounds containing such heteroatoms.
- the process includes heating a first mixture of elemental sulfur and particles comprising an alkali metal sulfide in a liquid hydrocarbon to a temperature of at least 150 °C, to provide a sulfur-treated mixture comprising agglomerated particles.
- the process further includes separating the agglomerated particles from the sulfur-treated mixture to provide a desulfurized liquid hydrocarbon and separated solids.
- the present technology further provides methods for removal of residual alkali metal from the desulfurized liquid hydrocarbons and for preparing the separated solids for electrochemical regeneration of the alkali metal.
- the desulfurized and demetallized liquid hydrocarbons produced typically have less than 0.5 wt% sulfur and less than 100 ppm alkali metal, and meet, for example, contaminant limits for bunker fuel without further processing. This process is also applicable to processes for converting carbon-rich solids into fuels.
- FIG. 1 shows a process flow diagram for an illustrative embodiment of a process for separating particles containing alkali metal sulfide from a liquid hydrocarbon and optional additional processes for removing residual alkali metal from the product hydrocarbon and preparing the separated solids for regeneration of alkali metal, as well as the process for removal of impurities from oil using an alkali metal which generates the mixtures of particles and liquid hydrocarbon.
- FIG. 2 shows a process flow diagram for an illustrative embodiment of the present technology for converting coke to a liquid fuel while simultaneously reducing or removing sulfur, metals and other heteroatoms.
- the present technology provides a process for separating particles containing alkali metal salts, including alkali metal sulfides, from liquid hydrocarbons.
- the separation process may be employed as part of a series of processes for desulfurizing and otherwise removing metals and other heteroatom contaminants from liquid hydrocarbons as well as carbon-rich solids in a liquid hydrocarbon including but not limited to bunker oil, as well as petroleum oil distillate, crude, heavy oil, bitumen, shale oil, and refinery intermediate streams (for example, solvent deasphalting tar, steam cracked tar, atmospheric or vacuum residuals, FCC slurry, visbreaker tar, hydrotreater, hydrocracker or hydroconversion bottoms, coke and asphalt).
- refinery intermediate streams for example, solvent deasphalting tar, steam cracked tar, atmospheric or vacuum residuals, FCC slurry, visbreaker tar, hydrotreater, hydrocracker or hydroconversion bottoms, coke and asphalt.
- Liquid hydrocarbons contaminated with sulfur compound(s), and optionally one or more nitrogen compounds, oxygen compounds and heavy metals may be desulfurized and decontaminated by contacting the hydrocarbons with a molten alkali metal (in its metallic state) such as sodium, potassium or lithium (or mixtures or alloys thereof) to remove the heteroatoms, and to provide a mixture of the liquid hydrocarbon and particles comprising alkali metal sulfides.
- a capping agent is typically used to cap the radicals formed when sulfur and other heteroatoms have been abstracted by the alkali metal.
- the capping agent may be hydrogen, a Ci-6 acyclic alkane, C 2- 6 acyclic alkene, hydrogen sulfide, ammonia, or a mixture of any two or more thereof.
- the contacting step may be carried out at a temperature of about 250 °C to about 400 °C, for example at about 250°C, about 300°C, about 350°C, about 400°C or a range between and including any two of the foregoing temperatures. In some embodiments the contacting takes place at about 300°C to about 400°C (e.g., 350°C).
- the contacting may take place at a pressure of about 400 to about 1500 psi, e.g., at about 400 psi, about 500 psi, about 600 psi, about 750 psi, about 1000 psi, about 1250 psi, about 1500 psi or a range between and including any two of the foregoing values.
- the amount of alkali metal in its metallic state used in the contacting step will vary with the level of heteroatom contaminants of the liquid hydrocarbon, the temperature used and other conditions. For example, 1-3 mole equivalents of metallic alkali metal and 1-1.5 moles of capping agent (e.g., hydrogen) may be needed per mole sulfur, nitrogen or oxygen. In addition an excess of metallic alkali metal may be used to drive the reaction towards completion, e.g., a 10%, 15%), 20%), 25%), 30%o, 40%>, 50%> or more excess on a mole equivalent basis may be used. In some embodiments the molten alkali metal used is sodium metal.
- any suitable source of molten alkali metal may be used, including, but not limited to electrochemically generated sodium, e.g., per US 8,088,270, incorporated by reference in its entirety herein.
- the reaction of metallic alkali metal with heteroatom contaminants in the liquid hydrocarbons is relatively fast, being complete within a few minutes, if not seconds. Mixing the combination of liquid hydrocarbon and metallic alkali metal further speeds the reaction and is commonly used for this reaction on the industrial scale.
- the contacting step is carried out for 1 minute to about 5, about 6, about 7, about 9, about 10, about 15 minutes, or about 20 minutes, or is conducted for a time ranging between and including any two of the foregoing values.
- the foregoing desulfurization reaction produces a mixture that includes the liquid hydrocarbon and particles comprising alkali metal sulfides.
- the particles are quite fine (e.g., ⁇ 10 ⁇ ) and cannot be completely removed by standard separation techniques (e.g., filtration or centrifugation) at this stage, especially when the liquid hydrocarbons have a high viscosity, e.g., bottoms and fuel oils.
- standard separation techniques e.g., filtration or centrifugation
- unreacted metallic alkali metal may be present in such mixtures. Further processing as described below is needed to separate the particles, and provide desulfurized liquid hydrocarbons.
- the hydrocarbon feeds are optionally thermally pretreated before the reaction with alkali metal, e.g., 300-450 °C for 30-60 minutes.
- alkali metal e.g. 300-450 °C for 30-60 minutes.
- Such thermal treatment can reduce the heteroatom content of the liquid hydrocarbon, reducing the amount of alkali metal needed, and simplifying the subsequent separation step.
- a separation process comprising heating a first mixture of elemental sulfur and particles comprising an alkali metal sulfide (e.g., sodium sulfide) in a liquid hydrocarbon to a temperature of at least 150 °C provides a sulfur-treated mixture comprising agglomerated particles that are now separable.
- the separation process thus further includes separating the agglomerated particles from the sulfur-treated mixture to provide a desulfurized liquid hydrocarbon and separated solids.
- the separation process may include mixing the first mixture during heating.
- the first mixture may be heated for a longer or shorter period of time.
- the period of time is at least 15 minutes.
- the first mixture is heated for a period of about 15 minutes to about 2 hours, e.g., about 15 minutes, about 30 minutes, about 45 minutes, about 1 hour, about 1.25 hours, about 1.5 hours, about 1.75 hours, about 2 hours, or a range between and including any two of the foregoing values.
- the first mixture is heated to a temperature of about 150°C to about 450°C, e.g., about 150°C, about 200°C, about 250°C, about 300°C, about 350°C, about 400°C, about 450°C, or to a temperature in a range between and including any two of the foregoing values. In some embodiments, the first mixture is heated to a temperature of about 300°C to about 400°C.
- the pressure at which the separation process takes place is not critical and may be carried out at a wide range of pressures, including atmospheric pressure.
- the pressure may be about 15 psi to about 1500 psi, e.g., about 15 psi, about 25 psi, about 50 psi, about 100 psi, about 200 psi, about 300 psi, about 400 psi, about 500 psi, about 750 psi, about 1000 psi, about 1250 psi, about 1500 psi, or a range between and including any two of the foregoing values. More commonly, the pressure may be about 100 psi to about 400 psi.
- the pressurized gas in the vessels in which the separation process takes place includes hydrogen (predominantly), but can also include one or more of CO, C0 2 , H 2 S and Ci- 6 alkanes and alkenes ⁇ e.g., methane, ethane, ethylene, propane, propene, butane, etc.).
- the first mixture may include alkali metal in its metallic state, also referred to herein as "residual alkali metal". This is especially true where a molar excess of metallic alkali metal was used to generate the mixture of liquid hydrocarbons and particles of alkali metal sulfide.
- the first mixture comprises 1-100 wt% alkali metal in its metallic state with respect to the weight of alkali metal in the alkali metal sulfide.
- the first mixture may also include alkali metal oxides and/or metals other than alkali metals.
- the amount of elemental sulfur to be added may range from about 0.5 equivalents to about 2 or even about 3 equivalents of sulfur atoms per two equivalents of free sodium atoms present ⁇ i.e., those in the metallic state, not ionic).
- the amount of elemental sulfur added is 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.5, 1.75, 2, 2.5, 3.0 equivalents or a range between and including any two of the foregoing values.
- 0.8 to 1.2 equivalents of elemental sulfur is added.
- the agglomerated particles may comprise an alkali metal sulfide and/or alkali metal hydrosulfide ⁇ e.g., sodium sulfide (Na 2 S) or sodium hydrosulfide (NaHS)).
- alkali metal hydrosulfide ⁇ e.g., sodium sulfide (Na 2 S) or sodium hydrosulfide (NaHS)
- Na 2 S sodium sulfide
- NaHS sodium hydrosulfide
- the alkali metal hydrosulfide may predominate.
- separating the agglomerated particles from the sulfur-treated mixture includes filtering, settling, or centrifuging the sulfur treated mixture to provide the separated solids. Separating the agglomerated particles from the sulfur-treated mixture may conveniently be performed by centrifuging the sulfur-treated mixture at, e.g., about 15 °C to about 150 °C. In some embodiments, the centrifuging takes place at about 120 °C to about 140 °C.
- the separating process further includes mixing the separated solids with an organic liquid (suitable for dissolving any liquid hydrocarbon on the separated solids ) and separating the separated solids from the organic liquid to provide washed solids.
- organic liquid suitable for dissolving any liquid hydrocarbon on the separated solids
- Any suitable organic liquid may be used, including but not limited to toluene, xylene, hexanes, diesel (e.g., coker diesel) and/or condensate (e.g., BTX condensate).
- the wash liquid containing residual desulfurized liquid hydrocarbons may be sent to a recovery process (e.g., distillation) to recover the organic liquid for reuse or may be mixed with the desulfurized liquid hydrocarbon as product oil.
- the washed solids may be dried if desired using standard means and electrolyzed as described in US Patent No. 8,088,270, to recover metallic alkali metal (e.g., sodium) for reuse.
- the desulfurized liquid hydrocarbon resulting from the separation process typically contains not more than 0.5 wt% sulfur.
- the desulfurized liquid hydrocarbon contains not more than 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt% or even 0.05 wt% sulfur.
- the desulfurized liquid hydrocarbon contains slightly more than 0.5 wt% sulfur, e.g., 0.6 wt%.
- the desulfurized liquid hydrocarbon contains from about 0.05 wt% to about 0.6 wt%.
- alkali metal content e.g., up to and sometimes exceeding 1% by weight.
- such residual alkali metal is present at a level of about 400 ppm to about 10,000 ppm, e.g., about 400, about 600, about 800, about 1,000, about 1,200, about 1,400, about 1,600, about 2,000, about 2,500, about 3,000, about 4,000, about 5,000, about 7,500 or even about 10,000 ppm or in a range between and including any two of the foregoing values.
- alkali metal content may be associated ionically at the sites where heavy metals originally held position or ionically associated with napthenates, or finely dispersed in the metallic state, or ionically associated with sulfur, oxygen, or nitrogen which is still bonded to the organic molecules of the oil.
- the present technology provides a demetallizing process which includes adding a salt-forming substance to the desulfurized liquid hydrocarbon to form a second mixture, wherein the salt-forming substance converts the residual alkali metal to an alkali metal salt.
- a salt-forming substance may be used so long as the resulting salt is readily removed from the liquid hydrocarbons.
- the salt-forming substance can be selected from the group consisting of elemental sulfur, hydrogen sulfide, formic acid, acetic acid, propanoic acid and water.
- acetic acid is used to form sodium acetate salts, which are relatively easy to remove in their solid form.
- the amount of salt-forming substance added is equal to about 1 to about 4 times the molar amount of residual alkali metal, e.g., 1, 1.25, 1.5, 2, 2.5, 3, 3.5 mole equivalents or a range between and including any two of the foregoing values.
- the amount is equal to about 1 to about 2 mole equivalents.
- the addition of salt-forming substance may be carried out at a temperature of at least 150°C, e.g., a temperature of about 150°C, about 200°C, about 250°C, about 300°C, about 350°C, about 400°C, about 450°C, or within a range between and including any two of the foregoing values. In some embodiments, the addition of salt-forming substance may be carried out at a temperature of about 150°C to about 450 °C.
- the addition of salt-forming substance is carried out at a pressure of at least about 15 psi. In some embodiments the addition of salt-forming substance is carried out at a pressure of about 15 psi, about 25 psi, about 50 psi, about 100 psi, about 150 psi, about 200 psi, about 250 psi, about 300 psi, about 400 psi, about 500 psi, about 1,000 psi, about 1,500 psi, about 2,000 psi, about 2,500 psi or at a pressure in a range between and including any two of the foregoing values. For example, in some embodiments, the addition is carried out at about 50 psi to about 2,500 psi.
- the demetallization process may include separating the alkali metal salts from the second mixture to provide a desulfurized and demetallized liquid hydrocarbon.
- separating the alkali metal salts from the second mixture may include filtering, settling, or centrifuging the second mixture to remove the alkali metal salts and provide the desulfurized and demetallized liquid hydrocarbon.
- FIG. 1 The present embodiments of the present technology can be understood by reference to the drawings, wherein like parts are designated by like numerals throughout. It will be readily understood that the components of the present technology, as generally described and illustrated in the figure herein, could be arranged and designed in a wide variety of different configurations. Thus, the following more detailed description of the embodiments of the methods and systems of the present technology, as represented in FIG. 1 is not intended to limit the scope of the technology, as claimed, but is merely representative of present embodiments of the technology. In particular, although the present technology may be employed to separate any mixture of alkali metal sulfides from liquid hydrocarbons, FIG.
- 1 shows an embodiment in which the mixture is generated by reaction of alkali metal with a liquid hydrocarbon contaminated with organosulfur compounds.
- Optional processes for removing residual alkali metal from the desulfurized hydrocarbon and for preparing the separated alkali metal sulfides for further processing are also described.
- an oil feedstock 10 may be fed through an optional heat exchanger 101 to be preheated to about 150 °C to about 350 °C before entering reactor 202.
- An alkali metal 12 in its molten state is also fed to the reactor, along with a radical capping agent 14 which may be hydrogen and/or a hydrocarbon such as methane, ethane, natural gas, and the like.
- the alkali metal is typically sodium metal but may also be lithium metal, potassium metal, or alloys or mixtures containing any two or more of these metals.
- the reactor may be operated batch-wise or continuously in the temperature range above the melting temperature of the alkali metal, typically between 150 - 400 °C but more preferably between 300 - 360 °C to provide faster reaction kinetics and reduce or avoid thermal cracking.
- the reaction typically is carried out at a pressure of 500 - 2000 psi.
- the alkali metal often reacts with the sulfur and other heteroatom contaminants in a matter of minutes (e.g., 1-20 minutes) to form fine particles of alkali metal salts, including alkali metal sulfides. See, e.g., U.S. Patent
- the resulting mixture of liquid hydrocarbon and alkali metal salt/sulfide particles exits the reactor through line 15 and is fed to a maturation vessel 204.
- elemental sulfur which may conveniently (but is not require to be) in a liquid form (e.g., at 130°C -160 °C) via line 16 and heated to a temperature of at least about 150 °C, typically with mixing, for a period of 15 - 120 minutes. More typically, the mixture is heated to about 300 °C to about 450 °C, or in some embodiments, about 300 °C to about 400 °C.
- the processes in reactor 202 and vessel 204 are preferably run continuously, they may be performed in the same vessel if the processes are run batch-wise.
- the sulfur-treated mixture includes agglomerated particles and exits vessel 204 via line 17, flowing into optional heat exchanger 103 where heat is removed and optionally can be transferred back to the liquid hydrocarbon feed via the heat exchanger 101.
- the cooled sulfur-treated mixture (at, e.g., about 60 - 180°C, or even, about 100-140°C) is fed via line 18 to a solid/liquid separation apparatus 206, which typically includes a centrifuge but may also include a filter.
- the separated solids 30 exit the separation apparatus for further processing.
- the resulting desulfurized liquid hydrocarbon is free or substantially free of solids but may contain about 400 to about 4,000 ppm or more residual alkali metal in its metallic form.
- the desulfurized liquid hydrocarbon is pumped from the separation apparatus 206 through line 19 using pump 105, and is sent through line 20 into an optional heat exchanger 107 which if present, heats the desulfurized liquid hydrocarbon to about 250 °C to about 350 °C. From there the desulfurized liquid hydrocarbon flows through line 21 and is combined with a salt forming substance such as acetic acid from line 24 as described above. The combination of acetic acid or other salt forming substance and the residual alkali metal forms additional solids comprising alkali metal salts. These solids are removed by a second separation apparatus 208 (e.g., a centrifuge) to yield the desulfurized and demetallized liquid hydrocarbon product 26 and alkali metal salt solids 28.
- a second separation apparatus 208 e.g., a centrifuge
- the separated solids 30 from apparatus 206 are transported via chute or other suitable means to the washing tank 210, where they are mixed with an organic liquid 32 (as defined above) such as toluene, xylene, hexanes, diesel, condensate or combinations of any two or more thereof or some other organic liquid suitable for washing.
- an organic liquid 32 (as defined above) such as toluene, xylene, hexanes, diesel, condensate or combinations of any two or more thereof or some other organic liquid suitable for washing.
- the now washed solids are pumped out of the washing tank through line 33 using pump 109 and through line 34 to another solids- liquids separation apparatus 212 where most of the organic liquid 35 is recovered. If the recovered organic liquid is, e.g., diesel, it is stored with other desulfurized liquid hydrocarbons for later sale as product. If the recovered organic liquid is not a fuel product, it is reused as a wash liquid.
- the washed solids are transported to a dryer where any residual organic wash liquid is removed in a dryer 214.
- the washed solids are heated in a non- oxidizing atmosphere to a temperature of, e.g., 150 - 350 °C to recover the wash liquid 38 which may be returned back to the process as a wash liquid in the wash tank 210.
- the dryer could be any commercially available process including paddle dryers, spray dryers or indirectly fired kilns.
- the dried washed solids are ready for recycling by, e.g., electrochemical treatment to recover the alkali metal in its metallic state as described, e.g., in US Patent No. 8,088,270 or 8,747,660.
- the present technology also provides processes for converting carbon-rich solids into fuels.
- Carbon-rich solids (at room temperature) are solids that contain at least 75 wt% carbon. Examples include petroleum coke, asphaltenes, and coal. Such carbon- rich solids generally have at least 0.5 wt% sulfur prior to treatment by the present process.
- the present technology provides a process that includes treating a slurry or suspension of a carbon-rich solid having at least 0.5 wt% sulfur in a liquid hydrocarbon with a molten alkali metal and a capping agent as above (hydrogen, a Ci -6 acyclic alkane, C 2 -6 acyclic alkene, hydrogen sulfide, ammonia, or a mixture of any two or more thereof).
- a molten alkali metal and a capping agent as above (hydrogen, a Ci -6 acyclic alkane, C 2 -6 acyclic alkene, hydrogen sulfide, ammonia, or a mixture of any two or more thereof).
- This process is carried out at an elevated temperature and pressure.
- the process converts at least a portion of the carbon-rich solids into a liquid fuel (e.g., residual fuel or refinery feedstocks) and particles comprising alkali metal sulfides.
- liquid fuels have a reduced sulfur, metal and heteroatom content compared to the starting solids, e.g., not more than 0.2 or even 0.1 wt% sulfur.
- Liquid fuels of the present technology include any hydrocarbon or hydrocarbon mixture that is/are used in a liquid state and may be burned as fuel.
- liquid fuels include not only gasoline, kerosene and diesel, but fuel oil, residual fuel, and the like.
- the present methods include treating a slurry or suspension of petroleum coke in a liquid hydrocarbon with a molten alkali metal and one or more capping agents at an elevated temperature and pressure to convert at least a portion of the petroleum coke into a liquid fuel and inorganic solids in admixture with the liquid hydrocarbon.
- the carbon-rich solids e.g., petroleum coke, are not soluble in the liquid
- the slurry or suspension may contain, e.g., from 1 wt% to 20 wt% based on the total mass of the solids and the liquid hydrocarbon. It will be understood that the slurries/suspensions may include any suitable percentage of carbon-rich solids within this range such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 wt%, or a range between and including any two of the foregoing values, such as 1-15 wt%, 3-15 wt%, or 4 or 5 wt% - 10 or 11 wt%.
- the liquid hydrocarbon used in the slurry or suspension is selected to provide both a good slurry or suspension and dissolve the liquid fuels produced.
- heavy hydrocarbons with sufficient densities to fluidize the petroleum coke or other carbon-rich solids may be used including, e.g., hydrocarbons having densities of 800 to 1100 kg/m 3 at room temperature.
- Suitable densities include 800, 900, 1000, and 1100 kg/m 3 or a range between and including any two of the foregoing values.
- Suitable liquid hydrocarbons include virgin crude oil, bitumen, refinery intermediates, such as fluid catalytic cracker slurry, hydrocracker bottoms or vacuum residual, shale oil, or a residual fuel oil, and may be the same or different from the liquid fuel being produced by the present process.
- the liquid hydrocarbon itself may be part of a composition that is in need of desulfurization because it includes sulfur and optionally other heteroatoms such as nitrogen, oxygen and metals (e.g., vanadium).
- the petroleum coke or other carbon-rich solids are crushed and milled to a powder or dust to reduce particle size and promote the reaction with the molten alkali metal.
- the solids may be milled so that the majority of particles have a diameter of not more than 1 mm. In some embodiments the majority of particles range in size from 1 um to 1 mm.
- molten alkali metal i.e., in its metallic state
- the alkali metal may be lithium, sodium, potassium or an alloy thereof. While not wishing to be bound by theory, it is believed that the during the present processes, the alkali metal, e.g., sodium, reacts with the coke and hydrogen according to the following reaction:
- R and R' represent carbon rich organic constituents found in coke, each covalently bonded to a sulfur atom. It is believed sodium oxidizes, giving up an electron to the carbon rich organic constituents R and R' to form reactive radicals. These radicals may react with capping agents such as hydrogen (i.e., H 2 ) to form the carbon rich hydrocarbon molecules R-H and R'-H.
- capping agents such as hydrogen (i.e., H 2 ) to form the carbon rich hydrocarbon molecules R-H and R'-H.
- the new molecules R-H and R'-H are shorter, and have lower specific gravity than the original molecule R-S-R' and are now suitable for dissolution into a hydrocarbon liquid, thus increasing the mass and volume of the resulting liquid phase.
- Solid phase comprises inorganic constituents including sodium sulfide and any coke which does not enter solution but also includes other inorganic constituents such as metals, alkali oxides and hydroxides, and nitrides.
- the solids can be separated from the liquid by one of many methods including centrifugation, filtration or gravimetric settling.
- reaction conditions for conversion of carbon-rich solids such as petroleum coke into fuel are within the same range for desulfurization of liquid hydrocarbon alone and are described above.
- the radical capping agent may be hydrogen, methane or other agents as described above for desulfurization of liquid hydrocarbons.
- the conversion reaction is run at the same range of elevated pressures and temperatures as the desulfurization reaction described above.
- a significant portion of the carbon-rich solids is converted into liquid fuel and particles comprising alkali metal sulfides.
- the portion of petroleum coke converted to liquid fuel and particles comprising alkali metal sulfides may be at least 20 wt%.
- the portion converted is at least 20, 30, 40, or 50 wt% or a range between and including any two of the foregoing values, e.g., 20-50 wt%.
- the alkali-metal treated slurry may contain not only unreacted particles of the carbon-rich solids, but particles including alkali metal salts. These particles may be separated from the liquid hydrocarbon/fuel mixture using the same elemental sulfur process as herein described. In addition, any of the subsequent processes described herein for processing the sulfur-treated liquid hydrocarbon and separated solids may also be employed. Alternatively, to aid in separation of alkali metal sulfide- containing solids form the fuel slurry, water or hydrogen sulfide may be used in place of sulfur, while mixing at the same temperatures and pressures described herein. In favorable cases, the separation process of U.S. Patent No.
- the processes of the present technology may further include separating the particles comprising alkali metal sulfides and any remaining carbon-rich solids (e.g., petroleum coke) from the mixture of liquid hydrocarbon and liquid fuel.
- carbon-rich solids e.g., petroleum coke
- heaters and coolers may be located between the various vessels and reactors to heat or cool the oil or slurry to appropriate process operating temperatures or to more easily recover heat generated in the process.
- FIG. 2 shows an illustrative embodiment of the present processes. Finely milled (e.g., majority of particles between 1 ⁇ and 1 mm) petroleum coke 40 is added to a stream of liquid hydrocarbon, e.g., oil feedstock 10. The resulting slurry or suspension is fed to a reactor 202 where it is combined with an alkali metal 12 (e.g., metallic sodium) and a radical capping agent 14, such as hydrogen gas, methane and/or other hydrocarbons, hydrogen sulfide, or ammonia, (or mixtures of any two or more) at elevated temperature and pressure. Under the reaction conditions the alkali metal is in a molten state.
- an alkali metal 12 e.g., metallic sodium
- a radical capping agent 14 such as hydrogen gas, methane and/or other hydrocarbons, hydrogen sulfide, or ammonia, (or mixtures of any two or more
- the reactants are mixed in the reactor by mixer 306 for a period of time (e.g., 5-60 minutes) to allow the conversion of the coke into a liquid fuel to take place and heteroatoms (such as sulfur and nitrogen) and other heavy metals to be removed from the liquid hydrocarbon feedstock 10 and coke 40.
- the product, a mixture of desulfurized feedstock, liquid fuel and inorganic solids such as alkali metal sulfides, nitrides, heavy metals and unreacted coke are sent to the maturation vessel 204, where the mixture is treated with elemental sulfur 16 as described above for FIG. 1.
- the (optionally cooled) sulfur- treated mixture is fed to a solid/liquid separation apparatus 206, which typically includes a centrifuge but may also include a filter.
- the separated solids 30 exit the separation apparatus for further processing, and the upgraded oil feedstock 39 containing the liquid fuel produced from the petroleum coke may be further treated as described above for FIG. 1.
- the solids 30 may include, e.g., alkali metal sulfides, alkali metal nitrides, heavy metals, and unreacted residual coke.
- the solids 110 may also be further processed as described for FIG. 1 to regenerate the alkali metal.
- Example 1 Desulfurization with Sodium followeded by Sulfur Treatment and Solids Separation
- a vacuum residuum oil feedstock was treated with sodium metal in a pilot plant using a continuous system essentially as shown in FIG. 1 under the following conditions to yield a mixture of treated oil and fine particles comprising sodium sulfide.
- a vacuum residuum oil feedstock was treated with sodium metal in a pilot plant using a continuous system essentially as shown in FIG. 1 under the following four trial conditions to yield a mixture of treated oil and fine particles comprising sodium sulfide.
- Table 2
- Trials 2A-2D provided four mixtures of sodium-reacted oil feedstock and particles containing sodium sulfide that were processed in a continuous fashion at a pilot plant using the present separation process in accordance with FIG. 1 and the conditions of Trials 3 A to 3D shown below in Table 3. The amount of sulfur was measured in the desulfurized liquid hydrocarbons.
- a 5 weight % mixture of the petroleum coke with balance residual fuel oil from Example 4 was prepared. 700 grams was placed into a 1.8L Parr reactor with a gas induction impellor and cooling loop. The reactor was purged with hydrogen. After purging, the sample was heated to operating temperature of 358 °C and pressure of 1514 psig. 22.71 grams molten sodium was pumped into the reactor using an electromagnetic pump. Hydrogen pressure was maintained by pumping hydrogen into the system while measuring the flow. At the end of the run the reactor contents were allowed to cool. Gases were slowly released. The flow rate of gases were measured using flow meters and analyzed using an Agilent Technologies Gas Chromatograph, Model 7890A.
- the reactor contents were centrifuged to separate the solids from the liquids and the solids were then rinsed with toluene to remove adhered liquids.
- the toluene rinse was evaporated using a rotary evaporator and the remaining liquid was added to the centrifuged liquid.
- the solids were rinsed again with pentane.
- the pentane rinse was evaporated off using a rotary evaporator and the remaining liquid was combined with the liquid from the centrifuge.
- the solids and liquids were characterized in the same manner as the original sample and a mass balance was calculated to determine the liquid yield.
- the final liquid had the composition shown in Table 6 below.
- Example 5 was repeated except rather than 5 wt% petroleum coke, 10 weight % coke was prepared then operated in the same manner except only 21.07 grams sodium was added and the operating pressure was slightly lower at 1499 psig. The final liquid had the composition shown in Table 7.
- the final fuel is still a residual fuel but now it meets the sulfur specification where there will be very large demand and will command a price similar to distillate while the starting materials, especially the coke would be priced substantially below the price of the product.
- the solids can be treated and according to the procedures of Gordon et. al. in U.S Pat. No 8,088,270 to regenerate the sodium so it may be recycled to the process.
- hydrocarbon liquids capable of dissolving organic molecules rich in carbon could have been utilized rather than the one selected.
- the dissolving liquid already has a low sulfur content then less sodium could be added to the reaction and less hydrogen donation required. It may be noted than when 5% coke was added, 34% of the desulfurized coke entered the liquid phase while when 10% coke was added only 29% of the desulfurized coke entered the liquid phase. But if the coke has extremely low value and the product is priced similar to distillate, then accepting lower portions entering the liquid phase may still be desirable. Conversely, adding a lower relative amount of coke the portion entering the liquid phase is expected to be greater.
- other liquids may be conducive to increasing the solubility of the treated coke. For example, asphaltenes are soluble in toluene. Adding particular hydrocarbons may be conducive to increasing the solubility of the molten sodium treated petroleum coke and are part of the scope of this invention.
- any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc.
- each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc.
- all language such as “up to,” “at least,” “greater than,” “less than,” and the like, include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above.
- a range includes each individual member.
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Priority Applications (7)
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EP17784812.4A EP3523396B1 (en) | 2016-10-04 | 2017-10-04 | Process for separating particles containing alkali metal salts from liquid hydrocarbons |
SG11201902990UA SG11201902990UA (en) | 2016-10-04 | 2017-10-04 | Process for separating particles containing alkali metal salts from liquid hydrocarbons |
JP2019539740A JP6817656B2 (en) | 2016-10-04 | 2017-10-04 | A method for separating particles containing alkali metal salts from liquid hydrocarbons |
CN201780067716.5A CN109890944B (en) | 2016-10-04 | 2017-10-04 | Process for separating particles containing alkali metal salts from liquid hydrocarbons |
ES17784812T ES2836679T3 (en) | 2016-10-04 | 2017-10-04 | Procedure for separating particles containing alkali metal salts from liquid hydrocarbons |
KR1020197012851A KR102211995B1 (en) | 2016-10-04 | 2017-10-04 | Method for separating particles containing alkali metal salts from liquid hydrocarbons |
CA3039380A CA3039380C (en) | 2016-10-04 | 2017-10-04 | Process for separating particles containing alkali metal salts from liquid hydrocarbons |
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US201662404119P | 2016-10-04 | 2016-10-04 | |
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US15/446,299 | 2017-03-01 | ||
US15/446,299 US20170253816A1 (en) | 2016-03-03 | 2017-03-01 | Method for recovering alkali metal from hydrocarbon feedstocks treated with alkali metal |
US201762513871P | 2017-06-01 | 2017-06-01 | |
US62/513,871 | 2017-06-01 |
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Cited By (3)
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WO2021236739A1 (en) * | 2020-05-19 | 2021-11-25 | Enlighten Innovations Inc. | Purification and conversion processes for asphaltene-containing feedstocks |
WO2021236827A1 (en) * | 2020-05-19 | 2021-11-25 | Enlighten Innovations Inc. | Processes for improved performance of downstream oil conversion |
WO2023042175A1 (en) * | 2021-09-17 | 2023-03-23 | Enlighten Innovations Inc. | Compositions and methods for making carbon fibers from asphaltenes |
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WO2022083587A1 (en) * | 2020-10-19 | 2022-04-28 | 中国石油化工股份有限公司 | Method and system for producing fuel oil and use thereof, and fuel oil and use thereof |
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US3791966A (en) * | 1972-05-24 | 1974-02-12 | Exxon Research Engineering Co | Alkali metal desulfurization process for petroleum oil stocks |
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- 2017-10-04 KR KR1020197012851A patent/KR102211995B1/en active IP Right Grant
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- 2017-10-04 CA CA3039380A patent/CA3039380C/en active Active
- 2017-10-04 EP EP17784812.4A patent/EP3523396B1/en active Active
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US1300816A (en) * | 1915-09-11 | 1919-04-15 | Standard Oil Co | Process of desulfurizing petroleum-oils. |
US3849297A (en) * | 1972-06-08 | 1974-11-19 | Exxon Research Engineering Co | Process for removing metals from petroleum residua |
US8088270B2 (en) | 2007-11-27 | 2012-01-03 | Ceramatec, Inc. | Process for recovering alkali metals and sulfur from alkali metal sulfides and polysulfides |
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WO2023042175A1 (en) * | 2021-09-17 | 2023-03-23 | Enlighten Innovations Inc. | Compositions and methods for making carbon fibers from asphaltenes |
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CA3039380C (en) | 2023-02-28 |
CN109890944B (en) | 2020-07-03 |
KR102211995B1 (en) | 2021-02-05 |
KR20190058616A (en) | 2019-05-29 |
EP3523396B1 (en) | 2020-11-25 |
JP6817656B2 (en) | 2021-01-20 |
CN109890944A (en) | 2019-06-14 |
JP2019536883A (en) | 2019-12-19 |
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EP3523396A1 (en) | 2019-08-14 |
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