WO2020041001A1 - Valorisation de déchets et systèmes associés - Google Patents

Valorisation de déchets et systèmes associés Download PDF

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Publication number
WO2020041001A1
WO2020041001A1 PCT/US2019/045623 US2019045623W WO2020041001A1 WO 2020041001 A1 WO2020041001 A1 WO 2020041001A1 US 2019045623 W US2019045623 W US 2019045623W WO 2020041001 A1 WO2020041001 A1 WO 2020041001A1
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Prior art keywords
stream
hydrocarbon
gasifier
reactor
coke
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Application number
PCT/US2019/045623
Other languages
English (en)
Inventor
Mohsen N. Harandi
Original Assignee
Exxonmobil Research And Engineering Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by Exxonmobil Research And Engineering Company filed Critical Exxonmobil Research And Engineering Company
Publication of WO2020041001A1 publication Critical patent/WO2020041001A1/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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/28—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid material
    • C10G9/32—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid material according to the "fluidised-bed" technique
    • 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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/005—Coking (in order to produce liquid products mainly)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
    • C10B55/02—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials
    • C10B55/04—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials
    • C10B55/08—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials in dispersed form
    • C10B55/10—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials in dispersed form according to the "fluidised bed" technique
    • 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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/28—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J1/00—Production of fuel gases by carburetting air or other gases without pyrolysis
    • C10J1/20—Carburetting gases other than air
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials
    • 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
    • C10G2300/70—Catalyst aspects
    • C10G2300/708—Coking aspect, coke content and composition of deposits
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/26—Fuel gas

Definitions

  • This application relates to upgrading waste to produce fuel and the related systems.
  • a method in accordance with aspects of the presently disclosed subject matter comprises: introducing a hydrocarbon feed stream into a coking zone at 450°C to l050°C of a reactor containing a fluidized bed of coke particles maintained at coking temperatures to produce a vapor phase hydrocarbon product while coke is deposited on the coke particles; allowing the coke particles to pass downwards in the reactor to a stripper section of the reactor; introducing a steam stream into the stripper section of the reactor; transferring the coke particles from the stripper section of the reactor to a gasifier/bumer; contacting the coke particles in the gasifier/bumer an oxygen-containing gas in an oxygen-limited atmosphere at 850°C to l200°C to heat the coke particles and form a fuel gas product that comprises carbon monoxide and hydrogen; recycling the heated coke particles from the gasifier/bumer to the coking zone of the reactor; and introducing at least one waste stream to the reactor and/or the gasifier/bumer.
  • a system in accordance with aspects of the presently disclosed subject matter comprises: a reactor that receives a hydrocarbon feed stream, a steam stream, and a hot coke stream and produces a vapor-phase hydrocarbon product stream and a cold coke stream; a gasifier/bumer that receives the cold coke stream and an oxygen-containing gas stream and produces the hot coke stream and a fuel gas stream; and one or more of: a first hydrocarbon-rich waste stream entrained in the hydrocarbon feed stream that is received by the reactor; a second hydrocarbon-rich waste stream received by the gasifier/bumer; a first water-rich waste stream entrained in the steam stream that is received by the reactor; and a first water-rich waste stream entrained in the oxygen- containing gas stream received by the gasifier/bumer.
  • An alternative system in accordance with aspects of the presently disclosed subject matter comprises: a reactor that receives a hydrocarbon feed stream, a steam stream, and a hot coke stream and produces a vapor-phase hydrocarbon product stream and a cold coke stream; a heater that receives the cold coke stream, a partly gasified coke stream, and a first fuel gas stream and produces the hot coke stream, a second fuel gas stream, and a heated coke stream; a gasifier/bumer that receives the heated coke stream and an oxygen-containing gas stream and produces the partly gasified coke stream and the first fuel gas stream; and one or more of: a first hydrocarbon-rich waste stream entrained in the hydrocarbon feed stream that is received by the reactor; a second hydrocarbon-rich waste stream received by the gasifier/bumer; a first water-rich waste stream entrained in the steam stream that is received by the reactor; and a first water-rich waste stream entrained in the oxygen-containing gas stream received by the gasifier/bumer.
  • FIG. 1 illustrates an example fluid-bed coking unit for producing fuel gas stream and vapor phase hydrocarbon product from one or more waste streams according to the present application.
  • FIG. 2 illustrates an example FLEXICOKINGTM unit with three reaction vessels for producing fuel gas stream and vapor phase hydrocarbon product from one or more waste streams according to the present application.
  • FIG. 3 illustrates another example FLEXICOKINGTM unit with two reaction vessels for producing fuel gas stream and vapor phase hydrocarbon product from one or more waste streams according to the present application.
  • the present application relates to upgrading waste to produce fuel and the related systems. More specifically, hydrocarbon-rich waste and optionally water-rich waste can be used as a portion of the feed for FLEXICOKINGTM methods and fluid-bed coking methods that produce fuel gas.
  • coal refers to the solid residue remaining from the pyrolysis of hydrocarbons.
  • hydrocarbon-rich waste refers to waste that at l5°C is a liquid or solid containing at least 10 wt%, preferably more than 50 wt%, compounds made from primarily carbon and hydrogen (that is, at least 75 mol% of the compounds are cumulatively carbon and hydrogen).
  • hydrocarbon-rich waste are refinery tank bottoms and plastics.
  • water-rich waste refers to waste that at l5°C is a liquid containing at least 10 wt%, preferably more than 50 wt%, water.
  • oxygen-limited atmosphere refers to a sub-stoichiometric usage of O2 for complete combustion of hydrocarbons include coke to CO2 and H2O.
  • O2 deficiency is maintained at a level to have minority moles of carbon oxides be carbon dioxide.
  • residuum refers to the complex mixture of heavy petroleum compounds otherwise known in the art as residuum or residual.
  • fuel gas refers to a gas comprising carbon monoxide and hydrogen in a combined concentration of at least 20 wt%, preferably at least 30 wt%, and more preferably at least 90 wt%. Carbon dioxide and/or nitrogen may also be included in fuel gas.
  • Heavy petroleum oils and residual fractions derived from them are characterized by a combination of properties which may be summarized as high initial boiling point, high molecular weight, and low hydrogen content relative to lower boiling fractions such as naphtha, gasoline, and distillates; frequently these heavy oils and high boiling fractions exhibit high density (low API gravity), high viscosity, high carbon residue, high nitrogen content, high sulfur content, and high metals content.
  • Carbon rejection redistributes hydrogen among the various components, resulting in fractions with increased H/C atomic ratios and products including fractions with lower H/C atomic ratios and solid coke-like materials.
  • Carbon rejection processes may be either non-catalytic or catalytic. Both can be said generally to operate at moderate to high temperatures and low pressures and suffer from a lower liquid yield of transportation fuels than hydrogen addition processes, because a large fraction of the feedstock is rejected as solid coke; light gases are also formed as by-products in the thermal cracking reactions and, being of high H/C ratio tend to degrade the quantity of the more valuable liquid products.
  • the liquids are generally of poor quality and must normally be hydrotreated before they can be used as feeds for catalytic processes to make transportation fuels.
  • Thermal cracking processes include those such as visbreaking, which operate under relatively mild conditions and are intended mainly to increase the yields of distillates from residual fractions.
  • Coking processes by contrast, operate at significantly higher severities and produce substantial quantities of coke as the by-product; the amount of the coke is typically of the order of one-third the weight of the feed.
  • the main coking processes now in use are delayed coking, fluid- bed coking, and a fluid-bed coking variant known as FLEXICOKINGTM.
  • the present application relates to upgrading waste like municipal and industrial waste by using it as a feedstock in FLEXICOKINGTM methods and fluid-bed coking methods that produce fuel gas and hydrocarbon products.
  • the waste streams can include hydrocarbon-rich waste and, optionally, water-rich waste.
  • the hydrocarbon-rich waste can include, for example, waste from municipal sources, commercial sources, industrial sources, and the like, and combinations thereof.
  • Specific examples of hydrocarbon-rich waste can include, but are not limited to, animal fats, plant fats (e.g., frying and cooking oil), plastics, wood chips, chemical solvents, pigments, sludge, paints, paper products (e.g., paper and cardboard), construction materials, compost, agricultural waste (e.g., spoiled or unwanted crops/fruits and watermelon shell), and combinations thereof.
  • the water-rich waste can include waste from municipal sources, commercial sources, industrial sources, or a combination thereof.
  • Specific examples of water-rich waste can include, but are not limited to, diapers, food waste (e.g., from restaurants and households), a benzene containing wastewater (e.g., benzene containing refinery water waste such as desalter bottoms), an industrial wastewater containing hydrocarbons (e.g., API separator waste), and combinations thereof.
  • the hydrocarbon-rich waste and the water-rich waste are absent metal (especially volatile metals like mercury) and glass.
  • metal especially volatile metals like mercury
  • small amounts of metal e.g., less than 1 wt%) may be tolerated provided that the metal is non-volatile. Such metals may lay on the produced coke particles and be recovered with further processing.
  • Hydrocarbon-rich waste and optionally water-rich waste can be used as a portion of the feed for FLEXICOKINGTM methods and fluid-bed coking methods that produce fuel gas.
  • a general method of the in accordance with aspects of the presently disclosed subject matter that applies to FLEXICOKINGTM methods and fluid-bed coking methods includes the following steps: introducing a hydrocarbon feed stream into a coking zone of a reactor containing a fluidized bed of coke particles maintained at coking temperatures (e.g., about 40 °C to about 1050 °C, preferably about 150 °C to about 900 °C, preferably about 300 °C to about 750 °C, and more preferably about 450 °C to about 650 °C) to about to produce a vapor phase hydrocarbon product while coke is deposited on the coke particles; introducing a steam stream into a stripper section of the reactor; allowing the coke particles to pass downwards in the reactor to a stripper section of the reactor; transferring the coke particles from the stripper section of the reactor to a gasifier/bumer; contacting the coke particles in the gasifier/burner an oxygen-containing gas in an oxygen-limited atmosphere at
  • a burner In fluid-bed coking methods, a burner is used. In FLEXICOKINGTM methods, a gasifier is used. In some FLEXICOKINGTM methods, a heater section (also referred to herein simply as a heater) is included between the reactor and the gasifier.
  • a cyclone system is typically used to remove coke fines from the fuel gas.
  • a cyclone system can include serially connected primary and secondary cyclones with diplegs that return the separated fines to the fluid bed in the vessel in which the cyclone system is connected or a part of.
  • the cyclone system can be a portion of the gasifier/bumer.
  • the cyclone system can be included as part of the heater section.
  • the coking zone of the reactor operates at about 450°C to about 850°C, and the combustion or gasification zone of the burner operate at about 850°C to about l000°C.
  • these zones of the reactor and burner or gasifier may be operated at a higher temperature to reduce buildup sticky, adherent high molecular weight hydrocarbon deposits on the particles that could lead to reactor fouling.
  • the coking zone of the reactor may be operated at a higher temperature to ensure cracking and mitigate reactor and coke particle fouling.
  • the coking zone of the reactor operates at about 850°C to about l050°C, and the combustion or gasification zone of the burner or gasifier operate at about l000°C to about l200°C where the combustion or gasification zone is at a higher temperature than the coking zone. Therefore, the methods described herein can be performed with the coking zone of the reactor operating at about 450°C to about l050°C and the combustion or gasification zone of the burner or gasifier operating at about 850°C to about l200°C where the combustion or gasification zone is at a higher temperature than the coking zone.
  • the coking zone of the reactor operates at about 600°C to about l050°C and the combustion or gasification zone of the burner or gasifier operate at about 950°C to about l200°C.
  • the methods in accordance with aspects of the presently disclosed subject matter advantageously upgrade waste (hydrocarbon-rich waste and/or water-rich waste) to fuel gas and hydrocarbon product.
  • the fuel gas also known as syngas
  • syngas is useful as an intermediate when producing, for example, ammonia, methanol, and synthetic hydrocarbon fuels. Additionally, fuel gas can be combusted to produce electricity.
  • the hydrocarbon products comprise C5+-rich hydrocarbons that can be used in various industrial processes and as components to be processed for blending into gasoline, jet, kerosene and diesel.
  • FIG. 1 illustrates an example fluid-bed coking unit 100 for producing fuel gas stream 101 and vapor phase hydrocarbon product 102 from one or more waste streams according to the present application.
  • three possible waste streams can be used in the fluid-bed coking unit 100: a first hydrocarbon-rich waste stream 103, a second hydrocarbon-rich waste stream 104, and a first water-rich waste stream 105. While each are referred to in the description below as optional, one or more are required for the present invention.
  • the fluid-bed coking unit 100 includes a reactor 107 containing coke particles that are maintained in the fluidized condition at the required reaction temperature for hydrocarbon cracking (e.g., at about 450°C to about l050°C).
  • a gaseous stream, preferably a steam stream 108 is injected at the bottom of the reactor 107 with the average direction of movement of the coke particles being downwards through the bed.
  • a first water-rich waste stream 105 can be used in combination with (shown) or in alternative of (not shown) the steam stream 108.
  • Hydrocarbon feed stream 109 is preheated to a temperature, typically in the range of 350°C to 400°C and introduced into the reactor 107.
  • the hydrocarbon feed stream 109 can include, but is not limited to, resids, petroleum vacuum distillation bottoms, aromatic extracts, asphalts, steam cracker tar, and bitumens (e.g., from tar sands, tar pits, and/or pitch lakes), and combinations thereof.
  • a first hydrocarbon-rich waste stream 103 can be entrained with the hydrocarbon feed stream 109.
  • the first hydrocarbon-rich waste stream 103 can be derived from liquid waste and/or solid waste. When using solid waste, the waste can, if needed, be chopped into small pieces so that it can be easily transported and distributed in the fluid-bed coking unit 100.
  • the first hydrocarbon-rich waste stream 103 can optionally have a carrier gas like air, steam, or a hydrocarbon gas, which may assist in transportation of the waste in the fluid-bed coking unit 100.
  • the hydrocarbon-rich waste stream 103 optionally in the carrier gas can also be heated before entraining in the hydrocarbon feed stream 109.
  • a carrier liquid such as heavy hydrocarbon streams may also be used. This stream may also dissolve the waste before injection.
  • the hydrocarbon feed stream 109 is fed through multiple feed nozzles which may be arranged at several successive levels in the reactor 107 including one or more coking zones of the reactor 107.
  • An advantage of utilizing a fluidized coke bed reactor for waste management is its robustness for handling various solid particle sizes in various concentrations.
  • the coking zone(s) can be at temperatures of about 450°C to about l050°C.
  • Steam stream 108 is injected into a stripping section at the bottom of the reactor 107 and passes upwards through the coke particles descending through the dense phase of the fluid bed in the main part of the reactor above the stripping section.
  • Part of the hydrocarbon feed stream 109 injected into the reactor 107 coats the coke particles in the fluidized bed and is subsequently cracked into (1) layers of solid coke and (2) a hydrocarbon product stream 102 that evolves as gas or vaporized liquid.
  • Reactor pressure is preferably relatively low in order to favor vaporization of the hydrocarbons.
  • the vapor-phase hydrocarbon product stream 102 are separated from the coke particles and extracted from the reactor 107.
  • the vapor-phase hydrocarbon product stream 102 comprises, in the majority (i.e., greater than 50 wt%, preferably greater than 75 wt%, most preferably greater than 85 wt%), a C5+-rich product.
  • the vapor-phase hydrocarbon product stream 102 can be fractionated where the heavier hydrocarbons can be recycled back to the reactor 107 (e.g., by being entrained with the hydrocarbon feed 109).
  • the coke particles formed in the coking zone pass downwards in the reactor 107 and leave the bottom of the reactor vessel through a stripper section where they are exposed to steam stream 108 in order to remove occluded hydrocarbons.
  • the coke particles at this point in the fluid- bed coking unit 100 are referred to herein as“cold coke.”
  • a cold coke stream 110 from the reactor 107 (consisting mainly of carbon with lesser amounts of hydrogen, sulfur, nitrogen, and traces of vanadium, nickel, iron, and other elements derived from the hydrocarbon feed 109 and optionally entrained first hydrocarbon-rich feed stream 103) passes through the stripper section and out of the reactor 107 to a burner (typically referred to as a gasifier in FLEXICOKINGTM processes/systems and burner in fluid-bed coking processes/systems) 111 where the coke in the gasifier is partly burned in a fluidized bed (e.g., at a temperature of about 850°C to about l200°C) with an oxygen-
  • the heated coke is removed (e.g., via a cyclone system (not shown)) from the fuel gas to produce a fuel gas stream 101.
  • Hot coke is extracted from the burner 111 and supplied to the reactor 107 as a hot coke stream 113.
  • the hot coke stream 113 supplies the heat required for the endothermic coking reactions occurring in the reactor 107.
  • a second hydrocarbon-rich waste stream 104 can also be supplied to the burner 111.
  • the illustrated fluid-bed coking unit 100 upgrades one or more waste streams 103, 104, 105 to a fuel gas stream 101 and a vapor phase hydrocarbon product stream 102.
  • FLEXICOKINGTM Units [0039]
  • the FLEXICOKINGTM process developed by Exxon Research and Engineering Company, is a non-catalytic thermal conversion process with a continuous and totally contained fluidized bed integrated coking and gasification technology.
  • fluid coke produced in the reactor is gasified with process steam and air to produce a higher value fuel gas (FLEXIGASTM).
  • the FLEXICOKINGTM unit may be a conventional three-vessel unit of cracking reactor, heater, and gasifier or, alternatively, a two-vessel unit of reactor and gasifier in which the coke from the reactor passes directly to the gasifier and hot, partly gasified coke particles from the gasifier are cycled back to the reactor to provide the heat for the endothermic cracking reactions.
  • a unit of this type is described in U.S. Patent Application Publication No. 2015/0368572 (Rajagopalan), to which reference is made for a description of the unit and its method of operation.
  • FIG. 2 illustrates an example FLEXICOKINGTM unit 220 with three reaction vessels (a reactor 221, a heater 222, and a gasifier 223) in side-by-side arrangement; although the footprint of the side-by-side arrangement is larger than that of the stacked units shown in U.S. Patent Nos. 3,661,543 (Saxton) and 3,816,084 (Moser), it is less subject to upsets and potential equipment failures as noted in U.S. Patent No. 3,759,676 (Lahn) and has now become conventional.
  • the FLEXICOKINGTM unit 220 includes four possible waste streams: a first hydrocarbon-rich waste stream 224, a second hydrocarbon-rich waste stream 225, a first water-rich waste stream 226, and a second water-rich waste stream 226. While each are referred to in the description below as optional, one or more are required for the present invention.
  • the FLEXICOKINGTM unit 220 comprises reactor section 221 with the coking zone (e.g., at about 450°C to about l050°C) and its associated stripping and scrubbing sections (not separately indicated as conventional), a heater section 222, and a gasifier section 223.
  • the relationship of the coking zone, scrubbing zone, and stripping zone in the reactor section is shown, for example, in U.S. Patent No. 5,472,596 (Kerby), to which reference is made for a description of the FLEXICOKINGTM unit and its reactor section.
  • a hydrocarbon feed stream 228 is introduced into the reactor 221, optionally with a hydrocarbon-rich waste stream 224 entrained therein.
  • a vapor phase hydrocarbon product 229 is withdrawn from the reactor 221.
  • a steam stream 230 is supplied to the reactor 221 for fluidizing and stripping the coke particles to produce cold coke.
  • the first water-rich waste stream 226 can be entrained in the steam stream 230 (shown) or used in alternative of the steam stream 230 (not shown).
  • a cold coke stream 232 passes from the reactor 221 to the heater 222.
  • the heater 222 raises the temperature of the coke particles.
  • a coke stream 233 from heater 222 is transferred to gasifier 223.
  • An oxygen-containing gas stream 234 is introduced to the gasifier 223 in an oxygen- limited atmosphere and used for combustion to produce fuel gas and hot, partly gasified particles of coke.
  • the gasification zone(s) of the gasifier 223 can be at temperatures of about 850°C to l200°C.
  • the oxygen-containing gas stream 234 can be entrained with a steam stream 235, which optionally can be entrained with the second water-waste stream 227 or be replaced with the second water-waste stream 227.
  • a second hydrocarbon-rich waste stream 225 can be introduced to the gasifier 223 where the hydrocarbons participate in combustion.
  • a stream 236 of hot, partly gasified particles of coke stream a separate first fuel gas stream 237 are supplied from the gasifier 223 to the heater 222.
  • the coke particles and fuel gas are further heated in the heater 222, which further gasifies the coke particles.
  • a cyclone system 238 is used to remove coke particles from the fuel gas to produce a second fuel gas stream 239.
  • the hot coke stream 240 (hot coke extracted from the heater 222) is then introduced back into the reactor 221. Excess coke is withdrawn from the heater 222 in excess coke stream 241.
  • the illustrated FLEXICOKINGTM unit 220 upgrades one or more waste streams 224, 225, 226, 227 to the second fuel gas stream 239 and the vapor phase hydrocarbon product stream 229.
  • FIG. 3 illustrates another FLEXICOKINGTM unit 350 with two reaction vessels: a reactor 351 and gasifier 352.
  • the illustrated FLEXICOKINGTM unit 350 includes four possible waste streams: a first hydrocarbon-rich waste stream 353, a second hydrocarbon-rich waste stream 354, a first water-rich waste stream 355, and a second water-rich waste stream 356. While each are referred to in the description below as optional, one or more are required for the present invention.
  • the reactor 351 operates in the same manner as reactor 221 of FIG. 2.
  • the reactor 351 receives hydrocarbon feed stream 357 (which optionally can have the first hydrocarbon-rich waste stream 353 entrained therein) and steam stream 358 (which optionally can have the first water-rich waste stream 355 entrained therein (shown) or in alternative is the first water-rich waste stream 355 (not shown)).
  • the reactor 351 produces vapor-phase hydrocarbon product stream 360 and cold coke stream 360.
  • the gasifier which has an oxygen-limited atmosphere, receives cold coke stream 360 from the reactor 351, an oxygen-containing gas stream 361 (optionally having a steam stream 362 entrained therein, where the steam stream optionally can have the second water-rich waste stream 356 entrained therein (shown) or in alternative is the first water-rich waste stream 356 (not shown)), and optionally a second hydrocarbon-rich waste stream 356.
  • Cyclone system 363 is included with the gasifier 352 to remove the hot coke from the fuel gas to produce a fuel gas stream 365.
  • the hot coke stream 364 (hot coke extracted from the gasifier 352) is recycled to the reactor 351.
  • the fuel gas stream 365 can optionally be split and recycled back into the gasifier 352 to assist with optimizing the flue gas composition and maintaining the optimum operating conditions.
  • the illustrated FLEXIC OKINGTM unit 350 upgrades one or more waste streams 353,
  • a first nonlimiting example method of the present invention comprises: introducing a hydrocarbon feed stream into a coking zone at 450°C to l050°C of a reactor containing a fluidized bed of coke particles maintained at coking temperatures to produce a vapor phase hydrocarbon product while coke is deposited on the coke particles; allowing the coke particles to pass downwards in the reactor to a stripper section of the reactor; introducing a steam stream into a stripper section of the reactor; transferring the coke particles from the stripper section of the reactor to a gasifier/bumer; contacting the coke particles in the gasifier/bumer an oxygen-containing gas in an oxygen-limited atmosphere at 850°C to l200°C to heat the coke particles and form a fuel gas product that comprises carbon monoxide and hydrogen; recycling the heated coke particles from the gasifier/bumer to the coking zone of the reactor; and introducing at least one waste stream to the reactor and/or the gasifier/bumer.
  • the first nonlimiting example method can include one or more of the following: Element 1 : wherein the at least one waste stream comprises a first hydrocarbon-rich waste stream and the method further comprises: entraining the first hydrocarbon-rich waste stream into the hydrocarbon feed stream before introduction into the reactor; Element 2: wherein the at least one waste stream comprises a second hydrocarbon-rich waste stream and the method further comprises: introducing the second hydrocarbon-rich waste stream to the gasifier/bumer; Element 3: one or more of Elements 1-2 wherein the first and/or second hydrocarbon-rich waste stream comprises tank bottoms and/or crude emulsion solids; Element 4: one or more of Elements 1-3 wherein the first and/or second hydrocarbon-rich waste stream comprises waste from one or more of: a municipal source, a commercial source, and an industrial source; Element 5: one or more of Elements 1-4 wherein the first and/or second hydrocarbon-rich waste stream comprises at least one selected from the group consisting of: an animal fat, a plant
  • Nonlimiting combinations of elements include: Elements 1 and 2 in combination; two or more of Elements 1, 2, 7, and 8 in combination; two or more of Elements 1, 2, 7, 8, and 17 in combination; two or more of Elements 13-15 in combination optionally in further combination with one or more of Elements 1, 2, 7, 8, and 17; and two or more of Elements 13, 14, and 16 in combination optionally in further combination with one or more of Elements 1, 2, 7, and 8.
  • a first nonlimiting example system of the present invention comprises: a reactor that receives a hydrocarbon feed stream, a steam stream, and a hot coke stream and produces a vapor- phase hydrocarbon product stream and a cold coke stream; a gasifier/bumer that receives the cold coke stream and an oxygen-containing gas stream and produces the hot coke stream and a fuel gas stream; and one or more of: a first hydrocarbon-rich waste stream entrained in the hydrocarbon feed stream that is received by the reactor; a second hydrocarbon-rich waste stream received by the gasifier/bumer; a first water-rich waste stream entrained in the steam stream that is received by the reactor; and a first water-rich waste stream entrained in the oxygen-containing gas stream received by the gasifier/bumer.
  • a second nonlimiting example system of the present invention comprises: a reactor that receives a hydrocarbon feed stream, a steam stream, and a hot coke stream and produces a vapor- phase hydrocarbon product stream and a cold coke stream; a heater that receives the cold coke stream, a partly gasified coke stream, and a first fuel gas stream and produces the hot coke stream, a second fuel gas stream, and a heated coke stream; a gasifier/bumer that receives the heated coke stream and an oxygen-containing gas stream and produces the partly gasified coke stream and the first fuel gas stream; and one or more of: a first hydrocarbon-rich waste stream entrained in the hydrocarbon feed stream that is received by the reactor; a second hydrocarbon-rich waste stream received by the gasifier/bumer; a first water-rich waste stream entrained in the steam stream that is received by the reactor; and a first water-rich waste stream entrained in the oxygen-containing gas stream received by the gasifier/bumer.
  • the first and nonlimiting example systems can, independently, include one or more of the following: Element 18: wherein the first and/or second hydrocarbon-rich waste stream comprises tank bottoms and/or cmde emulsion solids; Element 19: wherein the first and/or second hydrocarbon-rich waste stream comprises waste from one or more of: a municipal source, a commercial source, and an industrial source; Element 20: wherein the first and/or second hydrocarbon-rich waste stream comprises at least one selected from the group consisting of: an animal fat, a plant fat, a plastic, a wood chip, a chemical solvent, a pigment, sludge, a paint, a paper product, a construction material, compost, agricultural waste, and any combination thereof; Element 21 : a chopping unit along the first and/or second hydrocarbon-rich waste stream; Element 22: wherein the first and/or second water-rich waste stream comprises waste from one or more of: a municipal source, a commercial source, and an industrial source; Element 23
  • Nonlimiting combinations of elements include: Elements 21 and 24 in combination; two or more of Elements 18-20 in combination; two or more of Elements 22, 23, and 25 in combination; one or more of Elements 18-20 in combination with one or more of Elements 22, 23, and 25; two or more of Elements 26-28 in combination optionally in further combination with one or more of Elements 18-25; and two or more of Elements 26, 27, and 29 in combination optionally in further combination with one or more of Elements 18-25.
  • compositions and methods are described herein in terms of“comprising” various components or steps, the compositions and methods can also“consist essentially of’ or“consist of’ the various components and steps.
  • compositions and methods are described in terms of“comprising,”“containing,” or“including” various components or steps, the compositions and methods can also“consist essentially of’ or“consist of’ the various components and steps. All numbers and ranges disclosed above may vary by some amount. Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range is specifically disclosed. In particular, every range of values (of the form,“from about a to about b,” or, equivalently,“from approximately a to b,” or, equivalently,“from approximately a-b”) disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
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Abstract

L'invention concerne un procédé de valorisation de déchets pour produire du combustible, ledit procédé pouvant comprendre les étapes consistant à : introduire un courant d'alimentation d'hydrocarbures dans une zone de cokéfaction ayant une plage de température de 450 °C à 1050 °C d'un réacteur contenant un lit fluidisé de particules de coke maintenues à des températures de cokéfaction pour produire un produit hydrocarboné en phase vapeur tandis que du coke est déposé sur les particules de coke; permettre aux particules de coke de passer vers le bas vers une section de décapage du réacteur; introduire un courant de vapeur dans la section de décapage; transférer les particules de coke de la section de décapage à un gazéifieur/brûleur; mettre en contact les particules de coke dans le gazéifieur/brûleur avec un gaz contenant de l'oxygène dans une atmosphère à teneur limitée en oxygène à 850 °C à 1200 °C pour chauffer les particules de coke et former un produit de gaz combustible qui comprend du monoxyde de carbone et de l'hydrogène; recycler les particules de coke chauffées du gazéifieur/brûleur vers la zone de cokéfaction du réacteur; et introduire au moins un courant de déchets dans le réacteur et/ou le gazéifieur/brûleur.
PCT/US2019/045623 2018-08-22 2019-08-08 Valorisation de déchets et systèmes associés WO2020041001A1 (fr)

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WO2024006184A1 (fr) * 2022-06-29 2024-01-04 ExxonMobil Technology and Engineering Company Co-traitement de biomasse pendant une cokéfaction fluidisée avec gazéification

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WO2013062800A1 (fr) * 2011-10-26 2013-05-02 Rentech, Inc. Fluidisation de gazéifieur
US20150368572A1 (en) 2014-06-20 2015-12-24 Exxonmobil Research And Engineering Company Fluidized bed coking with fuel gas production
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US3661543A (en) 1969-11-26 1972-05-09 Exxon Research Engineering Co Fluid coking process incorporating gasification of product ore
US3702516A (en) 1970-03-09 1972-11-14 Exxon Research Engineering Co Gaseous products of gasifier used to convey coke to heater
US3816084A (en) 1970-04-16 1974-06-11 Exxon Research Engineering Co Cokeless coker with recycle of coke from gasifier to heater
US3759676A (en) 1971-01-22 1973-09-18 Exxon Research Engineering Co Integrated fluid coking gasification process
US4113602A (en) * 1976-06-08 1978-09-12 Exxon Research & Engineering Co. Integrated process for the production of hydrocarbons from coal or the like in which fines from gasifier are coked with heavy hydrocarbon oil
CA1091927A (fr) * 1976-06-14 1980-12-23 William J. Metrailer Procede de gazeification
US4213848A (en) 1978-07-27 1980-07-22 Exxon Research & Engineering Co. Fluid coking and gasification process
US4269696A (en) 1979-11-08 1981-05-26 Exxon Research & Engineering Company Fluid coking and gasification process with the addition of cracking catalysts
US4379046A (en) * 1981-06-11 1983-04-05 Exxon Research & Engineering Co. Integrated two stage coking and steam cracking process and apparatus therefor
US5472596A (en) 1994-02-10 1995-12-05 Exxon Research And Engineering Company Integrated fluid coking paraffin dehydrogenation process
WO2000026324A1 (fr) * 1998-11-03 2000-05-11 Scaltech Inc. Procede d'elimination des dechets de cokefaction
US20110232164A1 (en) * 2010-03-25 2011-09-29 Exxonmobil Research And Engineering Company Biomass oil conversion process
WO2013062800A1 (fr) * 2011-10-26 2013-05-02 Rentech, Inc. Fluidisation de gazéifieur
US20150368572A1 (en) 2014-06-20 2015-12-24 Exxonmobil Research And Engineering Company Fluidized bed coking with fuel gas production
US20170233667A1 (en) * 2015-02-23 2017-08-17 Exxonmobil Research And Engineering Company Fluidized bed coking with fuel gas production

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