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WO2018187699A1 - Liquéfaction de biomasse pour produire une huile biologique prête au raffinage - Google Patents

Liquéfaction de biomasse pour produire une huile biologique prête au raffinage Download PDF

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Publication number
WO2018187699A1
WO2018187699A1 PCT/US2018/026471 US2018026471W WO2018187699A1 WO 2018187699 A1 WO2018187699 A1 WO 2018187699A1 US 2018026471 W US2018026471 W US 2018026471W WO 2018187699 A1 WO2018187699 A1 WO 2018187699A1
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bio
oil
oil product
liquefied
product
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PCT/US2018/026471
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English (en)
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Santosh Gangwal
Jiajia MENG
Kevin Mccabe
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Southern Research Institute
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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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
    • C10G1/042—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction by the use of hydrogen-donor solvents
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
    • C10G1/047—Hot water or cold water extraction processes
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
    • C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/40—Solid fuels essentially based on materials of non-mineral origin
    • C10L5/44—Solid fuels essentially based on materials of non-mineral origin on vegetable substances
    • C10L5/442—Wood or forestry waste
    • 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
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • 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
    • C10G2400/04—Diesel oil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C10L2200/0476—Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/544—Extraction for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/58—Control or regulation of the fuel preparation of upgrading process
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to the production of bio-oil from a biomass liquefaction process.
  • Bio-oil obtained from fast pyrolysis of biomass is a green intermediate that can be further upgraded into a biofuel for blending in a petroleum refinery using a hydrodeoxygenation (HDO) process.
  • HDO hydrodeoxygenation
  • Co-processing pyrolysis bio-oil in a petroleum refinery is an attractive approach to leverage the refinery's existing capital.
  • the petroleum industry is reluctant to accept pyrolysis bio-oil because of a lack of a standard definition for an acceptable bio-oil feedstock in existing refinery processes.
  • fast pyrolysis-based bio-fuel is determined to be noncompetitive with petroleum-based transportation fuels.
  • biomass material such as woody biomass
  • a hydrothermal liquefaction process in which compressed and heated water is provided as a solvent to liquefy the biomass material.
  • This process must be operated under very high temperatures (e.g., about 350 °C or greater) and also very high pressures (e.g., about 3000 psig (about 20.7 MPa) or greater) and further utilizes catalysts to enhance the liquefaction process.
  • very high temperatures e.g., about 350 °C or greater
  • very high pressures e.g., about 3000 psig (about 20.7 MPa) or greater
  • the severe (high temperature/high pressure) operating conditions required for liquefying biomass material can make it difficult for converting the biomass material into a useful form of bio-oil for use as transportation fuel.
  • HDO low-severity thermal liquefaction and hydrodeoxygenation
  • a method of producing a bio-oil product from biomass material comprising subjecting the biomass material to a first stage liquefaction process, the first stage liquefaction process comprising combining the biomass material with a co-solvent comprising methanol and water to form a first slurry mixture, and providing the slurry mixture within a first liquefaction reactor and maintaining the first slurry mixture at a temperature between 200 °C and 310 °C and a pressure between 1000 psig (6.9 MPa) and 2000 psig (17.2 MPa) so as to convert a portion of the biomass material into a first liquefied bio-oil product as well as form a first aqueous product and a first solid product.
  • the first liquefied bio- oil product is separated from the aqueous and solid products, and the solid product obtained from the first stage liquefaction process is subjected to a second stage liquefaction process, the second stage liquefaction process comprising combining the first solid product with methanol to form a second slurry mixture, and providing the second slurry mixture within a second liquefaction reactor and maintaining the second slurry mixture at a temperature between 200 °C and 310 °C and a pressure between 1000 psig (6.9 MPa) and 2000 psig (17.2 MPa) so as to convert a portion of the first solid product to a second liquefied bio-oil product as well as form a second aqueous product and a second solid product.
  • the first liquefied bio-oil product can be combined with the second liquefied bio- oil product to form a combined liquefied bio-oil product, where the combined liquefied bio-oil product is further combined with hydrogen in a HDO reactor at a temperature between 200 °C and 300 °C and a pressure between 1000 psig (6.9 MPa) and 2000 psig (17.2 MPa) so as to remove oxygen from carbon-based compounds within the combined liquefied bio-oil product.
  • a system is provided to perform the operations of the first and second stage liquefaction processes as described herein.
  • the systems and methods as described herein facilitate the formation of a bio-oil under less harsh conditions (e.g., at temperatures no greater than 310 °C and pressures less than 3000 psig (20.7 MPa)) than conventional biomass to bio-oil conversion processes (e.g., utilizing conventional hydrothermal liquefaction techniques), where a significant portion of the solvents used to liquefy biomass material can be recovered and recycled for re-use, and the liquefied bio- oil product has a low oxygen content (e.g., no greater than 25% by weight of the bio-oil product), a low water content (e.g., no greater than about 10% by weight of the bio-oil product, such as no greater than about 5% by weight of the bio-oil product) and further a total acid number (TAN) of less than 5 (e.g., a TAN of no greater than 3, such as a TAN from about 1-3).
  • TAN total acid number
  • the resultant HDO bio-oil product can be further reduced in oxygen content to no greater than about 10% by weight of the HDO bio-oil product.
  • the systems and methods described herein provide a yield of at least 60% (e.g., 69% or greater) of bio-oil based upon amount of input biomass to the process.
  • FIG. 1 is a schematic view of a first stage liquefaction section for a system that converts biomass to bio-oil in accordance with an example embodiment of the present invention.
  • FIG. 2 is a schematic view of a second stage liquefaction section for the system located downstream from the first stage liquefaction section of FIG. 1.
  • FIG. 3 is a schematic view of a bio-oil HDO section for the system located downstream from the second stage liquefaction section of FIG. 2.
  • a liquefaction process and corresponding systems are described herein for enhanced biomass conversion, where the system and process include a two stage liquefaction process followed by a HDO process.
  • the first stage liquefaction process utilizes water and methanol as co-solvents to liquefy biomass material
  • the second stage liquefaction process utilized methanol as a solver to liquefy biomass material remaining from the first stage liquefaction process.
  • the system and process described herein increases the yield and stability of resulting pyrolysis oil, also referred to herein as bio-oil, where the resultant bio-oil has a reduced oxygen content, and reduced water content (e.g., no greater than 5% by weight, or even as low as no greater than 1% by weight of water within the bio-oil), and a total acid number (TAN) that is lower in relation to other bio-oils formed utilizing known or conventional processes.
  • both the first and second stage liquefaction processes are free from any catalyst (i.e., the presence of a catalyst is not required in each of the first and second liquefaction stages).
  • the solvents utilized in the liquefaction stages are also easily separated and can be recycled for re-use in the process.
  • the process comprises pumping a biomass slurry into a high pressure heated reactor.
  • the product stream is de-pressurized in order to vaporize some of the excess solvent for recapture and recycle.
  • the remaining stream is filtered and the solids (e.g., non-converted biomass material) and heavy oils adsorbed on the solid are recycled for further conversion.
  • the remaining liquid reaction products are separated between organic and aqueous phases. After removal of the aqueous phase, the remaining organic phase is purified (e.g., via vacuum distillation) to yield a bio-oil product.
  • the bio-oil product is subjected to HDO to yield an oil product lower in oxygen content.
  • the separated aqueous phase can be treated to remove organic acids that are present while the remaining water and soluble sugars within the aqueous phase can be recycled to start of the liquefaction process to further increase biomass conversion and bio-oil yield (as well as minimizing water consumption).
  • the biomass liquefaction process comprises a two-stage biomass liquefaction process using a co-solvent combination of supercritical methanol and subcritical water in the first stage liquefaction process and supercritical methanol in the second stage liquefaction process so as to maximize light bio-oil production.
  • the produced bio-oil is then subjected to a bio-oil HDO process to produce a low-oxygen-content fuel intermediate (HDO oil).
  • the HDO oil can be used, e.g., at a petroleum refinery where it is mixed with a petroleum feed for co-processing at the refinery to drop-in transportation fuels.
  • All the liquefaction preheaters and reactors can be heated using a centralized hot oil heating system. Solvent methanol can be recovered for recycling using flash evaporation and distillation.
  • the overall process can be divided into three operation blocks or sections, with each section depicted in FIG. 1, FIG. 2 and FIG. 3, where the biomass is subjected to a liquefaction process in a first stage 2 (FIG. 1), followed be further liquefaction and solvent recovery in a second stage 50 (FIG. 2) to produce a light bio-oil and a heavy bio-oil, with subsequent hydrodeoxygenation (HDO) of the light bio-oil at section 100 to produce refinery ready bio-oil (FIG. 3).
  • first stage 2 FIG. 1
  • FIG. 2 second stage 50
  • HDO hydrodeoxygenation
  • the biomass utilized herein can be any suitable organic material, such as pulverized wood. Any suitable type of wood can be utilized.
  • the biomass utilized to synthesize bio-oil comprises pulverized southern pine wood that is pulverized to an average particle size in the micrometer range (e.g., average particle size of no greater than about 1000 ⁇ , such as no greater than about 150 ⁇ , or an average particle size in the range of about 100 ⁇ ).
  • average particle size in the micrometer range e.g., average particle size of no greater than about 1000 ⁇ , such as no greater than about 150 ⁇ , or an average particle size in the range of about 100 ⁇ .
  • southern pine wood that has been pulverized has a chemical composition as follows:
  • the wood can be mixed with water and methanol to produce a biomass slurry that is heated in a liquefaction reactor in the initial stages of the bio-oil synthesis process.
  • a liquefaction reactor in the initial stages of the bio-oil synthesis process.
  • the combination of water and methanol as co-solvents facilitates sufficient liquefaction (conversion of solid to liquid) of the biomass at lower temperatures (e.g., less than 350 °C) and under less harsh conditions (e.g., operating pressures under 2000 psig or 13.8 MPa) than required when using water or other aqueous solvents.
  • the time required to achieve suitable liquefaction in the reactors can be significantly reduced (e.g., 30 minutes or less) in comparison to other processes which convert biomass to bio fuel.
  • the solid biomass material is delivered to a grinding vessel or grinder 5 of the first stage liquefaction section 2 for the system, where it is sufficiently pulverized within the grinder prior to delivery (via conduit or line 6, where the line 6 can comprise, e.g., a screw extruder) to a mixing unit or mixer 8.
  • the pulverized biomass material is combined and sufficiently mixed with a co-solvent comprising water and methanol.
  • a co-solvent comprising water and methanol.
  • water and methanol are added to the mixer 8 via conduit or line 9.
  • a portion of the co-solvent e.g., water, methanol or a combination of both
  • the co-solvent e.g., water, methanol or a combination of both
  • the equipment of the system e.g., various reaction vessels, pumps, heat exchangers, fluid conduits, and other vessels
  • a suitable amount of wood biomass e.g., about 1000 US ton per day, or about 907,185 kg per day
  • the mass ratio of water to methanol for making up the co-solvent is about 1 : 1 (i.e., about the same amount in weight for water and methanol, or about 50% by weight water and about 50% by weight methanol).
  • one of the water or methanol can comprise slightly more than the other, such that each of the water and methanol can comprise from about 40% to about 60% by weight of the co-solvent.
  • the amount by weight of pulverized woody biomass mass is much greater than co-solvent in the slurry mixture.
  • a mass ratio of pulverized woody biomass to co-solvent can be at least about 5: 1, or at least about 8: 1 (e.g., about 10: 1).
  • the biomass/solvent mixture or slurry that exits the mixer 8 is pressurized and heated to a sufficient temperature and sufficient pressure that facilitates suitable conditions for liquefying the biomass material.
  • the biomass/solvent slurry is directed through a series of pumps and a heat exchanger (e.g., two pumps 10 followed by a hot-oil heat exchanger 12 provided in series as depicted in FIG. 1) to pressurize and heat the slurry prior to deliver through conduit or line 15 into a first liquefaction reactor 20.
  • the slurry can be pressurized (via pumps 10) to a pressure ranging from about 1000 psig to about 2500 psig (e.g., from about 6.9 MPa to about 17.2 MPa), such as a pressure of about 1500 psig (about 10.3 MPa).
  • the slurry is further heated (via heat exchanger 12) to a temperature ranging from about 200 °C to about 310 °C, where the temperature is preferably no greater than about 300 °C. In example embodiments, the slurry is heated to about 200 °C prior to delivery to the liquefaction reactor 20.
  • a substantially oxygen free environment is maintained within the liquefaction reactor 20, the mixture is held within the reactor at a pressure ranging from about 1000 psig to about 2500 psig (e.g., from about 6.9 MPa to about 17.2 MPa) and a temperature ranging from about 200 °C to about 310 °C, where the temperature is preferably no greater than about 300 °C.
  • the operating conditions within the reactor 20 are maintained within a range from about 280 °C to 290 °C and about 1500 psig (about 10.3 MPa). The mixture is further maintained within the reactor vessel at these operating conditions until such time as sufficient liquefaction of the biomass material has occurred.
  • the residence time within the liquefaction reactor 20 can range from about 10 minutes to about 30 minutes.
  • the solvent mixture comprises methanol in a supercritical state and water in a subcritical state.
  • These conditions within the reactor 20 are less harsh (with lower temperatures and lower pressures, e.g.., temperatures no greater than about 300 °C and pressures no greater than about 2500 psig (about 17.2 MPa)) than conventional processes for breakdown and conversion of the biomass to bio-oil (e.g., conventional processes typically require temperatures much greater than 310 °C and pressures of about 3000 psig (20.7 MPa) or greater).
  • the term "liquefied”, as used herein, refers to conversion of a solid material to a liquid material (i.e., conversion of a solid biomass material into a liquid bio-oil product).
  • the first stage liquefaction process further does not require any catalyst to achieve such conversion (i.e., the first liquefaction reactor 20 is free from any catalyst).
  • the products exiting the reactor 20 include the following: a light bio-oil material in a liquid state (which is soluble in methanol); a solid product that includes unconverted biomass material and a heavy bio-oil material adsorbed on the solids, an aqueous liquid material (including water); and gaseous products (primarily CO2).
  • about 50% by weight or more of the products exiting the liquefaction reactor 20 comprise light bio-oil material, while less than 10% by weight of the products comprise a solid material (e.g., non-converted biomass solid material and heavy bio-oil material adsorbed on the solid material), about 30-40%) (e.g., about 35% by weight) of the products comprise aqueous organic product (e.g., water and liquefied biomass carbohydrates dissolved in water), and less than 10%> by weight (e.g., no more than about 5% by weight) of the products are in gaseous form (e.g., CO2).
  • aqueous organic product e.g., water and liquefied biomass carbohydrates dissolved in water
  • gaseous form e.g., CO2
  • the oxygen content within the liquefied light bio-oil product is less than 30%> by weight (e.g., about 25% by weight).
  • the mass distribution (weight percentage) and elemental distribution (percentage of elements) of products formed within the first stage liquefaction reactor are as follows:
  • the light bio-oil obtained from the first stage liquefaction has been characterized as including the following chemical compounds. It is noted that the bio-oil was found to contain complicated chemical compounds such that only about 60% of the total peaks recorded from the GC-MS analysis were identified (using a standard GC library).
  • the liquefied light bio-oil further has an oxygen content of no greater than about 25% by weight of the light bio-oil (e.g., an oxygen content that is no greater than about 20% by weight of the light bio-oil), a water content that is no greater than about 10% by weight of the light bio-oil (e.g., a water content that is no greater than about 5% or even no greater than about 1%) by weight of the bio-oil), and a TAN (total acid number, in mg KOH/g) that is less than 5 (e.g., a TAN that is no greater than 3, such as a TAN in the range of 1-3).
  • an oxygen content of no greater than about 25% by weight of the light bio-oil e.g., an oxygen content that is no greater than about 20% by weight of the light bio-oil
  • a water content that is no greater than about 10% by weight of the light bio-oil e.g., a water content that is no greater than about 5% or even no greater than about
  • the liquefaction products exiting the reactor 20 are provided to a flash evaporation unit or evaporator 25, where the pressure is sufficiently reduced (e.g., to about 500 psig (about 3.4 MPa)) to evaporate a mixture of methanol and water (e.g., about 65% by weight methanol and about 45% by weight water) for separation along with the gaseous products from the other liquefied products.
  • a flash evaporation unit or evaporator 25 where the pressure is sufficiently reduced (e.g., to about 500 psig (about 3.4 MPa)) to evaporate a mixture of methanol and water (e.g., about 65% by weight methanol and about 45% by weight water) for separation along with the gaseous products from the other liquefied products.
  • the evaporated and gaseous products mixture exiting the flash evaporator 25 are provided (via conduit or line 28) at the reduced pressure and also a reduced temperature (e.g., between about 220 °C to about 240 °C, such as from about 230 °C to about 235 °C) to a gas-liquid separator 30.
  • the gas-liquid separator 30 is maintained at sufficient reduced temperature and pressure conditions to condense the water and methanol mixture from the other gaseous products (e.g., CO2), where the gaseous products are separated from the condensed water/methanol mixture as off gases.
  • the methanol/water mixture exiting the separator 30 is then recycled (e.g., delivered via a recycle pump 35) into recycle conduit or line 10A for delivery to the mixer 8 (where it is combined with pulverized biomass material at the starting point of the system 2).
  • the other liquefied and solid liquefaction products including light bio-oil, aqueous soluble organics and heavy bio-oil adsorbed solid material, exit the flash evaporator 25 for further processing at a secondary stage liquefaction section 50 as depicted in FIG. 2 (where point A represents a continuation in conduit or line 36 from the first stage liquefaction section 2 depicted in FIG. 1 to the second stage liquefaction section 50 depicted in FIG. 2).
  • the liquefaction products from the first stage liquefaction process are delivered from the evaporator 25 (via line 36) to a filtration unit or filter 52, where the liquid phase (including light bio-oil and aqueous soluble organics dissolved in water/methanol mixture) is separated as filtrate from the solid product residue (e.g., any unconverted wood biomass and/or other solid material as well as heavy bio-oil adsorbed on the solid material).
  • Any suitable one or more types of filters with suitable filter media can be utilized to facilitate separation of liquid products (including liquefied light bio-oil) from solid products (including heavy bio-oil).
  • the filtration unit 52 can comprise a rotary drum filter including suitable filter media to facilitate separation of liquefied products from any solid product residue.
  • the filtrate including light bio-oil and aqueous soluble organics is provided (via a conduit or line 66) to a distillation unit 68, where methanol is removed from the liquid mixture leading to a phase separation between light bio-oil (bottom phase) and aqueous organics (top phase) (e.g., via vacuum distillation at reduced pressure) as described herein.
  • the heavy bio-oil and solid product residue exiting the filter 52 is delivered (via conduit or line 54) to a mixing unit 60, where the residue is combined with a solvent comprising substantially entirely methanol (e.g., the solvent comprises methanol in an amount of at least about 90% by weight of the solvent, such as at least 95% by weight of the solvent) prior to being subjected to further liquefaction treatment in section 50.
  • Methanol can be provided from a makeup source (e.g., via conduit or line 62) as well as from a recycle source (e.g., via recycle conduit or line 64) obtained from further processing within section 50 as described herein.
  • the heavy bio-oil / methanol mixture exiting the mixer 60 is provided (via conduit or line 65 to a series of pumps series of pumps and a heat exchanger (e.g., two high pressure slurry pumps 70 followed by a hot-oil heat exchanger 72 provided in series as depicted in FIG. 2) to pressurize and heat the slurry mixture prior to deliver into a second liquefaction reactor 80 of the secondary stage liquefaction section 50.
  • a heat exchanger e.g., two high pressure slurry pumps 70 followed by a hot-oil heat exchanger 72 provided in series as depicted in FIG. 2
  • the slurry can be pressurized (via pumps 70) to a pressure ranging from about 1000 psig to about 2500 psig (e.g., from about 6.9 MPa to about 17.2 MPa), such as a pressure of about 1500 psig (about 10.3 MPa), and the slurry can also be heated (via heat exchanger 72) to a temperature ranging from about 200 °C to about 310 °C. In example embodiments, the slurry is heated to about 200 °C prior to delivery to the second liquefaction reactor 80. Operating conditions within the second liquefaction reactor 80 can be maintained at about 250 °C and about 1500 psig (about 10.3 MPa).
  • the residence time for liquefaction of heavy oil and/or solid biomass to light bio-oil within the second liquefaction reactor 80 can be similar to that for the first liquefaction reactor 20 (e.g., from about 10 minutes to about 30 minutes). Similar to the first stage liquefaction process, the stage liquefaction process also does not require any catalyst to achieve liquefaction of solids into bio-oil (i.e., the second liquefaction reactor 80 is free from any catalyst).
  • the liquefaction products exiting the second liquefaction reactor 80 (which comprise a liquefied product including light bio-oil material (where the light bio-oil material is the same or substantially similar in its properties as the light bio-material formed in the first stage liquefaction reactor 20), solid material products, and gaseous products such as CO2) are delivered (via conduit or line 82) to a flash evaporation unit or evaporator 86, where the pressure and temperature are sufficiently reduced, e.g., to a pressure of about 500 psig (about 3.4 MPa) and a temperature between about 220 °C to about 240 °C (e.g., from about 230 °C to about 235 °C), to evaporate methanol within the liquefied products for separation from the other liquefied products.
  • a flash evaporation unit or evaporator 86 where the pressure and temperature are sufficiently reduced, e.g., to a pressure of about 500 psig (about 3.4 MPa) and
  • the methanol can be evaporated and separated from the liquefied products by the evaporator 86.
  • the evaporated methanol is pressurized (e.g., via pump 88) and recycled via the recycle line 64 to the mixer 60 for combining with the heavy bio-oil and solid residue.
  • the remaining liquefied products separated from methanol in the evaporator 86 are delivered (via conduit or line 89) to a filtration unit or filter 90.
  • the filter 90 can be similar as filter 52 and provided with a suitable filter media and/or suitable configuration to facilitate separation of liquefied products as filtrate from any other solid product residue.
  • the solid product residue separated from the filtrate can be burned for heat generation or processed in any suitable manner, e.g. as carbon-based sorbent, while the filtrate is delivered to the distillation unit 68 for further processing.
  • the filtrate including light bio-oil obtained from liquefaction in the first liquefaction reactor 2 of the first stage liquefaction section 2 is combined with filtrate including the light bio-oil obtained from liquefaction in the second liquefaction reactor 80 of the second stage liquefaction section 50.
  • the distillation unit 68 operates at a reduced pressure, such as a pressure of about 150-500 psig (1.1-3.4 MPa) and also a temperature (150-200°C) that is suitable to separate methanol as vapor from the remaining liquid products (including light bio-oil, aqueous soluble organics and water).
  • the methanol separated within the distillation unit 68 is recycled (via conduit or line 10B and recycle pump 69) back to the grinder 5 and/or mixer 8 of the first stage liquefaction section 2 for combining with pulverized biomass feed (where point B represents a continuation in conduit or line 10B from the second stage liquefaction section 50 depicted in FIG. 2 to the first stage liquefaction section 2 depicted in FIG. 1).
  • phase separation vessel 94 The remaining liquid products (including light bio-oil) exiting the distillation unit 68 are directed (via conduit or line 93) to a phase separation vessel 94, where an aqueous phase including water is separated from a light bio-oil phase due to differences in hydrophobicity and density of the two phases (i.e., separation of oil from water).
  • Operating conditions within the phase separator 94 can include a pressure of about 500 psig (about 3.4 MPa) and a temperature ranging from about 220 °C to about 240 °C (e.g., ranging from about 230 °C to about 235 °C).
  • the aqueous phase separated within vessel 94 can be discarded or, preferentially, directed (via conduits or lines 95, with one or more pumps provided along the one or more lines 95) to recycle water for use by the first stage liquefaction section 2 (e.g., combining with methanol to form the co-solvent mixture for combining with pulverized biomass feed) and/or for use downstream in section 100.
  • the first stage liquefaction section 2 e.g., combining with methanol to form the co-solvent mixture for combining with pulverized biomass feed
  • the various evaporators, gas and phase separators provided within the first and second stages 2 and 50 facilitate recovery of a significant portion of the water/methanol and methanol solvents for re-use during system operation. For example, about 90% of the separated aqueous phase (which includes water and methanol) formed from the first stage liquefaction process (i.e., within liquefaction reactor 20) can be recycled back to the first stage liquefaction section 2 for re-use.
  • the biomass feed has a moisture content that accounts for about 10% of the aqueous phase, this amount can be maintained within the light bio-oil phase that is separated from the aqueous phase and emerges from the separation vessel 94.
  • the light bio-oil phase exiting the separation vessel 94 is directed to the bio-oil hydrodeoxygenation (HDO) section 100 via conduit or line 98 (where point B represents a continuation in line 98 from the second stage liquefaction section 50 depicted in FIG. 2 to the bio-oil HDO section 100 depicted in FIG. 3).
  • HDO bio-oil hydrodeoxygenation
  • the light bio-oil phase is provided (via line 98) to a mixing unit or mixer 102 of bio-oil HDO section 100.
  • the light bio-oil stream (entering the mixer via line 98) is diluted with a recycled HDO oil stream which is output from an HDO reactor 110 as described herein.
  • the light bio-oil phase is combined with the recycled HDO oil stream in a suitable ratio (e.g., at about a 1 :4 weight ratio of light bio-oil to recycled HDO oil stream) so as ensure suitable flow of the mixture emerging from the mixer 102 through the remaining portions of section 100.
  • the mixture exiting the mixer 102 is provided via a conduit or line 104 to HDO reactor 110.
  • the mixer is pressurized and heated within line 104 via one or more high pressure pumps (e.g., pump 106) and a heat exchanger 108, such that the temperature of the mixed stream is between about 200 °C to about 250 °C (e.g., about 220°C) and a pressure from about 1000 psig to about 2000 psig (from about 6.9 MPa to about 17.2 MPa), such as a pressure of about 1500 psig (about 10.3 MPa).
  • high pressure pumps e.g., pump 106
  • a heat exchanger 108 such that the temperature of the mixed stream is between about 200 °C to about 250 °C (e.g., about 220°C) and a pressure from about 1000 psig to about 2000 psig (from about 6.9 MPa to about 17.2 MPa), such as a pressure of about 1500 psig (about 10.3 MPa).
  • the heat exchanger 108 for section 100 can be configured as a countercurrent heat exchanger in which heat is exchanged between the input stream in line 104 directed to the inlet of the HDO reactor 110 and an outlet stream in conduit or line 112 which exits the reactor 110 and is directed through heat exchanger 116 as shown in FIG. 3 (i.e., heat exchangers 108 and 116 are combined as a single heat countercurrent flow heat exchanger, in which heat exchange occurs between the fluids in the inlet flow line 104 and the outlet flow line 112).
  • any other suitable heat exchange system can be provided to heat the inlet stream in line 104 to a suitable temperature (as well as cool outlet stream in line 112 to a suitable temperature).
  • the pressurized and heated mixture in input line 104 is combined with compressed hydrogen feed provided in conduit or line 142, where the hydrogen in line 142 has been compressed by a high pressure compressor 140 to a pressure that is similar to the pressure of the fluid in input line 104 (e.g., a pressure of about 1500 psig or about 10.3 MPa).
  • the hydrogen feed can be provided as a recycle feed from the output of the HDO reactor 110.
  • the ratio of hydrogen to liquid feed entering the HDO reactor 110 can be selected to enhance or maximize hydrogenolysis of and removal of oxygen from the bio-oil so as to increase the amount of hydrocarbon compounds within the light bio-oil feed stream.
  • hydrogen is provided in an amount of about 1500 L/kg of the feed stream at an operating temperature of about 220 °C and an operating pressure of about 1500 psig (about 10.3 MPa) within the HDO reactor 110.
  • carbon-based compounds within the bio-oil liquid feed react with hydrogen to remove or cleave oxygen atoms from such compounds, resulting in a reduction in the oxygen content within the bio-oil emerging from the reactor 110.
  • the operating conditions within the HDO reactor 110 are maintained at a temperature ranging from about 200 °C to about 300 °C (e.g., about 280 °C or less, such as 250 °C) and a pressure between 1000 psig (6.9 MPa) and 2000 psig (17.2 MPa) (e.g., a pressure of about 1500 psig (about 10.3 MPa)).
  • Any suitable one or combination of catalysts can be provided within the HDO reactor 110 to achieve or enhance a desired HDO reaction of the light bio-oil with hydrogen to form the HDO bio-oil.
  • the HDO bio-oil i.e., the light bio-oil processed within the HDO reactor
  • the oxygen content of the light bio-oil (at about 25% by weight or less) can be significantly reduced to no greater than about 10% by weight of the HDO bio-oil, such as no greater than about 5% by weight of the HDO bio-oil, or even as low as no greater than about 1%) by weight of the HDO bio-oil.
  • the HDO bio-oil further has a low TAN of 1-3 and even as low as a TAN less than 1.
  • the HDO products emerging from the reactor in exit conduit or line 112 include HDO oil, aqueous products and gases (e.g., hydrogen and methane).
  • the HDO products are cooled in heat exchanger 116 from the HDO reaction temperature (e.g., the same heat exchanger 108 as previously described herein, where the HDO products are used to heat the input bio-oil stream to the HDO reactor 110) of 200-280°C to about 30°C and then delivered to a gas/liquid separation unit or gas/liquid separator 120.
  • the cooled HDO products are separated within the gas/liquid separator 120 between gaseous products and liquid products.
  • the gaseous products comprise substantially (e.g., 90% by weight or greater) hydrogen, but also include methane.
  • the gaseous products exiting the gas/liquid separator 120 are provided to an inlet of a pressure swing adsorption (PSA) unit 124, which operates at a pressure of about 300 psig (about 2.1 MPa) to separate some or all of the hydrogen from the remaining gases (e.g., where hydrogen is non-adsorbed or substantially non-adsorbed on a selected surface and therefore can be separated from the remaining adsorbed gases within the PSA unit) and exits the PSA unit 124 via recycle conduit or line 136.
  • the hydrogen in line 136 is provide to the compressor 140 where it is compressed to a suitable pressure and combined with the bio-oil stream in line 104 prior to input to the HDO reactor 110.
  • the liquid products exiting the gas/liquid separator 120 are directed to a further phase separation unit or phase separator 130 to separate the aqueous phase (i.e., phase including water) from the HDO bio-oil phase based upon differences in their hydrophobicity.
  • the separated aqueous phase exits the separator 130 via conduit or line 135, where it can be discarded or further processed for a particular application.
  • the separated HDO bio-oil phase exits the separator 130 via conduit or line 134, where it can be utilized as a fuel in certain applications.
  • a portion of the separated HDO bio-oil phase is also provided via line 132 to the mixer 102 for combining with the light oil feed of line 98 as previously described herein.
  • the system and process described herein and depicted in the figures results in the formation of a final (HDO) bio-oil product having a reduced water content and a reduced oxygen content in relation to other bio-oils formed from woody biomass.
  • the system and methods as described herein facilitates the formation of bio-oils having a water content of no greater than about 5% by weight of the bio-oil (or even as little as no greater than 1% by weight of the bio-oil).
  • the bio-oils formed herein can have an oxygen content of no greater than about 10% by weight of the bio-oil, in particular no greater than about 5% by weight of the bio- oil (e.g., no greater than about 1% by weight of the bio-oil) and also a TAN (total acid number, as measured in mg KOH/g of oil) within the range of about 1 to about 3 (where the final HDO bio-oil can further have a TAN of less than 1).
  • Bio-oils formed in accordance with the techniques described herein include hydrocarbons ranging from Cio to C24 carbon chains (where the bio- oils can also include hydrocarbons less than Cio and greater than C24), which facilitate blending and solubility with diesel oil and/or other petroleum products.
  • the two stage liquefaction process (utilizing the solvents and operating conditions as described herein) combined with the HDO process can result in an overall biomass conversion rate that is significant.
  • the system and process described herein and depicted in the figures can result in a yield of at least 60% (e.g., 69% or greater) of bio-oil based upon amount of input biomass to the process.
  • a biomass material can be converted at high yield to a bio-oil that is low in oxygen and water content, has a low acid content (low TAN), and is suitable for direct blending with petroleum products for a variety of applications.
  • the two stage liquefaction portion of the process utilizes solvents (methanol/water combination for the first stage and methanol for the second stage) that are readily recovered after liquefaction of the biomass and therefore available for recycling/reuse in the process, and the liquefaction is achieved in the absence of any catalyst (i.e., no catalyst present in either of the first and second stage liquefaction reactors).
  • the operating conditions required in the liquefaction stages are very mild, with much lower temperatures and pressures required to liquefy the woody biomass in comparison to conventional biomass liquefaction techniques.

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Abstract

La présente invention concerne un produit d'huile biologique qui est produit à partir d'un matériau de biomasse par soumission du matériau de biomasse à un processus de liquéfaction de premier étage, le processus de liquéfaction de premier étage comprenant la combinaison du matériau de biomasse avec un cosolvant comprenant du méthanol et de l'eau pour former un premier mélange de suspension concentrée, le transfert du mélange de suspension concentrée dans un premier réacteur de liquéfaction et le maintien du premier mélange de suspension concentrée à une température et une pression suffisantes de façon à convertir une partie du matériau de biomasse en un premier produit d'huile biologique liquéfié, ainsi que la formation d'un premier produit aqueux et d'un premier produit solide, et la séparation du premier produit d'huile biologique liquéfié des produits aqueux et solides. Le produit solide obtenu à partir du processus de liquéfaction de premier étage est soumis à un processus de liquéfaction de deuxième étage, le processus de liquéfaction de deuxième étage comprenant la combinaison du premier produit solide avec du méthane pour former un deuxième mélange de suspension concentrée, et le transfert du deuxième mélange de suspension concentrée dans un deuxième réacteur de liquéfaction et le maintien du deuxième mélange de suspension concentrée à une température et une pression suffisantes pour convertir une partie du premier produit solide en un deuxième produit d'huile biologique liquéfié, ainsi que la formation d'un deuxième produit aqueux et d'un deuxième produit solide.
PCT/US2018/026471 2017-04-07 2018-04-06 Liquéfaction de biomasse pour produire une huile biologique prête au raffinage WO2018187699A1 (fr)

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CN111808624B (zh) * 2020-07-08 2022-02-01 南京工程学院 一种具备跨季节储能功能的生物质热解-水热甲烷化多联产工艺及其装置
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KR20240032977A (ko) 2021-07-09 2024-03-12 카본 테크놀로지 홀딩스, 엘엘씨 고 고정-탄소 함량 및 최적화된 반응성을 갖는 바이오카본 펠릿을 생산하기 위한 공정, 및 이로부터 수득된 바이오카본 펠릿
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JP2024531101A (ja) * 2021-08-02 2024-08-29 カーボン テクノロジー ホールディングス， エルエルシー バイオマス熱分解液体から炭素を再捕捉するためのプロセス及びシステム
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