WO2014066594A1 - Procédé de préparation de biobrut à partir de biomasse humide caractérisé par un rendement amélioré - Google Patents

Procédé de préparation de biobrut à partir de biomasse humide caractérisé par un rendement amélioré Download PDF

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Publication number
WO2014066594A1
WO2014066594A1 PCT/US2013/066538 US2013066538W WO2014066594A1 WO 2014066594 A1 WO2014066594 A1 WO 2014066594A1 US 2013066538 W US2013066538 W US 2013066538W WO 2014066594 A1 WO2014066594 A1 WO 2014066594A1
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Prior art keywords
biocrude
wet biomass
temperature
biomass
time
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PCT/US2013/066538
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English (en)
Inventor
Phillip E. Savage
Julia FAETH
Peter J. VALDEZ
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The Regents Of The University Of Michigan
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Publication of WO2014066594A1 publication Critical patent/WO2014066594A1/fr

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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
    • C10G1/008—Controlling or regulating of liquefaction 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
    • C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • 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
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • 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 generally relates to a method of preparing a biocrude and, more specifically, a method of preparing a biocrude from a wet biomass, wherein the method achieves improved yield of the biocrude while having a faster reaction time.
  • Biocrude and bio-oil are generally derived from a biomass, e.g. organisms and/or organic materials, which may be used to produce energy. Because biocrude and bio-oil are derived from a biomass, the biocrude and the bio-oil are generally referred to as a renewable resource and, unlike fossil fuels, biocrude and bio-oil do not adversely impact the carbon cycle of the earth.
  • Bio-oil is generally classified as either “first generation” bio-oil, "second generation” bio-oil, or “third generation” bio-oil.
  • First generation bio-oil is produced from “edible” biomass such as corn, soybeans, or other crops. Generally, the edible biomass is processed in a manner which generates liquid bio-oil, such as grain ethanol and soy biodiesel.
  • Second-generation bio-oils are produced from non-food biomass, such as lignocellulosic biomass, e.g., jatropha oil.
  • Third-generation bio-oil may be referred to as algae fuel and is derived from algae. Third-generation bio-oil is generally derived from lipids in the algae.
  • hydrothermal liquefaction One conventional method of preparing biocrude from algae is generally referred to as hydrothermal liquefaction.
  • a slurry of algae and water is subjected to high temperature and pressure in a vessel.
  • a temperature of the reaction vessel is increased overtime to reach a desired setpoint temperature, and the slurry is maintained at the desired setpoint temperature for an extended period of time, e.g. 60 minutes or more, to prepare the biocrude.
  • conventional hydrothermal liquefaction is time consuming and, as such, there are significant costs associated with a high output of the biocrude.
  • the present invention provides a method of preparing a biocrude from a wet biomass.
  • the method comprises the step of providing the wet biomass.
  • the method further comprises heating the wet biomass for a first period of time from ambient temperature to a first temperature of from about 100 to about 600 °C to form a reaction mixture comprising the biocrude.
  • the method further comprises the step of heating the reaction mixture at the first temperature for a second period of time.
  • the first period of time and the second period of time are collectively less than about 180 seconds.
  • the present invention also provides an alternative method of preparing a biocrude from a wet biomass.
  • the alternative method comprises the step of providing the wet biomass.
  • the alternative method further comprises selecting a setpoint temperature of at least 300 °C.
  • the alternative method comprises the step of heating the wet biomass at the setpoint temperature such that the wet biomass is heated from ambient temperature at the setpoint temperature for a period of time of less than about 180 seconds, thereby forming a reaction mixture comprising the biocrude.
  • the methods of the present invention prepare a biocrude at a much faster rate than conventional methods, thereby decreasing significantly costs associated with obtaining a desired output or volume of the biocrude.
  • the instant method may be carried out numerous times in the same amount of time required to carry out but one conventional method, thus increasing considerably an output of the biocrude for the given volume of the reaction vessel.
  • Figure 1 is a graph of a temperature profile as a function of time for certain setpoint temperatures of a reaction vessel
  • Figure 2 is another graph of a temperature profile as a function of time for certain setpoint temperatures of a reaction vessel
  • Figure 3 is a graph of biocrude yield (wt. on a dry ash free basis) versus reaction time for a setpoint temperature of 600 °C;
  • Figure 4 is a graph of biocrude yield (wt.% on a dry ash free basis) versus a solids content of wet biomass time for a setpoint temperature of 600 °C and a reaction time of 1 minute;
  • Figure 5 is a graph of biocrude yield (wt.% on a dry ash free basis) versus a total mass loading in a reaction vessel for a setpoint temperature of 600 °C and a reaction time of 1 minute;
  • Figure 6 is a graph of biocrude yield (wt. %) on a dry basis of the biocrude formed via the instant method from certain microalgaes as compared to the biocrude yield formed via conventional hydrothermal liquefaction for these same microalgaes;
  • Figure 7 is a graph of biocrude yield (wt. ) on a dry ash free basis of the biocrude formed via the instant method from certain microorganisms as compared to the biocrude yield formed via conventional hydrothermal liquefaction for these same microorganisms.
  • the present invention provides a method of preparing a biocrude from a wet biomass.
  • the instant method is particularly suitable for preparing biocrude from a wet biomass at much faster rate than conventional methods, such as conventional hydrothermal liquefaction, while providing an even higher yield of the biocrude from the wet biomass than that which is obtainable from conventional methods.
  • the method comprises providing the wet biomass, which is typically a slurry or mixture of biomass solids and water.
  • the wet biomass comprises the biomass solids in an amount ranging from 1 to 66, alternatively from 10 to 30, alternatively, from 15 to 25, weight percent, based on the total weight of the wet biomass utilized in the instant method.
  • water is present in the wet biomass in an amount ranging from 34 to 99, alternatively from 70 to 90, alternatively from 75 to 85, weight percent, based on the total weight of the wet biomass utilized in the instant method.
  • the amount of the biomass solids in the wet biomass may be referred to as the solids content of the wet biomass.
  • the biomass solids of the wet biomass are typically generated by or derived from renewable sources, such as vegetation and/or organisms.
  • Common biomass solids include those derived or generated from lignocellulosic biomass or components thereof, such as cellulose, hemicellulose and/or lignin.
  • the biomass solids may be selected from, for example, agricultural residues, crops, wood residues, paper, etc.
  • the biomass solids of the wet biomass include, but are not limited to, paper, paper products, paper waste, wood, particle board, sawdust, agricultural waste, silage, grasses, rice hulls, bagasse, cotton, jute, hemp, flax, bamboo, sisal, abaca, straw, corn cobs, corn stover, switchgrass, alfalfa, hay, rice hulls, coconut hair, cotton, etc.
  • the wet biomass comprises an aquatic biomass.
  • One specific type of aquatic biomass particularly suitable for the instant method is algae.
  • the algae suitable for the aquatic biomass of the instant method may be any organism comprising chlorophyll but which does not include roots, stems, and leaves.
  • the algae may be single-celled or multicellular. Further, the algae may be selected from prokaryotic and/or eukaryotic organisms.
  • the algae may comprise macroalgae, which is colloquially referred to as seaweed, and/or the algae may comprise microalgae. Is various embodiments, the aquatic biomass comprises microalgae.
  • the microalgae may comprise any microscopic algae, photoautotrophic or photoauxotrophic protozoa, photoautotrophic or photoauxotrophic prokaryote, and/or cyanobacteria.
  • the microalgae may be in the form of an algae culture, a concentrated algae culture, or a dewatered mass of algae. Further, the microalgae may be in a liquid, semi-solid, or solid form (at least until combined with water to form the wet biomass). Additionally, the microalgae may comprise plankton, including phytoplankton, zooplankton, and/or bacterioplankton.
  • the microalgae may comprise a naturally-occurring microalgae, a genetically-modified microalgae, a transgenic microalgae, and/or a synthetic microalgae.
  • the microalgae may be from any geographic location or climate. Further, the microalgae may be from various aquatic environments, such as freshwater (e.g. from rivers, lakes, or ponds) and/or saltwater environments (e.g. the ocean).
  • the wet biomass may comprise any combination of microalgaes, including various combinations of multicellular organisms, single-celled organisms, cell fragments/components of the multicellular or single celled organisms, e.g., organelles, proteins, lipids, and the like. Further, the wet biomass may comprise any combination of different types of but one of these categories of microalgae, e.g. the wet biomass may comprise two or more different types of single-celled organisms.
  • microalgae particularly suitable for the instant method is Nannochloropsis sp, which may be obtained under the name Nannochloropsis 3600TM from Reed Mariculture of Campbell, California.
  • the algae may comprise Chlorella vulgaris (C. vulgaris).
  • suitable microalgaes include Neochloris oleoabundans (N. oleoabundans), and/or Botryococcus braunii (B. braunii). Any combination of microalgaes, or microalgae species within the genuses identified above, may be utilized in the method.
  • Various different types of biomass solids may be utilized based off of selection criteria including, but not limited to, lipid yields, fatty acid profile, growth/reproduction rate, photosynthetic efficiency, and combinations thereof.
  • the wet biomass may comprise an organism other than the aquatic biomass or algae.
  • the wet biomass may comprise bacteria and/or yeast.
  • Escherichia coli E. coli
  • E. coli E. coli
  • E. coli TB and E. coli MM designates E. coli grown in different media.
  • the acronym "TB” stands for "terrific broth”
  • the acronym "MM” stands for minimal medium.
  • the biomass solids may be purchased or otherwise obtained and subsequently mixed with water to provide the wet biomass, or the wet biomass may be purchased or otherwise obtained such that no preparation is necessary.
  • water When water is added to the biomass solids to form the wet biomass, the water may be derived from any source. However the water is typically deionized and may be purified via reverse osmosis, distillation, etc. so as to minimize any impurities present in the wet biomass.
  • the method may include the step of producing biomass solids.
  • the biomass solids comprise algae
  • the biomass solids can be produced through growing algae.
  • the algae are grown in at least one bioreactor.
  • bioreactors suitable for growing algae or supporting algae cultures include, but are not limited to, continuously-fed bubble column reactors and stir tanks.
  • the algae may be grown phototrophically and/or heterotrophically.
  • the algae are grown phototrophically in a series of continuously-fed bubble column reactors and then heterotrophically in a stir tank. Without being bound to any particular theory, it is believed that sequential phototrophic and heterotrophic growth of the algae increases biomass density, lipid productivity, lipid content, lipid profile, fatty acid content, and carbon substrate utilization efficiency of the algae, which is advantageous for the instant method.
  • the algae may be treated during its growth to maximize lipid productivity and/or biomass solids density.
  • the algae are typically treated by chemical and/or physical stimulation.
  • chemical and/or physical stimulation include, but are not limited to, manipulating nutrient concentration, pH, temperature, irradiance, genes, and combinations thereof.
  • the algae are subjected to nitrogen stress.
  • the algae are grown on glucose and in heterotrophic growth conditions for a period of time, which may range from 1 to 10, alternatively from 4 to 8, alternatively from 6 to 8, days. Without being bound to any particular theory, it is believed that treating the algae with nitrogen stress in heterotrophic growth conditions also improves lipid productivity of the algae.
  • the method may further include the step of dewatering the biomass solids.
  • suitable dewatering techniques include, but are not limited to, centrifugation, gravity sedimentation, autoflocculation, flocculation with organic or microbial products, in-situ microbial flocculation, dissolved air flotation, belt filtration, membrane filtration, and combinations thereof.
  • Dewatering techniques may be used to further modify, e.g. increase, the density of the biomass solids.
  • the biomass solids may be prepared from an algae paste and subsequently mixed with water to form the wet biomass.
  • the biomass solids may be prepared raw, i.e., the source of biomass solids may be used without dewatering.
  • the lipid content of the biomass solids is typically measured as a percentage by weight of all lipids present in the biomass solids, based on the total weight of the biomass solids.
  • the biomass solids have a lipid content of from 20 to 80, alternatively from 30 to 60, weight percent, based on the total weight of the biomass solids.
  • the instant method further comprises heating the wet biomass for a first period of time from ambient temperature to a first temperature to form a reaction mixture comprising the biocrude.
  • the method further comprises the step of heating the reaction mixture at the first temperature for a second period of time.
  • the method disclosed herein may be carried out in a variety of devices or vessels, as will be appreciated by one of ordinary skill in the art.
  • the method may be performed in a biomass refinement system.
  • the biomass refinement system generally includes a reaction vessel, which may optionally be utilized as part of a biocrude reactor or as part of an upgrading reactor.
  • the reaction vessel is typically selected so as to have a design and configuration capable of withstanding the temperature and pressure conditions associated with the method disclosed herein, as described below.
  • the reaction vessel comprises an autoclave.
  • the reaction vessel may further include or otherwise be fitted with a heating system, e.g. a heating jacket, which contacts at least an exterior of the reaction vessel.
  • the heating jacket may be used in conjunction with other components that may be present in the biomass refinement system, such as a thermal sand bath.
  • the reaction vessel may be heated with a fluidized sand bath.
  • the reaction vessel may be connected and/or coupled to other devices, such as a resistance heater, an induction heater, or a microwave heater, for rapid heating of the reaction vessel.
  • the biomass refinement system may also include a temperature controller operative to control the temperature of and within the reaction vessel.
  • the biomass refinement system may additionally comprise a mixer device and a mixer controller.
  • the mixer device may be selected from various paddles, stirrers, and/or agitators, etc. as understood in the art.
  • the mixer device may serve to mix the wet biomass throughout the step of heating the wet biomass to the first temperature and/or at the first temperature.
  • the mixer controller is generally coupled to the mixer device to control the mixing speed of the mixer device.
  • the biomass refinement system may further comprise various input and output valves and/or associated piping.
  • the biomass refinement system may further comprise at least one water inlet and at least one water outlet connected to the interior of the reaction vessel.
  • the biomass refinement system may include an H 2 system connected to the reaction vessel to provide pressurized hydrogen to the interior of the reaction vessel.
  • the biomass refinement system comprises a reaction vessel with a heating system comprising a thermal sand bath.
  • the biomass refinement system may include a vacuum pump coupled to the interior of the reaction vessel to remove air.
  • the biomass refinement system may also include the H 2 system and and/or inert gas system, which, if present, are in fluid communication with the interior of the reaction vessel.
  • the biomass refinement system may include two or more reaction vessels.
  • the biomass refinement system includes a first reactor to heat the wet biomass to the first temperature to form the reaction mixture.
  • the biomass refinement system may optionally include a second reactor to heat the reaction mixture at the first temperature.
  • the method comprises heating the wet biomass for a first period of time from ambient temperature to the first temperature.
  • Ambient temperature is generally an ambient temperature at a location where the method is carried out.
  • ambient temperature is from about 15 to about 30 °C.
  • ambient temperature may vary based on geographical location and climate, i.e., ambient temperature may deviate from the ranges set forth above depending upon the geographical location and climate in which the method is carried out.
  • the wet biomass may optionally be slightly cooled or heated to temperature slightly below or above ambient temperature (e.g. room temperature) prior to carrying out the method without deviating from the scope of the instant invention.
  • the method is typically free from such a step.
  • the first temperature to which the wet biomass is heated is from 100 to 600, alternatively from 100 to 500, alternatively from 100 to 400, alternatively from 125 to 375, °C.
  • the method is typically carried out in a reaction vessel, as introduced above and described in greater detail below.
  • the first temperature to which the wet biomass is heated refers to the temperature of the wet biomass itself and not merely a setpoint temperature of the reaction vessel in which the wet biomass is heated.
  • a temperature of the reaction vessel may be much greater than the a temperature of the contents of the reaction vessel, yet the first temperature relates solely to the temperature of the wet biomass within the reaction vessel independent of the temperature of the reaction vessel itself (and independent of any of the temperature of any heating source utilized in heating the reaction vessel).
  • the wet biomass may be heated at 600 °C, but only heated to 175- 200 °C.
  • the instant method optionally further comprises the step of heating the reaction mixture at the first temperature for a second period of time.
  • the method is free from the step of heating the reaction mixture at the first temperature.
  • the method typically comprises heating the wet biomass from ambient temperature to the first temperature without continued heating at the first temperature once the wet biomass reaches the first temperature.
  • heating the reaction mixture at the first temperature for the second period of time is generally defined as heating at a steady state temperature of the reaction mixture, as distinguished heating the wet biomass to the first temperature.
  • the first temperature is 300 °C
  • heating the wet biomass or the reaction mixture from 100 °C to the first temperature of 300 °C constitutes heating to the first temperature, as opposed to heating at the first temperature, because the wet biomass or the reaction mixture has not yet reached steady state temperature of 300 °C.
  • the first period of time and the second period of time are collectively less than about 180, alternatively less than about 150, alternatively less than about 120, alternatively less than about 100, alternatively less than about 90, alternatively less than about 80, alternatively less than about 70, alternatively less than about 60, alternatively less than about 50, alternatively less than about 40, alternatively less than about 30, alternatively less than about 20, alternatively less than about 10, alternatively less than about 5, seconds.
  • the first period of time and the second period of time are collectively from 30 to 60, alternatively from 35-45, alternatively from 40-50, seconds.
  • the first period of time and the second period of time account for the total time that the wet biomass is heated, including the time required for the contents of the reaction vessel to reach steady state temperature (in the event that the contents of the reaction vessel actually reach steady state temperature in the method).
  • the first period of time and the second period of time may be collectively referred to as the reaction time.
  • the reaction time When the method is free from the step of heating for the second period of time, the first period of time alone may be referred to as the reaction time.
  • the method comprising selecting a setpoint temperature.
  • the setpoint temperature is typically at least 300, alternatively at least 400, alternatively at least 500, alternatively at least 600, °C.
  • the setpoint temperature is the temperature at which the reaction vessel including the wet biomass is heated.
  • the setpoint temperature is typically 500- 700 °C, although higher setpoint temperatures are contemplated, e.g. 700-1,000 °C.
  • the method further comprises heating the wet biomass at the setpoint temperature such that the wet biomass is heated from ambient temperature at the setpoint temperature for a period of time less than about 180 seconds, thereby forming the reaction mixture comprising the biocrude.
  • the period of time is correlated to the combined first and second periods of time of the embodiment described above.
  • the setpoint temperature is merely the temperature at which the reaction vessel is heated, i.e., the wet biomass or reaction mixture may not actually reach the setpoint temperature in the method.
  • the wet biomass or reaction mixture may only reach a temperature of, for example, 250-400 °C, depending on a rate at which the wet biomass is heated and the first period of time.
  • the greater the setpoint temperature the greater the rate at which the temperature of the wet biomass or reaction mixture increases, because the wet biomass or reaction mixture is generally heated at the setpoint temperature.
  • the setpoint temperature is generally greater than the first temperature to which the wet biomass is heated because the first period of time during which the wet biomass is heated is typically less than the time required for the wet biomass to reach the setpoint temperature.
  • the step of heating the wet biomass to the first temperature, and/or the step of heating the wet biomass at the setpoint temperature typically comprises heating the wet biomass at a rate of at least about 100, alternatively at least about 125, alternatively at least about 150, alternatively at least about 175, alternatively at least about 200, alternatively at least about 225, alternatively at least about 250, °C/min.
  • the rate at which the wet biomass is heated may vary significantly from the rates disclosed above.
  • the wet biomass may be heated at a rate of at least about 500, or even at least about 1000, °C/min.
  • Such rates may be utilized when the first and second periods of time are collectively less than about, for example, 30 seconds.
  • heating the wet biomass at a rate of 1,000 °C/min for about 30 seconds would result in heating the wet biomass to a temperature of about 500 °C, i.e., the first temperature would be about 500 ° C in this particular embodiment.
  • this rate may be a factor of the first temperature and/or the setpoint temperature, with the rate and the first temperature (or the setpoint temperature) being directly proportional to one another.
  • the wet biomass may be heated to the first temperature without necessarily having a setpoint temperature.
  • Heating to the first temperature and heating at the setpoint temperature are two equivalent ways to describe similar heating steps, although the actual temperatures associated with the first temperature and the setpoint temperature are not equivalent, as described above.
  • the method can be described in different ways.
  • the setpoint temperature is 400 °C
  • the first temperature to which the wet biomass is heated is generally less than the setpoint temperature of 400 °C, assuming that the wet biomass does not reach steady state temperature.
  • this embodiment can be described as heating the wet biomass from ambient temperature to a first temperature of from 100 to 400 °C for a first period of time of less than about 180 seconds.
  • this embodiment can be described as heating the wet biomass from ambient temperature to a first temperature of 400 °C for a first period of time to form a reaction mixture, and heating the reaction mixture at the first temperature of 400 °C for a second period of time such that the first period of time and the second period of time are collectively less than 180 seconds.
  • this embodiment can be described as selecting a setpoint temperature of 400 °C, heating the wet biomass for a first period of time at the setpoint temperature such that the wet biomass is heated from ambient temperature at the setpoint temperature of 400 °C for a period of time of less than about 180 seconds, thereby forming a reaction mixture comprising the wet biomass.
  • the step of heating the wet biomass from ambient temperature to the first temperature may be considered, at least in part, hydrothermal liquefaction.
  • Hydrothermal liquefaction is the aqueous-phase conversion of the wet biomass into biocrude.
  • hydrothermal liquefaction converts the wet biomass into an oily or tarry fluid via reactions in and with liquid water at elevated temperatures and above the saturation pressure of water.
  • water may serve as a solvent, a catalyst (or catalyst precursor), and/or a reactant (e.g., in hydrolysis reactions).
  • the various components of the biomass solids are converted from carbonaceous solids to various hydrocarbons, phenolic compounds, and other fluids during hydrothermal liquefaction which may have heating value.
  • the instant method is distinguishable from conventional hydrothermal liquefaction methods, as described below.
  • a starting pressure of the reaction vessel before the step of heating the wet biomass to the first temperature may be increased with various mediums.
  • the wet biomass is pressurized to a pressure of from about 10 to about 4,000, alternatively from about 50 to about 3,800, alternatively from about 70 to about 3,500, kPa, prior to the step of heating the wet biomass to the first temperature.
  • the wet biomass may be pressurized via various gases, such as helium and/or hydrogen.
  • the reaction vessel is not pressured prior to the step of heating the wet biomass to the first temperature. Instead, in these embodiments, the reaction vessel may be loaded with the wet biomass in an amount sufficient to provide a desired pressure within the reaction vessel based on the first temperature and corresponding steam tables for water.
  • Heating the wet biomass to and at the first temperature in the reaction vessel causes the pressure within the reaction vessel to rise.
  • the pressure within the reaction vessel may be selectively controlled during the instant method according to known methods dependent upon a desired pressure.
  • the density of the contents within the reaction vessel may be monitored in order to indirectly ascertain the pressure within the reaction vessel during the steps of heating the wet biomass to and at the first temperature.
  • the reaction vessel is loaded with the wet biomass in an amount to provide a pressure of from 300 to 500, alternatively from 350 to 450, bar when the wet biomass reaches the first temperature.
  • the starting pressure of the reaction vessel may be greater than atmospheric pressure, and because the pressure within the reaction vessel generally increases during the method, the pressure within the reaction vessel may be greater than the pressures described above during the step of heating the wet biomass to the first temperature. Further, because the pressure within the reaction vessel may increase as the wet biomass is heated to the first temperature, i.e., as the temperature within the reaction vessel increases, the pressure within the reaction vessel may be dynamic rather than static in the instant method.
  • the step of heating the wet biomass to the first temperature and/or the step of heating the reaction mixture at the first temperature may be conducted in the presence of a catalyst.
  • the catalyst is typically a heterogeneous catalyst selected from the group consisting of Pd/C, Pt/C, Ru/C, Ni/Si0 2 -Al 2 0 3 , sulfided CoMo/D -Al 2 0 3 , zeolite, activated carbon, and combinations thereof.
  • noble metal catalysts including, but not limited to, Pd/C, Pt/C, Ru/C, maximize the hydrogen to carbon molar ratio of the biocrude.
  • Ru/C and Ni/Si0 2 -Al 2 C>3 are capable of providing in situ denitrogenation during the step of heating of the wet biomass to the first temperature.
  • the biocrudes obtained with utilizing as a catalyst Pd/C, Pt/C, Ru/C and/or CoMo/D - AI2O 3 may be less viscous than the biocrude obtained with uncatalyzed or zeolite- catalyzed heating, all other factors being equal.
  • the biocrude obtained with utilizing as a catalyst Ni/Si0 2 -Al 2 C>3 generally has a dark red hue.
  • the amount of catalyst utilized may range in an amount ranging from 0 to 75, alternatively from 10 to 50, alternatively from 10 to 40, alternatively from 20 to 30, weight percent, based on the total weight of the wet biomass prior to any reaction. In certain embodiments, the method does not utilize the catalyst.
  • the step of heating the wet biomass to the first temperature and/or the step of heating the reaction mixture at the first temperature may be conducted in the presence of various additives including, but not limited to, metal salts and bases.
  • the metal salts include, for example, NaCl, MnCl 2 , ZnCl 2 , CoCl 2 , Q1SO4, and MgS0 4 .
  • the bases include, for example, NaOH and KOH. Without being limited by theory, it is believed that the additions of metal salts and/or bases may affect the extent of decarboxylation of the biocrude. In certain embodiments, the method does not utilize metal salts and/or bases.
  • the step of heating the wet biomass to the first temperature and/or the step of heating the reaction mixture at the first temperature may be conducted in a reducing atmosphere. It is believed that utilizing the reducing atmosphere yields reduced amounts of C0 2 in the gas produced along with the biocrude and eliminates or minimizes production of C 2 H4, which results in the biocrude having a more desirable quality.
  • the reducing atmosphere may be present in the reaction vessel prior to the step of heating the wet biomass to the first temperature. Alternatively, the reducing atmosphere may be introduced into the reaction vessel during the step of heating the wet biomass to the first temperature and/or during the step of heating the reaction mixture at the first temperature.
  • the reducing atmosphere comprises pressurized hydrogen gas.
  • the reducing atmosphere may comprise gaseous reducing agents other than or in addition to hydrogen.
  • the pressurized hydrogen gas may have a pressure ranging from 0.1 to 30, alternatively from 20 to 30, alternatively from 5 to 25, MPa.
  • the pressurized hydrogen may hydrogenate the unsaturated heterocyclic ring and hydrocrack the subsequent products during the step of heating the wet biomass and/or heating the reaction mixture.
  • the reducing atmosphere may optionally be utilized in combination with the catalyst described above.
  • the step of heating the wet biomass to the first temperature and/or the step of heating the reaction mixture at the first temperature may be conducted in an inert atmosphere, e.g. in the presence of at least one inert gas.
  • the inert gas may be utilized in concert with the catalyst described above, which may improve yield of the biocrude formed via the method.
  • the inert atmosphere may replace air inside of the reaction vessel and minimize undesirable reactions that occur between the wet biomass and components in the air.
  • the inert atmosphere may be present in the reaction vessel prior to the step of heating the wet biomass to the first temperature.
  • the inert atmosphere may be introduced into the reaction vessel during the step of heating the wet biomass to the first temperature and/or during the step of heating the reaction mixture at the first temperature.
  • an inert gas suitable for the inert atmosphere is helium.
  • inert gases other than or in addition to helium may also be utilized in the instant method.
  • the inert atmosphere may have, for example, a pressure ranging from 0 to about 250, alternatively from about 50 to about 225, alternatively from about 70 to about 200, alternatively from about 90 to about 150, kPa.
  • the inert atmosphere may be provided in the reaction vessel after evacuating at least a portion of the air from the reaction vessel. The evacuation of the air may be performed with a vacuum pump or other suitable methods.
  • the step of heating the wet biomass to the first temperature and/or the step of heating the reaction mixture at the first temperature are conducted in the absence of a reducing or an inert atmosphere.
  • a headspace of the reaction vessel generally comprises air.
  • the reaction product typically comprises an organic phase, an aqueous phase, and a gas phase.
  • the reaction product may further include a solid phase.
  • the gas of the reaction mixture above the biocrude may comprise C0 2 , H 2 , CH 4 , and/or combinations thereof.
  • the gas above the biocrude may additionally comprise, for example, 0 2 , CO, N 2 , C 2 H 4 , C 2 H 6 , and/or combinations thereof.
  • the biocrude is generally present in the organic phase and is in liquid form.
  • the method further comprises recovering, e.g. isolating, the biocrude from the reaction mixture.
  • the biocrude may be recovered from the reaction mixture via known methods.
  • a solvent such as dichloromethane may be utilized to rinse the reaction vessel, and the reaction mixture, along with the solvent, may be vortexted and/or centrifuged.
  • the solid phase accumulates at an interface of the aqueous phase and the organic phase.
  • the organic phase may be separated from the aqueous phase (and the solid phase) via various methods, e.g. by decanting or via a pipette.
  • the solvent may be removed from the organic phase by flowing N 2 over the organic phase.
  • the remaining product which is typically soluble in the solvent, is classified as the biocrude.
  • the biocrude may include phenolic compounds, long-chain alkanes, and/or fatty acids.
  • fatty acids include, but are not limited to, palmitic acid and palmitoleic acid.
  • long-chain alkanes include, but are not limited to, pentadecane, heptadecane, substituted hexadecanes, nonadecane, docosane, heptacosane, nonacosane, triacontane, hentriacontane, and heptacosane.
  • the phenolic compounds may include alkyl phenols and benzenes.
  • the biocrude may also include other organic acids, long-chain hydrocarbons (unsaturated and saturated), indoles, piperidine derivatives, cholesterol, cholestane, cholestene, amides, other N-containing compounds, and combinations thereof.
  • the biocrude may be further classified as comprising a light biocrude and a heavy biocrude.
  • the method further comprises refining or separating the biocrude into the light biocrude and the heavy biocrude.
  • a second solvent such as n-hexane
  • the mixture may be vortexed and/or centrifuged.
  • the soluble biocrude is classified as the light biocrude, whereas the insoluble biocrude is classified as the heavy biocrude.
  • the light and heavy biocrudes may be isolated from one another by, for example, decanting the solvent phase including the light biocrude from the mixture.
  • the solvent may be removed from the light biocrude via N 2 .
  • the relative amounts of the light biocrude and the heavy biocrude within the biocrude are typically a function of the first temperature (or setpoint temperature) and the period of time during which the wet biomass is heated. For example, generally speaking, at greater temperatures, the relative amount of light biocrude is maximized when the first temperature (or setpoint temperature) is minimized, i.e., the relative amount of light biocrude is inversely proportional to the first temperature (or setpoint temperature).
  • the relative amount of light biocrude may be as high as 87% by weight based on the total weight of the biocrude, whereas when the setpoint temperature is 600 °C, the relative amount of light biocrude may be merely 40% by weight based on the total weight of the biocrude, all else being equal (including the period of time).
  • the biocrude typically has an elemental composition of carbon in an amount ranging from 50 to 80, alternatively from 60 to 80, weight percent, based on the total weight of the biocrude.
  • the biocrude generally has an elemental composition of hydrogen in an amount ranging from 1 to 20, alternatively from 5-15, alternatively from 8-12, weight percent, based on the total weight of the biocrude.
  • the biocrude typically has an elemental composition of nitrogen in an amount ranging from 1 to 10, alternatively from 3 to 8, weight percent, based on the total weight of the biocrude.
  • the biocrude typically has an elemental composition of sulfur in an amount ranging from 0 to 1.5, alternatively from 0.2 to 1, weight percent, based on the total weight of the biocrude.
  • the biocrude typically has an elemental composition of oxygen in an amount ranging from 5 to 25, alternatively from 8 to 20, weight percent, based on the total weight of the biocrude.
  • the biocrude may retain at least 50, at least 60, at least 70, or at least 80% of carbon and hydrogen atoms originally present in the biomass solids utilized to form the wet biomass of the method.
  • the biocrude has a hydrogen to carbon molar ratio ranging from 1.0 to 2.0, or ranging from 1.5 to 2.0.
  • the biocrude also typically has an oxygen to carbon molar ratio ranging from 0.01 to 0.50, ranging from 0.01 to 0.20, or, alternatively, ranging from 0.06 to 0.10.
  • the biocrude has a sulfur content below detection limits.
  • the biocrude typically has a heating value of from 30 to 50, alternatively from 30 to 40, alternatively from 33 to 37, MJ/kg.
  • the method of the instant invention generally has a yield of the biocrude from the wet biomass of at least 30, alternatively at least 40, alternatively at least 50, alternatively at least 55, alternatively at least 60, alternatively at least 65, weight percent, on a dry ash free basis.
  • the instant method provides numerous advantages relative to conventional hydrothermal liquefaction processes.
  • a wet biomass is heated for a comparatively significant period of time, e.g. from 30 to 90 minutes.
  • the period of time during which the wet biomass is heated solely relates to the time during which the wet biomass is heated at steady state temperature, i.e., these times do not account for the additional heating time required for the wet biomass to reach steady state temperature.
  • the total time the wet biomass (or the reaction mixture, as the case may be) is heated is less than about 180 seconds, including the time required for the wet biomass to be heated from ambient temperature to reach steady state temperature (in the event that the contents of the reaction vessel actually reach steady state temperature in the method).
  • the instant method is performed in a fraction of the amount of time required in conventional hydrothermal liquefaction methods, significantly more biocrude can be obtained from the instant method for a given period of time as compared to conventional methods. This is particularly advantageous when the instant method is a batch process. For example, much of the cost associated with the instant method relates to the reaction vessel in which the method is carried out, and numerous vessels operating in parallel are required for a similar output of biocrude from conventional hydrothermal liquefaction processes as compared to the output of biocrude obtained from the instant method with but one vessel.
  • the instant method can be performed much faster than conventional hydrothermal liquefaction methods, but it has been surprisingly found that the yield of the biocrude from the wet biomass is appreciably higher for the instant method than conventional hydrothermal liquefaction methods.
  • yield of the biocrude from the wet biomass has generally not exceed 50 weight percent on a dry ash free basis, whereas the instant method is capable of providing a yield of up to and exceeding 65 weight percent on a dry ash free basis, as described above. This improved yield is contrary to conventional wisdom that longer heating times will continue to improve yield.
  • a 316-stainless steel reaction vessel having an internal volume of 1.5 mL is utilized.
  • the reaction vessel is a 3/8" Swagelok® port connector extending between a first end and a second end.
  • the port connector has a cap coupled to each of the first and second ends.
  • dummy reaction vessels are constructed from 316-stainless steel.
  • the dummy reaction vessels are each a 3/8" Swagelok® port connector extending between a first end and a second end.
  • the dummy reaction vessels each have a cap coupled to the first end and a bored-through reducing union (3/8" to 1/8") coupled to the second end.
  • a stainless steel clad thermocouple having a diameter of 1/8" and a length of 18" from Omega Engineering, Inc. of Stamford, Connecticut is disposed in the reducing union and is sealed.
  • the dummy reaction vessels each have an internal volume of 1.5 mL and are merely filled with air.
  • the wet biomass utilized is a microalgae.
  • the wet biomass comprises Nannochloropsis sp.
  • the Nannochloropsis sp. is obtained under the name Nannochloropsis 3600 from Reed Mariculture of Campbell, California in the form of a slurry having a solids content of 35 weight percent.
  • Nannochloropsis 3600TM has a protein content of 59 weight percent, a lipid content of 14 weight percent, and a carbohydrate content of 20 weight percent.
  • the slurry is diluted as needed with deionized water.
  • the reaction vessel is loaded with the slurry such that liquid water will expand to fill 95% of the reaction vessel volume at the subcritical reaction temperatures, while maintaining a constant slurry concentration of 15 weight percent.
  • the reaction vessel is sealed with ambient air in a headspace of the reaction vessel.
  • reaction vessel and dummy reaction vessels are placed in a preheated isothermal Techne IFB-51 fluidized sandbath with a Eurotherm 3216 PID controller. Steam tables are relied upon for determining the water density at each setpoint temperature utilized in the method that would result in a pressure of about 400 bar at the setpoint temperature. Because algae paste contributes to less than about 15% of the total thermal mass of contents of the reaction vessel, the dummy reaction vessels (which do not include the wet biomass) provide an estimate of the thermal profile of the reaction vessel that does include the wet biomass therein.
  • setpoint temperatures of interest for the reaction vessel are identified. These setpoint temperatures vary from 300 to 600 °C.
  • the setpoint temperatures relate solely to the desired temperature of the reaction vessel itself, i.e., the setpoint temperature does not reflect the temperature of the contents of the reaction vessel. It generally takes at least 3 minutes, depending on a rate at which the reaction vessel is heated, for the contents of the reaction vessel to reach the setpoint temperature from ambient temperature. The greater the setpoint temperature, the greater the rate at which the reaction vessel is heated.
  • Trials are carried out at setpoint temperatures of 300, 400, 500, and 600 °C.
  • the period of time in which the wet biomass is heated in each of the reaction vessels is varied. In particular, for each of these setpoint temperatures, the period of time in which the wet biomass is heated is separately carried out for 1 minute, 3 minutes, and 5 minutes, respectively, to form a reaction mixture including the biocrude.
  • the temperature to which the wet biomass is heated is less than the setpoint temperature.
  • the reaction vessel and the dummy reaction vessel are immediately removed from the fluidized sandbath and quenched in cold water for 5 minutes.
  • the cooled reaction vessel and cooled dummy reaction vessels are equilibrated at ambient temperature for about 60 minutes.
  • the reaction mixture is removed from the reaction vessel and the biocrude is recovered, i.e., separated, from the reaction mixture.
  • one of the caps is removed from the reaction vessel, and the contents of the reaction vessel are poured into a conical tube.
  • the reaction product separated naturally in the conical tube into a biocrude phase, an aqueous phase, and a solid phase.
  • the interior of the reaction vessel is rinsed with 9 mL of dichloromethane in small aliquots to ensure that all of the contents of the reaction vessel are collected.
  • the contents of the reaction vessel are partitioned in accordance with the method disclosed in Valdez PJ, et al., Hydrothermal liquefaction of Nannochloropsis sp.: Systematic study of process variables and analysis of the product fractions, Biomass and Bioenergy (2012) ("Valdez”).
  • the conical tube is vortexted at 3000 rpm for 1 minute and is then centrifuged in an Eppendorf 5810 centrifuge at 500 relative centrifugal force (rcf) for 1 minute. After centrifugation, the solid products accumulate at the interface between the aqueous (top layer) and organic (bottom layer) phases.
  • the organic phase is transferred via pipette to another tube and the conical tube is again centrifuged at 1500 rcf for 3 minutes to remove suspended solids from the aqueous phase.
  • the aqueous phase is transferred to another tube via pipette.
  • the remaining material is dried in the conical tube in a 70 °C oven for 72 hours to drive off residual dichloromethane and water.
  • the resulting dried solids are weighed and analyzed. Dichloromethane is removed from the organic phase by flowing N 2 over the organic phase tubes for approximately 6 hours.
  • the dichloromethane-soluble product that remains is classified as the biocrude. After removing the dichloromethane from the organic phase, the biocrude is scraped from the walls of the tube with a metal spatula. 8 mL of n-hexane is added to the tube and the tube is vortexed at 1000 rpm for 60 minutes. The tube is then centrifuged for 3 minutes at 1500 rcf and the hexane phase is decanted into another tube. [0092] The hexane is removed by flowing N 2 over the hexane phase tubes for 6 hours. The hexane-soluble biocrude is classified as light biocrude, while the hexane- insoluble but dichloromethane- soluble fraction is classified as the heavy biocrude.
  • the light and heavy biocrude products are analyzed. Samples of the light biocrude are analyzed via gas chromatography with previously described methods. A 500 mL aliquot of the aqueous phase is transferred to a pre-weighed 1 dram vial and water is removed by flowing N 2 over the vial for 6 hours. The dried material is classified as the water-soluble products and its gravimetric yield and elemental composition is determined. The remaining aqueous phase is analyzed for ammonia, total nitrogen, total carbon, inorganic carbon (carbonate and bicarbonate), total phosphorus, and free phosphate (orthophosphate).
  • the pure aqueous phase is diluted 1 :70 with deionized water for phosphorus and phosphate measurement, 1 :200 for ammonia assay, 1:600 for carbon measurement, and 1 :4000 for total nitrogen assay.
  • Total carbon and inorganic carbon is measured via a Shimadzu TOC-VCSH total organic carbon analyzer, and total organic carbon (TOC) is calculated by the difference.
  • Hach® Nitrogen- ammonia reagent set (high-range) test kits are utilized to measure ammonia and a persulfate method is utilized to measure total N.
  • Free phosphate (orthophosphate) is measured via a vanadomolybdophosphoric acid method and total P is measured by first converting all P to phosphate via an oxidative digestion procedure used to measure total N.
  • Absorbance of the analyte solutions for N and P assays is measured via the method disclosed in Valdez.
  • absorbance of the analyze solutions for N and P assays is measured with a Thermo Scientific Genesys20 or Molecular Devices Spectramax M5 spectrophotometer.
  • a 2.5 weight percent slurry is centrifuged at 18,500 rcf, the supernatant is filtered through a 0.22 mm acetate filter to remove all of the microalgae cells, and the N and P content of the filtrate is measured.
  • An Agilent 1200 Refractive Index detector is used to identify and quantify certain organic compounds.
  • the work-up procedure is modified to determine the yields of the various solubility-based product fractions originally present in the wet biomass feedstock.
  • An identical mount of algae slurry that was utilized in the reaction vessels is disposed into a glass test tube and then dried in an oven at 70 °C for 72 hours to remove the water. After adding 9 mL of dichloromethane to the tube and vortexing the tube at 1000 rpm for 1 hour, the amount of water that would be present in the reaction system is added and the algae, solvent, and water are vortexed for 1 hour at 1000 rpm. After this step, the phases are easily separated using the procedure described above.
  • Triplicate samples of the slurry mixture are measured and averages are reported with one standard deviation being the reported uncertainty.
  • the dry mass of the algae remaining is measured to determine the weight percent of solids in the slurry.
  • To measure ash content the dried algae is placed in a laboratory furnace and heated to 250 °C at a rate of 15 °C/minute. The sample is held at 250 °C for 30 minutes and then heated to 580 °C at a rate of 20 °C/min and held at this temperature for 3 hours. The sample is cooled in a desiccator for 1 hour and the remaining material is weighed.
  • Trace metals are identified in the microalgae by dissolving 15 mg of algae into 3 mL concentrated nitric acid, diluting to 12 mL with deionized water, and then injecting a sample into a Varian 710ES inductively coupled plasma optical emission spectrometer. T emission results are scanned for positive identification of trace metals.
  • the light and heavy biocrudes, solids, and water-soluble product fractions are weighed to calculate gravimetric yields and the dried algae and product fractions were sent to Atlantic Microlab Inc. for measurement of C, H, N, and S composition. O composition in the light and heavy biocrude is measured by difference, assuming a minimal contribution of other elements were present.
  • Midwest Microlab measured total P in the solid and biocrude product fractions.
  • the heating value (HHV) of the products is calculated using Dulong's formula and the C, H, O, and S weight percentages:
  • HHV (MJ/kg) 0.338C + 1.428(H - 0/8) + 0.095S.
  • the gravimetric yield, elemental composition, elemental distribution, and energy distribution are defined as follows:
  • Elemental Distribution (%) (Mass of Element in Product Fraction/Mass of Element in Algae) x 100% ;
  • the reaction ordinate (R 0 ) is a parameter that has been utilized in the biomass industry to combine effects of both reaction time and temperature into a single parameter. Because these trials utilized a variety of times and setpoint temperatures, as well as non-isothermal conditions, the reaction ordinate is generally utilized to analyze how the processing conditions influenced the results of the trials.
  • the reaction ordinate includes a factor to account for the temperature dependence of the relative reaction rate, which is relative to a standard rate of unity at an arbitrarily selected temperature, often 100 °C.
  • the reaction ordinate for each trial is calculated from the experimental temperature profile by numerically integrating the following equation, where t represents the reaction time
  • Figure 1 illustrates the average temperature profile of the reaction vessel as a function of time based upon a particular setpoint temperature of the reaction vessel, i.e., 300 °C and 500 °C, respectively.
  • Figure 1 also includes the corresponding yield (wt. ) on a dry ash free basis of the biocrude for each setpoint temperature at a period of time of 1 minute, 3 minutes, and 5 minutes.
  • Figure 2 illustrates the average temperature profile of the reaction vessel as a function of time based upon a particular setpoint temperature of the reaction vessel, i.e., 400 °C and 600 °C, respectively.
  • Figure 2 also includes the corresponding yield (wt. ) on a dry ash free basis of the biocrude for each setpoint temperature at a period of time of 1 minute, 3 minutes, and 5 minutes.
  • Table 1 and Figures 1 and 2 it has been surprisingly found that, contrary to conventional wisdom, improved yields of the biocrude from the wet biomass are obtained at much faster reaction times for setpoint temperatures of 400 °C, 500 °C, and 600 °C, respectively.
  • the wet biomass is heated for extended periods of time, e.g. from 30 to 90 minutes, with the assumption that yield increases with the time during which the wet biomass is heated. However, this is not the case.
  • the yield of the biocrude after about 1 minute is 66 + 11 weight percent (on a dry ash free basis).
  • the yield of the biocrude drops precipitously after heating the wet biomass for 3 minutes to 14 + 4 weight percent (on a dry ash free basis). This decrease in yield continues, albeit at a lower rate, after heating the wet biomass for 5 minutes, where the yield of the biocrude is merely 10 + 3 weight percent (on a dry ash free basis).
  • the yield of the biocrude after about 1 minute is 55 + 12 weight percent (on a dry ash free basis).
  • the yield of the biocrude drops somewhat significantly after heating the wet biomass for 3 minutes to 45 + 7 weight percent (on a dry ash free basis). This decrease in yield continues after heating the wet biomass for 5 minutes, where the yield of the biocrude is merely 28 + 9 weight percent (on a dry ash free basis).
  • the energy recovery generally decreases over time, as illustrated in Table 1.
  • the energy recovery (%) is 73 + 15 percent after heating the wet biomass for 1 minute, yet this energy recovery decreases to 38 + 12 percent after heating the wet biomass for 5 minutes.
  • An energy recovery of 100% indicates that all of the chemical energy in the wet biomass has been transferred to the biocrude.
  • the energy recovery was maximized at 91 + 14 percent after heating the wet biomass for but 1 minute.
  • reaction times ranging from 0 to 2 minutes are investigated in 15 second intervals. More specifically, biocrude yield is investigated at a setpoint temperature of 600 °C at 0 seconds, 15 seconds, 30 seconds, 45 seconds, 60 seconds, 75 seconds, 90 seconds, 105 seconds, and 120 seconds (while starting at ambient or room temperature). All other process parameters (e.g. reaction vessel volume, solids content, wet biomass utilized, etc.) are constant such that reaction time is the only variable in Example 2.
  • the wet biomass utilized in Example 2 is Nannochloropsis sp. having a solids content of 15 wt. .
  • the wet biomass has a solids content of 15 wt.% with a total mass loading in the reaction vessel of 0.2 g (10% of reaction vessel volume).
  • Figure 3 illustrates the biocrude yield (wt. %) on a dry ash free basis of the biocrude formed in Example 2. More specifically, Figure 3 illustrates the biocrude yield as a function of reaction time. Multiple runs were carried out for each specified reaction time (but for 0 seconds), and Figure 3 illustrates the standard deviation of the multiple runs for each particular reaction time with margins of uncertainty.
  • solids content of the wet biomass is investigated. More specifically, biocrude yield is investigated while modifying the solids content of the wet biomass utilized.
  • the solids content is manipulated by varying water (e.g. by adding water to wet biomass so as to reduce the solids content thereof) and by varying total mass loading in the reaction vessel.
  • biocrude yield is investigated at a solids content of 5 wt.%, 7.5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, and 25 wt.%.
  • the setpoint temperature utilized is 600 °C.
  • the wet biomass utilized in Example 3 is Nannochloropsis sp.
  • the reaction time is 1 minute for each of the trials in Example 3.
  • the reaction time is the total time during which the contents of the reaction vessel are heated from ambient temperature at the setpoint temperature.
  • Other process steps and the corresponding measurements/calculations are the same as those in Example 1.
  • the total mass loading in the reaction vessel ranges from 0.2 to 0.6 grams (10% to 36% of reaction vessel volume).
  • Figure 4 illustrates the biocrude yield (wt. %) on a dry ash free basis of the biocrude formed in Example 3. More specifically, Figure 4 illustrates the biocrude yield as a function of solids content in the wet biomass. Multiple runs were carried out for each specified solids content, and Figure 3 illustrates the standard deviation of the multiple runs for each particular reaction time with margins of uncertainty.
  • Example 3 involved the simultaneous manipulation of solids content and total mass loading into the reaction vessel, these variables (i.e., solids content and total mass loading) are decoupled so as to isolate but one variable.
  • the solids content of the wet biomass is maintained at 15 wt.%, whereas the total mass loading in the reaction vessel ranged from 0.2 to 1.2 grams with increments averaging around 0.2 grams.
  • the total mass loading correlated to 10-60% of the reaction vessel volume.
  • Other parameters e.g. setpoint temperature, reaction time, etc. are the same as in Example 3.
  • Figure 5 illustrates the biocrude yield (wt. %) on a dry ash free basis of the biocrude formed in Example 4. More specifically, Figure 5 illustrates the biocrude yield as a function the total mass loading in the reaction vessel. Multiple runs were carried out for each specified total mass loading, and Figure 5 illustrates the standard deviation of the multiple runs for each particular reaction time with margins of uncertainty.
  • reaction vessels similar to those of Example 1 but having an internal volume of 1.67 mL are utilized.
  • the reaction vessels are loaded with the particular microalgaes of interest in freeze dried form, which are combined with water to form a rehydrated slurry having a solids content of about 15 wt. .
  • reaction vessels are loaded such that the respective rehydrated slurries fill 95% of the reaction vessel volumes at the setpoint temperatures of interest.
  • the reaction vessels are sealed with ambient air in the headspaces of the reaction vessels. Table 2 below illustrates the microalgae and water loadings for each of the rehydrated slurries utilized.
  • reaction vessels are submerged in a hot fluidized sandbath and heated at a desired setpoint temperature for a period of time.
  • the desired setpoint temperature is 600 °C and the period of time is one minute.
  • the desired setpoint temperature is 350 °C and the period of time is 60 minutes.
  • Figure 6 illustrates the biocrude yield (wt. %) on a dry basis of the biocrude formed via the instant method from N. oleoabundans, C. vulgaris, and B. braunii.
  • Figure 6 additionally illustrates the comparative biocrude yield (wt. %) on a dry basis of the biocrude formed via conventional hydrothermal liquefaction from N. oleoabundans, C. vulgaris, and B. braunii. Multiple runs were carried out for each specified total mass loading, and Figure 6 illustrates the standard deviation of the multiple runs for each particular reaction time with margins of uncertainty.
  • the biocrude yield for the instant method when utilizing N. oleoabundans, C. vulgaris, and B. braunii is nearly identical to the biocrude yield for conventional hydrothermal liquefaction for these species of microalgae. This is true despite the fact that conventional hydrothermal liquefaction requires significantly more time, and thus increases costs associated with heating, as compared to the inventive method. Moreover, the instant method can provide a much greater yield for a set period of time due to the decreased reaction time associated therewith.
  • E. coli TB E. coli MM
  • P. putida B. subtilis
  • S. cerevisiae S. cerevisiae
  • the terminology E. coli TB and E. coli MM designates E. coli grown in different media.
  • the acronym “TB” stands for "terrific broth”
  • the acronym “MM” stands for minimal medium, which are each defined above.
  • These microorganisms are additionally subjected to a conventional hydrothermal liquefaction process so as to compare the respective biocrude yields between the instant method and conventional hydrothermal liquefaction.
  • reaction vessels similar to those of Example 1 but having an internal volume of 2.2 mL are utilized.
  • the reaction vessels are loaded with the particular microorganisms of interest. More specifically, for the conventional hydrothermal liquefaction process, 1.35 grams of a slurry having a solids content of 12 wt. is loaded into the reaction vessel, with water filing 95% of the reaction vessel volume at reaction conditions. In contrast, for the inventive method, 0.3 grams of a slurry having a solids content of 12 wt.% is loaded into the reaction vessel.
  • the reaction vessels are sealed with ambient air in the headspaces of the reaction vessels.
  • reaction vessels are submerged in a hot fluidized sandbath and heated at a desired setpoint temperature for a period of time.
  • the desired setpoint temperature is 600 °C and the period of time is one minute.
  • the desired setpoint temperature is 350 °C and the period of time is 60 minutes.
  • Figure 7 illustrates the biocrude yield (wt. %) on a dry ash free basis of the biocrude formed via the instant method from E. coli TB, E. coli MM, P. putida, B. subtilis, and S. cerevisiae.
  • Figure 7 additionally illustrates the comparative biocrude yield (wt. ) on a dry ash free basis of the biocrude formed via conventional hydrothermal liquefaction from N. oleoabundans, C. vulgaris, and B. braunii. Multiple runs were carried out for each specified total mass loading, and Figure 7 illustrates the standard deviation of the multiple runs for each particular reaction time with margins of uncertainty.
  • Figure 7 illustrates the relative amounts of light biocrude and heavy biocrude in the biocrude produced for each microorganism/method.
  • the biocrude yield for the instant method when utilizing E. coli TB, E. Coli MM, P. putida, B. subtilis, and S. cerevisiae is improved as compared to the biocrude yield for conventional hydrothermal liquefaction for these species of microorganisms, particularly with respect to the heavy biocrude, which is desirable.
  • conventional hydrothermal liquefaction requires significantly more time, and thus increases costs associated with heating, as compared to the inventive method.
  • the instant method can provide a much greater yield for a set period of time due to the decreased reaction time associated therewith.
  • biocrude yield was slightly reduced for B. subtilis.
  • B. subtilis the biocrude yield for B. subtilis is attributable to its cellular structure as a Gram-positive organism.
  • Gram-positive organism such as B. subtilis
  • Gram-positive organisms generally have a comparatively thick layer of peptidoglycans, which are polysaccharides cross-linked by polypeptides.
  • peptidoglycans which are polysaccharides cross-linked by polypeptides.
  • Such gram-positive organisms may hydrolyze to simple sugars and amino acids that reside within the aqueous phase of the reaction product including the biocrude.
  • Continued heating, as in conventional hydrothermal liquefaction is believed to form organic soluble products from the amino acids and simple sugars.
  • any ranges and subranges relied upon in describing various embodiments of the present invention independently and collectively fall within the scope of the appended claims, and are understood to describe and contemplate all ranges including whole and/or fractional values therein, even if such values are not expressly written herein.
  • One of skill in the art readily recognizes that the enumerated ranges and subranges sufficiently describe and enable various embodiments of the present invention, and such ranges and subranges may be further delineated into relevant halves, thirds, quarters, fifths, and so on.
  • a range "of from 0.1 to 0.9" may be further delineated into a lower third, i.e., from 0.1 to 0.3, a middle third, i.e., from 0.4 to 0.6, and an upper third, i.e., from 0.7 to 0.9, which individually and collectively are within the scope of the appended claims, and may be relied upon individually and/or collectively and provide adequate support for specific embodiments within the scope of the appended claims.
  • a range such as "at least,” “greater than,” “less than,” “no more than,” and the like, it is to be understood that such language includes subranges and/or an upper or lower limit.
  • a range of "at least 10" inherently includes a subrange of from at least 10 to 35, a subrange of from at least 10 to 25, a subrange of from 25 to 35, and so on, and each subrange may be relied upon individually and/or collectively and provides adequate support for specific embodiments within the scope of the appended claims.
  • an individual number within a disclosed range may be relied upon and provides adequate support for specific embodiments within the scope of the appended claims.
  • a range "of from 1 to 9" includes various individual integers, such as 3, as well as individual numbers including a decimal point (or fraction), such as 4.1, which may be relied upon and provide adequate support for specific embodiments within the scope of the appended claims.

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Abstract

La présente invention concerne un procédé de préparation de biobrut à partir d'une biomasse humide comprenant une étape consistant à se procurer ladite biomasse humide. Le procédé comprend une autre étape consistant à chauffer ladite biomasse humide pendant un premier laps de temps pour la faire passer de la température ambiante à une première température pouvant varier d'environ 100 à environ 600 °C afin de former un mélange réactionnel comprenant ledit biobrut. Le procédé comprend éventuellement une autre étape consistant à chauffer le mélange réactionnel ayant atteint ladite première température pendant un second laps de temps. Dans le cadre de ce procédé, les premier et second laps de temps cumulés ne dépassent pas 180 secondes environ.
PCT/US2013/066538 2012-10-25 2013-10-24 Procédé de préparation de biobrut à partir de biomasse humide caractérisé par un rendement amélioré WO2014066594A1 (fr)

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CN112779044A (zh) * 2021-01-05 2021-05-11 江苏大学 一种基于水相养藻的污泥和微藻超临界共快速水热液化制油系统及工艺

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US20110232344A1 (en) * 2008-09-11 2011-09-29 Aquaflow Bionomic Corporation Limited Concentration of algal biomass
WO2012060767A1 (fr) * 2010-11-01 2012-05-10 Reac Fuel Ab Procédé pour une liquéfaction contrôlée d'une charge d'alimentation à base de biomasse par un traitement dans de l'eau comprimée chaude
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US20100050502A1 (en) * 2008-08-21 2010-03-04 LiveFuels, Inc. Systems and methods for hydrothermal conversion of algae into biofuel
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WO2012060767A1 (fr) * 2010-11-01 2012-05-10 Reac Fuel Ab Procédé pour une liquéfaction contrôlée d'une charge d'alimentation à base de biomasse par un traitement dans de l'eau comprimée chaude

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