US20100223839A1 - Systems and processes for producing bio-fuels from lignocellulosic materials - Google Patents
Systems and processes for producing bio-fuels from lignocellulosic materials Download PDFInfo
- Publication number
- US20100223839A1 US20100223839A1 US12/717,833 US71783310A US2010223839A1 US 20100223839 A1 US20100223839 A1 US 20100223839A1 US 71783310 A US71783310 A US 71783310A US 2010223839 A1 US2010223839 A1 US 2010223839A1
- Authority
- US
- United States
- Prior art keywords
- biomass
- temperature
- pyrolysis
- heating
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B47/00—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion
- C10B47/28—Other processes
- C10B47/32—Other processes in ovens with mechanical conveying means
- C10B47/44—Other processes in ovens with mechanical conveying means with conveyor-screws
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/02—Multi-step carbonising or coking processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
- C10J3/60—Processes
- C10J3/64—Processes with decomposition of the distillation products
- C10J3/66—Processes with decomposition of the distillation products by introducing them into the gasification zone
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/001—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by thermal treatment
- C10K3/003—Reducing the tar content
- C10K3/006—Reducing the tar content by steam reforming
-
- 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
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/08—Treating solid fuels to improve their combustion by heat treatments, e.g. calcining
- C10L9/083—Torrefaction
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M21/00—Bioreactors or fermenters specially adapted for specific uses
- C12M21/12—Bioreactors or fermenters specially adapted for specific uses for producing fuels or solvents
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M43/00—Combinations of bioreactors or fermenters with other apparatus
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M45/00—Means for pre-treatment of biological substances
- C12M45/20—Heating; Cooling
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/06—Ethanol, i.e. non-beverage
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K1/00—Glucose; Glucose-containing syrups
- C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02C—GAS-TURBINE PLANTS; AIR INTAKES FOR JET-PROPULSION PLANTS; CONTROLLING FUEL SUPPLY IN AIR-BREATHING JET-PROPULSION PLANTS
- F02C3/00—Gas-turbine plants characterised by the use of combustion products as the working fluid
- F02C3/20—Gas-turbine plants characterised by the use of combustion products as the working fluid using a special fuel, oxidant, or dilution fluid to generate the combustion products
- F02C3/26—Gas-turbine plants characterised by the use of combustion products as the working fluid using a special fuel, oxidant, or dilution fluid to generate the combustion products the fuel or oxidant being solid or pulverulent, e.g. in slurry or suspension
- F02C3/28—Gas-turbine plants characterised by the use of combustion products as the working fluid using a special fuel, oxidant, or dilution fluid to generate the combustion products the fuel or oxidant being solid or pulverulent, e.g. in slurry or suspension using a separate gas producer for gasifying the fuel before combustion
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0903—Feed preparation
- C10J2300/0909—Drying
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/094—Char
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0956—Air or oxygen enriched air
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
- C10J2300/1643—Conversion of synthesis gas to energy
- C10J2300/165—Conversion of synthesis gas to energy integrated with a gas turbine or gas motor
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1671—Integration of gasification processes with another plant or parts within the plant with the production of electricity
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1681—Integration of gasification processes with another plant or parts within the plant with biological plants, e.g. involving bacteria, algae, fungi
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
- C10J2300/1846—Partial oxidation, i.e. injection of air or oxygen only
-
- 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
Definitions
- This disclosure relates to systems and processes for producing liquid fuels from lignocellulosic materials (e.g., agricultural and forestry residues and energy crops).
- lignocellulosic materials e.g., agricultural and forestry residues and energy crops.
- Biomass is an attractive feedstock to offset fossil fuels because it is carbon neutral (or negative), renewable, and may be domestically produced.
- One conversion platform uses a thermo-chemical process (commonly referred to as “pyrolysis”) to convert biomass into bio-oil.
- Bio-oils are similar in appearance and color as crude oil though bio-oil contains considerably more oxygenated and functional compounds.
- bio-oil can be used directly for stationary diesel engines, bio-oil may be too corrosive and viscous as a transport fuel. There is however great potential to use bio-oil as a feedstock for centralized refineries to produce chemical products and/or transportation fuels.
- bio-oil as a feedstock.
- bio-oils are highly acidic and may be corrosive to pipes and storage vessels.
- bio-oils can be unstable when stored for prolonged periods of time.
- bio-oils typically contain a wide variety of molecules including a substantial amount of small molecules, which are difficult to upgrade. Accordingly, several improvements in converting biomass to bio-oils are needed.
- FIG. 1 is a schematic flow diagram illustrating a system for converting biomass into bio-oils in accordance with embodiments of the technology.
- FIG. 2 is a schematic diagram illustrating a system for performing bio-oil refining in accordance with embodiments of the technology.
- FIGS. 3A and 3B are schematic diagrams illustrating a reactor in accordance with embodiments of the technology.
- FIG. 4 is a graph showing ratios of peaks in Py-GC/MS chromatogram assigned to levoglucosan and to hydroxyacetaldehyde in accordance with embodiments of the technology.
- FIG. 5 shows the changes of levoglucosan/furfural ratios as a function of pyrolysis temperature in accordance with embodiments of the technology.
- FIGS. 6 and 7 show the ratio of levoglucosan and other products of oxidation reactions in accordance with embodiments of the technology.
- FIG. 8 shows levoglucosan/2-methoxy phenol ratios as a function of pretreatment temperature in accordance with embodiments of the technology.
- FIG. 9 shows levoglucosan/hydroxyacetaldehyde ratios as a function of pyrolysis temperature in accordance with embodiments of the technology.
- FIG. 10 shows a glucose content as a function of fermentation time in accordance with embodiments of the technology.
- FIG. 11 shows a rate of microbial growth in solutions derived from bio-oils and in control solutions produced with glucose in accordance with embodiments of the technology.
- FIG. 12 shows ethanol concentration as a function of fermentation time in accordance with embodiments of the technology.
- FIG. 13 shows sugar consumption and production of fatty acids as a function of fermentation time in accordance with embodiments of the technology.
- lignocellulosic materials generally refers to materials containing cellulose, hemicelluloses, and lignin.
- lignocellulosic materials include wood chips, straws, grasses, corn stover, corn husks, weeds, aquatic plants, hay, paper, paper products, recycled paper and/or paper products, and other cellulose containing biological materials or materials of biological origin.
- lignocellulosic materials include wood chips, straws, grasses, corn stover, corn husks, weeds, aquatic plants, hay, paper, paper products, recycled paper and/or paper products, and other cellulose containing biological materials or materials of biological origin.
- FIG. 1 is a schematic flow diagram illustrating a system 100 for converting biomass into bio-oils in accordance with embodiments of the disclosure.
- the system 100 includes a drier 102 , a torrefaction unit (with an optional grinder) 104 , a pyrolysis reactor 106 , a first condenser 108 , a second condenser 110 , and a combustor 112 operatively coupled in series.
- the system 100 also includes an evaporator 114 , a steam reformer 116 , and a gasification reactor 118 operatively coupled to one another as well as to the pyrolysis reactor 106 and the second condenser 110 .
- FIG. 1 other embodiments of the system 100 can also include washers, decanters, filters, and/or other suitable components in addition to or in lieu of the foregoing components of the system 100 .
- the dryer 102 can include a direct-contact dryer, an indirect-contact dryer, and/or other suitable types of dryer.
- the dryer 102 includes a direct-contact dryer configured to receive and contact the biomass 1 with a hot combustion gas 6 from the combustor 112 .
- the exhaust from the dryer 102 is vented to atmosphere.
- the dryer 102 can also be coupled to an optional hot gas source (e.g., hot air, not shown) for start-up, supplementing the hot combustion gas 6 , and/or other suitable purposes.
- the dryer 102 provides a dried biomass 2 to the torrefaction unit 104 .
- the dryer 102 and the torrefaction unit 104 can be integrated in a single unit (not shown).
- the torrefaction unit 104 can be configured to pre-treat the dried biomass 2 before subjecting the dried biomass 2 to pyrolysis.
- the torrefaction unit 104 can include any vessel capable of controllably heating the dried biomass 2 to a desired temperature.
- the torrefaction unit 104 can also include a grinder and/or other suitable components to reduce the size of the dried biomass 2 .
- the torrefaction unit 104 can include an auger reactor configured to controllably heat the dried biomass 2 while reducing the size of the dried biomass 2 , as described in more detail below with reference to FIG. 4 .
- the torrefaction unit 104 may also use a synthesis gas 16 from the reformer 116 as a carrier gas for the pretreatment reactions.
- the pyrolysis reactor 106 can include a fluidized bed, a fixed bed, an ablative reactor, vacuum pyrolysis reactor, auger pyrolysis reactor, and/or other suitable types of pyrolysis reactors.
- the pyrolysis reactor 106 can include embodiments of the auger reactor shown in FIG. 3 .
- the pyrolysis reactor 106 can include other types of reaction vessels.
- the torrefaction unit 104 and the pyrolysis reactor 106 are shown as separate components in FIG. 1 , in certain embodiments, the torrefaction unit 104 and the pyrolysis reactor 106 can be combined into a single component.
- a single component e.g., the reactor of FIG. 3
- the torrefaction unit 104 and the pyrolysis reactor 106 may be integrated into a single unit.
- the first and second condensers 108 and 110 , the boiler 114 , and the reformer 116 can individually include a plate-and-frame, tube-and-shell, brazed aluminum, and/or other types of heat exchanger.
- the first condenser 108 can be an empty scrubber. In other embodiments, the first condenser 108 can operate in other suitable fashion. Even though the first and second condensers 108 and 110 are shown as separate components in FIG. 1 , in certain embodiments, the first and second condensers 108 and 110 may be combined into a single heat exchanger. In further embodiments, one of the first and second heat exchangers 108 and 110 may be omitted.
- the combustor 112 can be configured to react a combustible gas with air and/or oxygen to produce electrical, heat, and/or other forms of energy.
- the combustor 112 includes a gas turbine coupled to an electrical generator.
- the combustor 112 can also include a gasoline engine, a diesel engine, a ramjet, and/or other suitable combustion components.
- the combustor 112 may be omitted.
- the gasification reactor 118 can be configured to convert a carbonaceous material into a combination of hydrogen, carbon monoxide, carbon dioxide, and/or other suitable gaseous components.
- the gasification reactor 118 can include a counter-current fixed bed gasifier, a co-current fixed bed gasifier, a fluidized bed reactor, an entrained flow gasifier, and/or other suitable types of gasifier.
- the biomass 1 is provided to drier 102 .
- the drier 102 dries the biomass 1 with, for example, the combustion gas 6 from the combustor 112 .
- the dried biomass 2 then enters the torrefaction unit 104 to be pre-treated prior to pyrolysis.
- the torrefaction unit 104 heats the dried biomass 2 to a desired temperature (e.g., about 200° C. to about 300° C.) for a treatment period (e.g., 3 min to about 10 hours) with a portion of the synthetic gas 15 from the reformer 116 as a carrier gas.
- pre-treatment temperature and time may depend on each other. For example, a high pre-treatment temperature may require a short treatment time and vice versa.
- pre-treating the biomass 1 in the torrefaction unit 104 can (1) remove at least part of the hemicellulose and acetic acid from the solid matrix; (2) reduce the degree of polymerization of cellulose and increase crystallinity of the cellulose; (3) de-polymerize at least part of the lignin; and (4) weaken biomass fibrous structure for ease of grinding.
- the pre-treated biomass is then provided to the pyrolysis reactor 106 in which the biomass is thermally converted at temperatures between 400 and 500° C. into a vapor phase pyrolysis product 3 and bio-char 8 .
- the pre-treated biomass provided to the pyrolysis reactor 106 may contain additives (e.g., H 2 SO 4 , (NH 4 ) 2 HPO 4 and (NH 4 ) 2 SO 4 ) at concentrations of about 0.1 mass % or other suitable concentration values. The additional of such additives are believed to enhance the production of anhydrosugars from biomass.
- the pyrolysis reactor 106 may contain other suitable compositions.
- the first and second condensers 108 and 110 may then condense the pyrolysis product 3 with ambient air 17 (and/or other suitable coolant) to separate and collect different fractions from the pyrolysis product 3 and produce heated air streams 18 and 19 , which is provided to the combustor 112 .
- the first and second condensers 108 and 110 may both cool the pyrolysis product 3 with ambient air.
- the temperature in the first condenser 108 can be controlled to separate heavier compounds (e.g., phenols and sugars) from light compounds (e.g., acetic and formic acid).
- a bio-oil 9 can be separated via solvent extraction (e.g., with ethyl acetate) and/or other suitable techniques to produce a stream rich in phenols and pyrolytic sugars.
- a first fraction of the bio-oil 9 which is rich in sugar can then be hydrolyzed, detoxified and fermented to produce ethanol and/or can be subject to other types of suitable processing to produce other hydrocarbons.
- a second fraction of the bio-oil 9 which is rich in phenols can be converted into green gasoline via hydro-treatment and/or other suitable processes, as described in more detail below with reference to FIG. 2 .
- the second condenser 110 can then receive an output stream 4 from the first condenser 106 and collect an aqueous stream 10 from the pyrolysis product 3 .
- the aqueous stream 10 is then supplied to the reformer 116 via the boiler 114 to produce a synthetic gas 20 .
- the synthetic gas 20 is then provided to the combustor 112 for conversion into electricity and/or other forms of energy.
- the aqueous stream 10 can be gasified with the bio-char 8 .
- the gasification reactor 118 can convert at least a portion of the bio-char 8 into a synthetic gas 14 provided to the reformer 116 and output the rest of the bio-char 8 as char and ash.
- the bio-char 8 may be provided to the combustor 112 and/or otherwise processed.
- the bio-char 8 may form a final product of the process.
- biomass degradation via pyrolysis may be classified into three general categories: de-polymerization, fragmentation, and polycondensation.
- Depolymerization reactions are believed to yield primarily monomers that are greater than five carbons. Such monomers may be either carbohydrodrate (from cellulose/hemicellulose) or aromatic (from lignin). Fragmentation reactions are believed to lead to the formation of small molecules that are typically smaller than five carbons.
- Poly-condensation reactions are believed to result in the formation of charcoal.
- Pyrolysis reactors can reduce the formation of char by having very high heating rates which may reduce the time the material is in the temperature range of 270-350° C. in which dehydratation and crosslinking reactions are favored.
- Several embodiments of the system 100 can alter the structural properties of the biomass 1 for improving the selectivity to favor depolymerization reactions and improve the bio-oil quality produced during pyrolysis.
- Several factors are believed to influence whether degradation proceeds via fragmentation or de-polymerization reactions. The presence of alkaline is believed to strongly catalyze fragmentation reactions.
- Other factors such as degree of polymerization, crystallinity, and the interactions lignin/cellulose are also factors that can be adjusted to improve reaction selectivity toward de-polymerization (formation of precursors of transportation fuels).
- the reaction selectivity to de-polymerization may be improved.
- inventions of the systems and processes can also have substantial energy savings as a result of pretreatment for grinding operations.
- the pretreatment not only removes components of the material, it may also attenuate the physical integrity and reduce the energy required to reduce particle sizes to what is required for the pyrolysis reactor. It should be noted that grinding can contribute to as much as 10% of the total energy in the biomass.
- FIG. 2 is a schematic diagram illustrating a process 200 for performing bio-oil refining in accordance with embodiments of the disclosure.
- the process 200 can include separating a phenolic fraction from an aqueous fraction in the bio-oil 9 . Techniques suitable for this separation can include liquid-liquid extraction with water, an organic solvent, and/or other suitable materials.
- the phenolic fraction can then be hydro-treated with hydrogen to produce green gasoline.
- the aqueous fraction can be (1) hydro-treated under high pressure to produce green diesel; (2) hydrolyzed, neutralized, and detoxified to produce lipids; and/or (3) hydrolyzed, neutralized, detoxified, and fermented to produce alcohol.
- FIG. 3A is a schematic diagram illustrating an reactor 300 in accordance with embodiments of the technology.
- the reactor 300 includes a feeder 302 coupled to a treatment zone 304 having a first end 303 a and a second end 303 b .
- the feeder 302 can include a screw pump and/or other suitable material moving components.
- the treatment zone 30 can include a generally helical auger (or screw) 307 and/or other suitable structures inside a housing 305 and a motor 320 operatively coupled to the auger 320 .
- the reactor 300 also includes a heat exchanger 306 and a furnace 308 on the housing 305 and a power supply/controller 310 operatively coupled to the furnace 308 .
- the reactor 300 further includes a solid container 312 and a condenser 314 proximate to the second end 303 b of the treatment zone 304 .
- the reactor 300 includes a plurality of cooling traps 316 coupled to the condenser 314 for collecting condensed materials.
- the feeder 302 forces biomass (shown as separate spheres in FIG. 3A for illustration purposes) to enter the treatment zone 304 via the first end 303 a along with an optional carrier gas.
- the heat exchanger 306 and the furnace 308 then heats the biomass to a desired temperature while the auger 307 moves the biomass toward the second end 303 b and reduces the size of the biomass.
- Solid portions of the biomass are then collected at the solid container 312 while volatile portions are collected at the condenser 314 and/or the cooling traps 316 .
- a single reactor 300 may be used for both pre-treating and pyrolysis of the biomass.
- the biomass may be processed in the reactor 300 at a first temperature (e.g., about 200° C. to about 300° C.).
- the collected solid portions may then be returned to the feeder 302 to be provided to the auger 304 and processed at a second temperature (e.g., about 500° C. to about 600° C.).
- the reactor 300 may include more than one treatment zones (e.g., by having more than one furnaces) such that the pre-treatment and pyrolysis operations may be performed in a continuous fashion.
- the pre-treatment and pyrolysis operations may be performed in a continuous fashion.
- FIG. 3B Several components shown in FIG. 3B are generally similar in structure and function as those shown in FIG. 3A . As a result, common acts and structures are identified by the same reference numbers.
- the reactor 300 can include a first treatment zone 304 a coupled to a second treatment zone 304 b .
- the first treatment zone 304 a can include a first auger (or screw) 307 a inside a first housing 305 a having a first end 303 a and a second end 303 b .
- the first auger 307 a can be operatively coupled to a first motor 320 a .
- the first treatment zone 304 a also includes a first furnace 308 a proximate to the first housing 305 a and operatively coupled to a first power supply/controller 310 a .
- the first treatment zone 304 a also includes a carrier gas inlet 324 a and a carrier gas outlet 324 b in fluid communication with the auger 307 a.
- the first treatment zone 304 a can also include a grinder 322 and/or other suitable components configured to reduce a physical size of the biomass in the first treatment zone 304 a .
- the grinder 322 is proximate to the second end 303 b of the first treatment zone. In other embodiments, the grinder 322 may be at other locations of the first treatment zone or may be omitted.
- the second treatment zone 304 b can have generally similar components as the first treatment zone 304 a .
- the second treatment zone 304 b can include a second auger 307 b in a second housing 305 b and operatively coupled to a second motor 320 b .
- the second treatment zone 304 b can also include a second furnace 308 b proximate to the second housing 305 b and operatively coupled to a second power supply/controller 310 b.
- the feeder 302 forces biomass to enter the first treatment zone 304 a via the first end 303 a along with an optional carrier gas via the carrier inlet 324 a .
- the heat exchanger 306 and the first furnace 308 a then heats the biomass to a first temperature (e.g., about 200° C. to about 300° C.) while the auger 307 moves the biomass toward the second end 303 b .
- the optional grinder 322 can then reduce the biomass from the first treatment zone 304 a to particle sizes less than about 2 mm before the biomass is provided to the second treatment zone 304 b .
- the second furnace 308 b can then heat the biomass to a second temperature (e.g., about 500° C. to about 600° C.) to thermally convert the biomass via pyrolysis. Solid portions of the biomass are then collected at the solid container 312 while volatile portions are collected at the condenser 314 and/or the cooling traps 316 .
- the reactor 300 may utilize other components for conveying and/or reducing size of the biomass.
- at least one of the first and second augers 307 a and 307 b may be omitted in the reactor 300 shown in FIG. 3B .
- the reactor 300 may carry the biomass through the treatment zones 304 a and 304 b pneumatically, hydraulically, and/or via other suitable means.
- the biomass may be treated in at least one of the first and second treatment zones 304 a and 304 b in a batch mode.
- the reactor 300 can include three, four, and/or other suitable number of treatment zones with similar or different configurations.
- the Py-GC/MS tests were carried using a CDS pyro-probe 5000 connected in-line to an Agilent GC/MS. Samples were loaded into a quartz tube and gently packed with quartz wool prior to pyrolysis. The samples were kept for 3 minutes at the pretreatment temperature before the oven temperature was reduced to 210° C. The samples were kept in these conditions for 1 minute. Samples were pyrolysed by near instantaneous heating to the final temperature and held at this temperature for 3 minutes.
- the GC/MS inlet temperature was maintained at 250° C. and the resulting pyrolysis vapors were separated by means of a 30 m ⁇ 0.25 ⁇ m inner diameter column.
- the column was heated at 3° C./min from 40 to 280° C.
- the gas was then sent into a mass spectrometer and the spectra of the most important peaks were compared to an NBS mass spectra library to establish the identity of each compound.
- FIG. 4 shows the ratio of the area of the peaks in the Py-GC/MS chromatogram assigned to levoglucosan (a product of cellulose depolymerization reactions) and to hydroxyacetaldehyde (a product of cellulose fragmentation reactions). This ratio can be used as an index of the selectivity of thermochemical reactions towards the production of anhydrosugars.
- FIG. 4 shows that a mild torrefaction in the range of temperature between 200 and 320° C. can enhance the production of levoglucosan for ⁇ -cellulose, wheat straw and the wood fraction of Douglas Fir.
- FIG. 5 shows the changes of levoglucosan/furfural ratios as a function of pyrolysis temperature in accordance with embodiments of the technology.
- the pretreatment temperature does not have any effect on the Levoglucosan/furfural ratios for the Avicel. This result suggests that Avicel was not dehydrated in the pretreatment conditions tested.
- ⁇ -cellulose an increase in the levoglucosan/furfural ratio was observed as the pretreatment temperature increases.
- the presence of oxygen during pretreatment of ⁇ -cellulose and Avicel causes a reduction in the levogluocan/Furfural ratio for most of the materials but not for the wheat straw.
- the conditions improving the ratio levoglucosan/furfural are very similar to those improving the ratio levoglucosan/hydroxyacetaldehyde.
- FIGS. 6 and 7 show the ratio of levoglucosan and other products of oxidation reactions in accordance with embodiments of the technology.
- the shapes of the curves describing the evolution of the levoglucosan/carbon dioxide and levoglucosan/acetic acid ratio are similar to those shown in FIGS. 4 and 5 .
- FIG. 8 shows levoglucosan/2-methoxy phenol ratios as a function of pretreatment temperature.
- the conditions improving this ratio were similar to those improving the levoglucosan/CO2 and levoglucosan/acetic acid ratios.
- pre-treating biomass in the presence of oxygen considerably increases the production of mono-phenols due to the oxidation of lignin linkages.
- the levoglucosan/2-methoxy phenol ratio can be improved if the wheat straw is pretreated at a 270° C. in the presence of oxygen. The presence of oxygen was detrimental for the Douglas Fir.
- Douglas Fir wood was pre-treated at select conditions identified by Py-GC/MS and was subject to pyrolysis in the Auger Pyrolysis reactor built at Washington State University (generally similar to that shown in FIG. 3A ). During testing, 200 g of Douglas Fir samples were added into 3 L of deionized water. The biomass and the water were heated in an autoclave (Consolidated Stills & Sterilizers) at 120° C. for 20 min.
- autoclave Consolidated Stills & Sterilizers
- the softwood bark derived oil produced at Monash contains significantly less water than the oil provided by Dynamotive.
- the content of phenols in the softwood bark derived oil is higher than in the oil provided by Dynamotive.
- Table 3 shows the content of sugars in the oil produced by Dynamotive.
- the glucose quantified in this oil was derived from the hydrolysis of levoglucosan, cellobiosan and other oligo-anhydrosugars.
- the content of glucose (a fermentable sugar) in these oils is approximately 5.02 mass %. This concentration of sugar is suitable for fermentation.
- the other sugars derived from hemicelluloses flacose, arabinose, galactose, mannose/xylose, fructose, ribose) accounted for 1.08 mass % of this oil.
- bio-oil compounds acetic acid, propanoic acid, cyclopentanone, 2-furaldehyde, furfuryl alcohol, phenol, eugenol, acetol, 2-(5H)-furanone, stilbene, vanillin, syringaldehyde, o-cresol
- concentration of each of the compounds tested was 25, 50, 75 and 100% of the concentration found in bio-oils (CFBO) for a fast pyrolysis oil derived from Mallee which was produced at a pyrolysis temperature of 500° C.
- the inhibition rate estimated for the compounds studies is shown in Table 4.
- the carboxylic acids acetic acid and propanoic acid
- the phenols phenol, eugenol, vanillin, syringaldehyde, pyrocatechol
- the furans furfuryl alcohol, 2-(5H)-furanone
- the alkanes tetradecane, pentadecane
- Ethyl-acetate was the solvent used for the extraction of compounds from the bio-oil.
- the method employed to separate the phenols is similar to the one patented by NREL for the production of resins. Briefly, blends of ethyl acetate/bio-oil with mass ratio of 1:1 were prepared. The blends were shaken for 10 minutes at 30° C. and were left to equilibrate for over 6 hours. The organic phase rich in ethyl acetate which contains most of the phenols was separated by decantation and the ethyl acetate solubilised in the aqueous phase removed with a rotary evaporator at 80° C.
- the sugars in the aqueous phase were hydrolysed using H 2 SO 4 as catalyst to produce glucose.
- the phenols remaining in the aqueous phase were removed by adsorption on activated carbon.
- An activated carbon/aqueous solution volume ratio of 1:1 was employed.
- the aqueous solution was left overnight at 4° C. in the refrigerator and the slurry formed was filtrated to obtain a colorless liquid.
- the aqueous solution containing the sugars was then neutralized to pH 7 with solid barium hydroxide. Under these conditions the free sulfuric acid and the acetic acid present in the aqueous phase are removed as precipitated salts.
- YPD media was prepared by taking 25 ml of the detoxified solution obtained in the previous step, 2 mass % yeast extract and 1% mass peptone. 10 vol of Saccharomyces cerevisiae seed culture media was then inoculated in the YPD media. The media was cultured at 30° C. and the micro-organism growth, sugar consumption and ethanol production were monitored by UV-Vis, ion exchange chromatography, and GC-FID.
- FIG. 10 shows a glucose content as a function of fermentation time. Based on the consumption of glucose it appears that the fermentation process happened mainly during the first 5 hours. No major difference was observed between the behavior of the control and the solutions derived from pyrolysis oils.
- FIG. 11 shows a rate of microbial growth in solutions derived from bio-oils and in control solutions produced with glucose. As shown in FIG. 11 , most of the growth happened in the first 5 hours and that the growth in the solution derived from bio-oil was comparable with the growth obtained with the control solution prepared with glucose. Very little microbial growth was observed after the first 5 hours.
- FIG. 12 shows ethanol concentration as a function of fermentation time. High concentrations of ethanol were produced (12-16 g/L) during the first 5 hours. The production of ethanol slowed down after almost the same time that the content of glucose in the solution was depleted. The production of ethanol from the solutions derived from bio-oils was comparable to the production of ethanol from the control. The effect of any inhibitor remaining in the solution was negligible.
- Fatty acids were produced from glucose using oleaginous yeasts ( Cryptococcus curvatus and Rhodotorula glutinis yeasts). These yeasts were cultured for periods varying between 24 and 144 hours on a mixture rich in xylose and glucose which were derived from pyrolysis oils. The initial content of glucose in the solution was 6.8 mass %.
- FIG. 13 shows sugar consumption and production of fatty acids as a function of fermentation time in accordance with embodiments of the technology.
- Microorganisms with fat content ranging from 28 to 68 mass % were obtained with the Cryptococcus curvatus .
- Lower fat contents (between 13 and 45 mass %) were obtained with Rhodotorula glutinis .
- the most important fatty acids found in Cryptococcus curvatus were: palmitic (C16:O) (20 mass %), stearic (C18:O) (20 mass %) and oleic (48 mass %) acids.
- a slightly different fatty acid profile was observed for the Rhodotorula glutinis : palmitic (15 mass %), stearic (20 mass %) and oleoic: (51 mass %).
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Health & Medical Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Genetics & Genomics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biotechnology (AREA)
- Microbiology (AREA)
- Materials Engineering (AREA)
- Biomedical Technology (AREA)
- Sustainable Development (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Molecular Biology (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Emergency Medicine (AREA)
- Processing Of Solid Wastes (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A selective pyrolysis process for the production of bio-oils enriched in pyrolytic sugars and phenols and conversion of these compounds into second generation bio-fuels is disclosed herein. One embodiment of the process comprises pre-treating a biomass with superheated steam or gases in a selected range of temperatures, followed by fast pyrolysis using synthesis gas as a carrier, and a two-step condensation operation. The aqueous phase from the second condenser can then be reformed to produce hydrogen or can be gasified together with the charcoal to produce syngas.
Description
- This application claims priority to U.S. Provisional Application No. 61/157,338, filed on Mar. 4, 2009, the disclosure of which is incorporated herein by reference in its entirety.
- This disclosure relates to systems and processes for producing liquid fuels from lignocellulosic materials (e.g., agricultural and forestry residues and energy crops).
- Biomass is an attractive feedstock to offset fossil fuels because it is carbon neutral (or negative), renewable, and may be domestically produced. One conversion platform uses a thermo-chemical process (commonly referred to as “pyrolysis”) to convert biomass into bio-oil. Bio-oils are similar in appearance and color as crude oil though bio-oil contains considerably more oxygenated and functional compounds.
- Although bio-oil can be used directly for stationary diesel engines, bio-oil may be too corrosive and viscous as a transport fuel. There is however great potential to use bio-oil as a feedstock for centralized refineries to produce chemical products and/or transportation fuels. However, several technical challenges exist for the utilization of bio-oil as a feedstock. First, bio-oils are highly acidic and may be corrosive to pipes and storage vessels. Secondly, bio-oils can be unstable when stored for prolonged periods of time. Third, bio-oils typically contain a wide variety of molecules including a substantial amount of small molecules, which are difficult to upgrade. Accordingly, several improvements in converting biomass to bio-oils are needed.
-
FIG. 1 is a schematic flow diagram illustrating a system for converting biomass into bio-oils in accordance with embodiments of the technology. -
FIG. 2 is a schematic diagram illustrating a system for performing bio-oil refining in accordance with embodiments of the technology. -
FIGS. 3A and 3B are schematic diagrams illustrating a reactor in accordance with embodiments of the technology. -
FIG. 4 is a graph showing ratios of peaks in Py-GC/MS chromatogram assigned to levoglucosan and to hydroxyacetaldehyde in accordance with embodiments of the technology. -
FIG. 5 shows the changes of levoglucosan/furfural ratios as a function of pyrolysis temperature in accordance with embodiments of the technology. -
FIGS. 6 and 7 show the ratio of levoglucosan and other products of oxidation reactions in accordance with embodiments of the technology. -
FIG. 8 shows levoglucosan/2-methoxy phenol ratios as a function of pretreatment temperature in accordance with embodiments of the technology. -
FIG. 9 shows levoglucosan/hydroxyacetaldehyde ratios as a function of pyrolysis temperature in accordance with embodiments of the technology. -
FIG. 10 shows a glucose content as a function of fermentation time in accordance with embodiments of the technology. -
FIG. 11 shows a rate of microbial growth in solutions derived from bio-oils and in control solutions produced with glucose in accordance with embodiments of the technology. -
FIG. 12 shows ethanol concentration as a function of fermentation time in accordance with embodiments of the technology. -
FIG. 13 shows sugar consumption and production of fatty acids as a function of fermentation time in accordance with embodiments of the technology. - Specific details of several embodiments of the disclosure are described below with reference to systems and processes to selectively convert lignocellulosic materials into a bio-oil that is rich in anhydrosugars (e.g., levoglucosan and cellobiosan) and phenols as well as the further conversion of the anhydrosugars to ethanol and/or lipids. The term “lignocellulosic materials” generally refers to materials containing cellulose, hemicelluloses, and lignin. Examples of lignocellulosic materials include wood chips, straws, grasses, corn stover, corn husks, weeds, aquatic plants, hay, paper, paper products, recycled paper and/or paper products, and other cellulose containing biological materials or materials of biological origin. Several embodiments can have configurations, components, or procedures different than those described in this section, and other embodiments may eliminate particular components or procedures. A person of ordinary skill in the relevant art, therefore, may understand that the technology may have other embodiments with additional elements, and/or may have other embodiments without several of the features shown and described below with reference to
FIGS. 1-13 . -
FIG. 1 is a schematic flow diagram illustrating asystem 100 for converting biomass into bio-oils in accordance with embodiments of the disclosure. As shown inFIG. 1 , thesystem 100 includes adrier 102, a torrefaction unit (with an optional grinder) 104, apyrolysis reactor 106, afirst condenser 108, asecond condenser 110, and acombustor 112 operatively coupled in series. Thesystem 100 also includes anevaporator 114, asteam reformer 116, and agasification reactor 118 operatively coupled to one another as well as to thepyrolysis reactor 106 and thesecond condenser 110. Even though only particular components are shown inFIG. 1 , other embodiments of thesystem 100 can also include washers, decanters, filters, and/or other suitable components in addition to or in lieu of the foregoing components of thesystem 100. - The
dryer 102 can include a direct-contact dryer, an indirect-contact dryer, and/or other suitable types of dryer. In the illustrated embodiment, thedryer 102 includes a direct-contact dryer configured to receive and contact thebiomass 1 with ahot combustion gas 6 from thecombustor 112. The exhaust from thedryer 102 is vented to atmosphere. In other embodiments, thedryer 102 can also be coupled to an optional hot gas source (e.g., hot air, not shown) for start-up, supplementing thehot combustion gas 6, and/or other suitable purposes. After drying, thedryer 102 provides adried biomass 2 to thetorrefaction unit 104. In further embodiments, thedryer 102 and thetorrefaction unit 104 can be integrated in a single unit (not shown). - The
torrefaction unit 104 can be configured to pre-treat thedried biomass 2 before subjecting the driedbiomass 2 to pyrolysis. Thetorrefaction unit 104 can include any vessel capable of controllably heating the driedbiomass 2 to a desired temperature. Optionally, thetorrefaction unit 104 can also include a grinder and/or other suitable components to reduce the size of the driedbiomass 2. For example, in one embodiment, thetorrefaction unit 104 can include an auger reactor configured to controllably heat thedried biomass 2 while reducing the size of thedried biomass 2, as described in more detail below with reference toFIG. 4 . In other embodiments, thetorrefaction unit 104 may also use asynthesis gas 16 from thereformer 116 as a carrier gas for the pretreatment reactions. - The
pyrolysis reactor 106 can include a fluidized bed, a fixed bed, an ablative reactor, vacuum pyrolysis reactor, auger pyrolysis reactor, and/or other suitable types of pyrolysis reactors. In one embodiment, thepyrolysis reactor 106 can include embodiments of the auger reactor shown inFIG. 3 . In other embodiments, thepyrolysis reactor 106 can include other types of reaction vessels. Even though thetorrefaction unit 104 and thepyrolysis reactor 106 are shown as separate components inFIG. 1 , in certain embodiments, thetorrefaction unit 104 and thepyrolysis reactor 106 can be combined into a single component. In further embodiments, a single component (e.g., the reactor ofFIG. 3 ) may perform the function of both thetorrefaction unit 104 and thepyrolysis reactor 106. As a result, thetorrefaction unit 104 and thepyrolysis reactor 106 may be integrated into a single unit. - The first and
second condensers boiler 114, and thereformer 116 can individually include a plate-and-frame, tube-and-shell, brazed aluminum, and/or other types of heat exchanger. In one embodiment, thefirst condenser 108 can be an empty scrubber. In other embodiments, thefirst condenser 108 can operate in other suitable fashion. Even though the first andsecond condensers FIG. 1 , in certain embodiments, the first andsecond condensers second heat exchangers - The
combustor 112 can be configured to react a combustible gas with air and/or oxygen to produce electrical, heat, and/or other forms of energy. In the illustrated embodiment, thecombustor 112 includes a gas turbine coupled to an electrical generator. In other embodiments, thecombustor 112 can also include a gasoline engine, a diesel engine, a ramjet, and/or other suitable combustion components. In further embodiments, thecombustor 112 may be omitted. - The
gasification reactor 118 can be configured to convert a carbonaceous material into a combination of hydrogen, carbon monoxide, carbon dioxide, and/or other suitable gaseous components. Thegasification reactor 118 can include a counter-current fixed bed gasifier, a co-current fixed bed gasifier, a fluidized bed reactor, an entrained flow gasifier, and/or other suitable types of gasifier. - In operation, the
biomass 1 is provided to drier 102. The drier 102 dries thebiomass 1 with, for example, thecombustion gas 6 from thecombustor 112. The driedbiomass 2 then enters thetorrefaction unit 104 to be pre-treated prior to pyrolysis. In certain embodiments, thetorrefaction unit 104 heats the driedbiomass 2 to a desired temperature (e.g., about 200° C. to about 300° C.) for a treatment period (e.g., 3 min to about 10 hours) with a portion of thesynthetic gas 15 from thereformer 116 as a carrier gas. - The pre-treatment temperature and time may depend on each other. For example, a high pre-treatment temperature may require a short treatment time and vice versa. Without being bound by theory, it is believed that pre-treating the
biomass 1 in thetorrefaction unit 104 can (1) remove at least part of the hemicellulose and acetic acid from the solid matrix; (2) reduce the degree of polymerization of cellulose and increase crystallinity of the cellulose; (3) de-polymerize at least part of the lignin; and (4) weaken biomass fibrous structure for ease of grinding. - The pre-treated biomass is then provided to the
pyrolysis reactor 106 in which the biomass is thermally converted at temperatures between 400 and 500° C. into a vaporphase pyrolysis product 3 andbio-char 8. In certain embodiments, the pre-treated biomass provided to thepyrolysis reactor 106 may contain additives (e.g., H2SO4, (NH4)2HPO4 and (NH4)2SO4) at concentrations of about 0.1 mass % or other suitable concentration values. The additional of such additives are believed to enhance the production of anhydrosugars from biomass. In other embodiments, thepyrolysis reactor 106 may contain other suitable compositions. - In the illustrated embodiment, the first and
second condensers pyrolysis product 3 with ambient air 17 (and/or other suitable coolant) to separate and collect different fractions from thepyrolysis product 3 and produce heated air streams 18 and 19, which is provided to thecombustor 112. In other embodiments, the first andsecond condensers pyrolysis product 3 with ambient air. - The temperature in the
first condenser 108 can be controlled to separate heavier compounds (e.g., phenols and sugars) from light compounds (e.g., acetic and formic acid). A bio-oil 9 can be separated via solvent extraction (e.g., with ethyl acetate) and/or other suitable techniques to produce a stream rich in phenols and pyrolytic sugars. A first fraction of the bio-oil 9, which is rich in sugar can then be hydrolyzed, detoxified and fermented to produce ethanol and/or can be subject to other types of suitable processing to produce other hydrocarbons. A second fraction of the bio-oil 9, which is rich in phenols can be converted into green gasoline via hydro-treatment and/or other suitable processes, as described in more detail below with reference toFIG. 2 . - The
second condenser 110 can then receive anoutput stream 4 from thefirst condenser 106 and collect anaqueous stream 10 from thepyrolysis product 3. Theaqueous stream 10 is then supplied to thereformer 116 via theboiler 114 to produce asynthetic gas 20. Thesynthetic gas 20 is then provided to thecombustor 112 for conversion into electricity and/or other forms of energy. Optionally, theaqueous stream 10 can be gasified with thebio-char 8. Thegasification reactor 118 can convert at least a portion of thebio-char 8 into asynthetic gas 14 provided to thereformer 116 and output the rest of thebio-char 8 as char and ash. In other embodiments, thebio-char 8 may be provided to thecombustor 112 and/or otherwise processed. In further embodiments, thebio-char 8 may form a final product of the process. - Several embodiments of the technology utilize pretreatment with specific temperatures to produce the bio-oil 9 that is more enriched in sugars, less corrosive, more stable than conventional bio-oils. Without being bound by theory, it is believed that biomass degradation via pyrolysis may be classified into three general categories: de-polymerization, fragmentation, and polycondensation. Depolymerization reactions are believed to yield primarily monomers that are greater than five carbons. Such monomers may be either carbohydrodrate (from cellulose/hemicellulose) or aromatic (from lignin). Fragmentation reactions are believed to lead to the formation of small molecules that are typically smaller than five carbons. Poly-condensation reactions are believed to result in the formation of charcoal. Pyrolysis reactors can reduce the formation of char by having very high heating rates which may reduce the time the material is in the temperature range of 270-350° C. in which dehydratation and crosslinking reactions are favored.
- Several embodiments of the
system 100 can alter the structural properties of thebiomass 1 for improving the selectivity to favor depolymerization reactions and improve the bio-oil quality produced during pyrolysis. Several factors are believed to influence whether degradation proceeds via fragmentation or de-polymerization reactions. The presence of alkaline is believed to strongly catalyze fragmentation reactions. Other factors such as degree of polymerization, crystallinity, and the interactions lignin/cellulose are also factors that can be adjusted to improve reaction selectivity toward de-polymerization (formation of precursors of transportation fuels). Thus, by increasing the crystallinity and reducing the degree of polymerization via heating in the temperature range of about 200° C. to about 300° C. (in the presence or absence of steam), the reaction selectivity to de-polymerization may be improved. - Several embodiments of the systems and processes can also have substantial energy savings as a result of pretreatment for grinding operations. The pretreatment not only removes components of the material, it may also attenuate the physical integrity and reduce the energy required to reduce particle sizes to what is required for the pyrolysis reactor. It should be noted that grinding can contribute to as much as 10% of the total energy in the biomass.
-
FIG. 2 is a schematic diagram illustrating aprocess 200 for performing bio-oil refining in accordance with embodiments of the disclosure. As shown inFIG. 2 , theprocess 200 can include separating a phenolic fraction from an aqueous fraction in thebio-oil 9. Techniques suitable for this separation can include liquid-liquid extraction with water, an organic solvent, and/or other suitable materials. The phenolic fraction can then be hydro-treated with hydrogen to produce green gasoline. The aqueous fraction can be (1) hydro-treated under high pressure to produce green diesel; (2) hydrolyzed, neutralized, and detoxified to produce lipids; and/or (3) hydrolyzed, neutralized, detoxified, and fermented to produce alcohol. -
FIG. 3A is a schematic diagram illustrating anreactor 300 in accordance with embodiments of the technology. As shown inFIG. 3A , thereactor 300 includes afeeder 302 coupled to atreatment zone 304 having afirst end 303 a and asecond end 303 b. Thefeeder 302 can include a screw pump and/or other suitable material moving components. Thetreatment zone 30 can include a generally helical auger (or screw) 307 and/or other suitable structures inside ahousing 305 and amotor 320 operatively coupled to theauger 320. - The
reactor 300 also includes aheat exchanger 306 and afurnace 308 on thehousing 305 and a power supply/controller 310 operatively coupled to thefurnace 308. Thereactor 300 further includes asolid container 312 and acondenser 314 proximate to thesecond end 303 b of thetreatment zone 304. Optionally, thereactor 300 includes a plurality of coolingtraps 316 coupled to thecondenser 314 for collecting condensed materials. - In operation, the
feeder 302 forces biomass (shown as separate spheres inFIG. 3A for illustration purposes) to enter thetreatment zone 304 via thefirst end 303 a along with an optional carrier gas. Theheat exchanger 306 and thefurnace 308 then heats the biomass to a desired temperature while theauger 307 moves the biomass toward thesecond end 303 b and reduces the size of the biomass. Solid portions of the biomass are then collected at thesolid container 312 while volatile portions are collected at thecondenser 314 and/or the cooling traps 316. - A
single reactor 300 may be used for both pre-treating and pyrolysis of the biomass. For example, the biomass may be processed in thereactor 300 at a first temperature (e.g., about 200° C. to about 300° C.). The collected solid portions may then be returned to thefeeder 302 to be provided to theauger 304 and processed at a second temperature (e.g., about 500° C. to about 600° C.). - In other embodiments, as shown in
FIG. 3B , thereactor 300 may include more than one treatment zones (e.g., by having more than one furnaces) such that the pre-treatment and pyrolysis operations may be performed in a continuous fashion. Several components shown inFIG. 3B are generally similar in structure and function as those shown inFIG. 3A . As a result, common acts and structures are identified by the same reference numbers. - As shown in
FIG. 3B , thereactor 300 can include afirst treatment zone 304 a coupled to asecond treatment zone 304 b. Thefirst treatment zone 304 a can include a first auger (or screw) 307 a inside afirst housing 305 a having afirst end 303 a and asecond end 303 b. Thefirst auger 307 a can be operatively coupled to afirst motor 320 a. Thefirst treatment zone 304 a also includes afirst furnace 308 a proximate to thefirst housing 305 a and operatively coupled to a first power supply/controller 310 a. Thefirst treatment zone 304 a also includes acarrier gas inlet 324 a and acarrier gas outlet 324 b in fluid communication with theauger 307 a. - Optionally, the
first treatment zone 304 a can also include agrinder 322 and/or other suitable components configured to reduce a physical size of the biomass in thefirst treatment zone 304 a. In the illustrated embodiment, thegrinder 322 is proximate to thesecond end 303 b of the first treatment zone. In other embodiments, thegrinder 322 may be at other locations of the first treatment zone or may be omitted. - The
second treatment zone 304 b can have generally similar components as thefirst treatment zone 304 a. For example, thesecond treatment zone 304 b can include asecond auger 307 b in asecond housing 305 b and operatively coupled to asecond motor 320 b. Thesecond treatment zone 304 b can also include asecond furnace 308 b proximate to thesecond housing 305 b and operatively coupled to a second power supply/controller 310 b. - In operation, the
feeder 302 forces biomass to enter thefirst treatment zone 304 a via thefirst end 303 a along with an optional carrier gas via thecarrier inlet 324 a. Theheat exchanger 306 and thefirst furnace 308 a then heats the biomass to a first temperature (e.g., about 200° C. to about 300° C.) while theauger 307 moves the biomass toward thesecond end 303 b. Theoptional grinder 322 can then reduce the biomass from thefirst treatment zone 304 a to particle sizes less than about 2 mm before the biomass is provided to thesecond treatment zone 304 b. Thesecond furnace 308 b can then heat the biomass to a second temperature (e.g., about 500° C. to about 600° C.) to thermally convert the biomass via pyrolysis. Solid portions of the biomass are then collected at thesolid container 312 while volatile portions are collected at thecondenser 314 and/or the cooling traps 316. - Even though embodiments of the
reactor 300 are shown inFIGS. 3A and 3B as being carried by a cart, in other embodiments, various components of thereactor 300 may be separately and/or fixedly installed. In other embodiments, thereactor 300 may utilize other components for conveying and/or reducing size of the biomass. For example, in certain embodiments, at least one of the first andsecond augers reactor 300 shown inFIG. 3B . Instead, thereactor 300 may carry the biomass through thetreatment zones second treatment zones reactor 300 can include three, four, and/or other suitable number of treatment zones with similar or different configurations. - Tests were conducted to understand the effect of torrefaction conditions (temperature and presence of oxygen) and pyrolysis temperatures on the selectivity of pyrolysis reactions towards the production of anhydrosugars were carried out in our Py-GC/MS. The pretreatment was performed at temperatures ranging from 200 to 320° C. Pyrolysis tests were conducted at temperatures between 350 and 550° C. The tests were carried out with Avicel (crystalline cellulose with low degree of polymerization), α-cellulose (a blend of cellulose and hemicellulose), wheat straw and the woody fraction of Douglas Fir (containing cellulose, hemicelluloses and lignin). Before conducting the Py-GC/MS studies, the alkalines in all the samples were removed with hot water (at 120° C.).
- The Py-GC/MS tests were carried using a CDS pyro-probe 5000 connected in-line to an Agilent GC/MS. Samples were loaded into a quartz tube and gently packed with quartz wool prior to pyrolysis. The samples were kept for 3 minutes at the pretreatment temperature before the oven temperature was reduced to 210° C. The samples were kept in these conditions for 1 minute. Samples were pyrolysed by near instantaneous heating to the final temperature and held at this temperature for 3 minutes.
- The GC/MS inlet temperature was maintained at 250° C. and the resulting pyrolysis vapors were separated by means of a 30 m×0.25 μm inner diameter column. The column was heated at 3° C./min from 40 to 280° C. The gas was then sent into a mass spectrometer and the spectra of the most important peaks were compared to an NBS mass spectra library to establish the identity of each compound.
-
FIG. 4 shows the ratio of the area of the peaks in the Py-GC/MS chromatogram assigned to levoglucosan (a product of cellulose depolymerization reactions) and to hydroxyacetaldehyde (a product of cellulose fragmentation reactions). This ratio can be used as an index of the selectivity of thermochemical reactions towards the production of anhydrosugars.FIG. 4 shows that a mild torrefaction in the range of temperature between 200 and 320° C. can enhance the production of levoglucosan for α-cellulose, wheat straw and the wood fraction of Douglas Fir. - The presence of oxygen during torrefaction had a positive effect on wheat straw. For all the other biomasses, the presence of oxygen during pretreatment is detrimental to the yield of sugar obtained. In the case of Wheat Straw the highest selectivity towards the production of anhydrosugars was obtained for samples pretreated at temperature over 270° C. in the presence of oxygen. For Douglas Fir the best results were achieved for samples pretreated in the absence of oxygen at temperatures over 230° C. It is noteworthy that a drastic increase in the selectivity towards the production of levoglucosan was also observed when the Douglas Fir wood was heated in the presence of oxygen at temperatures over 310° C.
-
FIG. 5 shows the changes of levoglucosan/furfural ratios as a function of pyrolysis temperature in accordance with embodiments of the technology. The pretreatment temperature does not have any effect on the Levoglucosan/furfural ratios for the Avicel. This result suggests that Avicel was not dehydrated in the pretreatment conditions tested. In the case of α-cellulose, an increase in the levoglucosan/furfural ratio was observed as the pretreatment temperature increases. The presence of oxygen during pretreatment of α-cellulose and Avicel causes a reduction in the levogluocan/Furfural ratio for most of the materials but not for the wheat straw. The conditions improving the ratio levoglucosan/furfural are very similar to those improving the ratio levoglucosan/hydroxyacetaldehyde. -
FIGS. 6 and 7 show the ratio of levoglucosan and other products of oxidation reactions in accordance with embodiments of the technology. With the exception of wheat straw, the shapes of the curves describing the evolution of the levoglucosan/carbon dioxide and levoglucosan/acetic acid ratio are similar to those shown inFIGS. 4 and 5 . For the wheat straw there is a maximum for samples pretreated in the presence of oxygen. This maximum could indicate the temperature at which oxidation reactions responsible for the formation of CO2 and acetic acid accelerate. -
FIG. 8 shows levoglucosan/2-methoxy phenol ratios as a function of pretreatment temperature. The conditions improving this ratio were similar to those improving the levoglucosan/CO2 and levoglucosan/acetic acid ratios. But, pre-treating biomass in the presence of oxygen considerably increases the production of mono-phenols due to the oxidation of lignin linkages. According to our results the levoglucosan/2-methoxy phenol ratio can be improved if the wheat straw is pretreated at a 270° C. in the presence of oxygen. The presence of oxygen was detrimental for the Douglas Fir. - The effect of pyrolysis temperatures on the selectivity of thermochemical reactions towards the production of levoglucosan in unpretreated samples is shown in
FIG. 9 . The results indicate that as the pyrolysis temperature increases the fragmentation reactions responsible for the formation of hydroxyacetaldehyde are favored over the depolymerization reactions responsible for the formation of anhydrosugars. Although this behavior was observed for all the samples, the effect of temperature was more pronounced for the Avicel and for the α-cellulose. Materials containing lignin show a much less pronounced effect. - Tests on auger pyrolysis were also conducted. Douglas Fir wood was pre-treated at select conditions identified by Py-GC/MS and was subject to pyrolysis in the Auger Pyrolysis reactor built at Washington State University (generally similar to that shown in
FIG. 3A ). During testing, 200 g of Douglas Fir samples were added into 3 L of deionized water. The biomass and the water were heated in an autoclave (Consolidated Stills & Sterilizers) at 120° C. for 20 min. - The water and the solid were separated by filtration. The solid was dried overnight at 105° C. For every 200 g of biomass 175 g of pre-treated samples were obtained (87.5 mass %). These samples were further subject to a mild torrefaction in the same Auger reactor but using lower wall temperatures (e.g., 270° C.). The reactor was operated under a nitrogen atmosphere (flow rate of nitrogen: 3 l/min) and the biomass particles were conveyed through the Auger at 5.2 rpm (Pretreatment time: 2.5 minutes).
- Pyrolysis tests on the pre-treated samples were carried out in the same Auger Pyrolysis reactor. The reaction conditions were the following: Auger speed: 13 rpm (residence time of particles in the reactor: 1 minute), hopper feeding rate: 43.6 rpm, pressure inside the reactor: 1 atm., carrier gas: N2, flow rate: 10 l/min, temperature in the wall of the reactor: 500° C., post-oven temperature 420° C.; estimated heating rate: (4-7° C./s or 240-420° C./min). Although the heating rates achieved are lower than the 10-1000° C./s needed for fast pyrolysis reactors it is still faster than the 10° C./min typically reported for slow pyrolysis. The yield of products obtained with Douglas Fir as received and after hot water and thermal pretreatment at 270° C. for 3 minutes are shown in Table 1. The oil produced in our system is a single phase oil very similar to those produced in fast pyrolysis reactors.
-
TABLE 1 Hot Water Hot Water + Oven Original Douglas Fir Pretreatment Pretreatment Bio-oil 55.4 ± 4.6 57.1 ± 1.1 56.8 ± 3.6 Char 22.7 ± 5.0 17.4 ± 0.5 19.5 ± 4.8 Gas 21.7 ± 0.6 25.5 ± 1.6 23.7 ± 1.3 - Production of ethanol from pyrolytic sugars was also investigated. Two bio-oils were used to produce ethanol. The first bio-oil produced from a hardwood provided by Dynamotive. The second bio-oil studied was produced in a fast pyrolysis reactor at Monash University (Australia) using as a feedstock a softwood bark. The name and the content of each of the species quantified by GC/MS and by Karl Fischer Titration are listed in Table 2.
-
TABLE 2 Softwood Bark Dynamotive Compound Oil (Monash) Oil 1 Water 13.92 29.35 2 Glycolaldehyde 1.41 1.62 3 Acetic Acid 1.17 3.30 4 Acetol 1.56 2.67 5 Toluene 0.003 0.001 6 Cyclopentanone 0 0.002 7 2-Furaldehyde 0 0.52 8 2-Cyclopenten-1-one, 2-methyl- 0 0.04 9 2(5H)-Furanone 0 0.36 10 2-Furanethanol, b-methoxy-(S)- 0.35 0.83 11 Phenol 0.58 0.29 12 O-Cresol 0.28 0.14 13 p-Cresol and m-Cresol 0.55 0.18 14 Phenol, 2-methoxy- 1.81 1.07 15 Phenol, 2,4-dimethyl- and 0.31 0.12 Phenol, 2,5-dimethyl- 16 Phenol, 4-ethyl- 0.26 0.08 17 Phenol, 3,4-dimethyl- 0.22 0 18 Phenol, 2-methoxy-4-methyl- 0.80 0.29 19 Pyrotechol 1.14 0.67 20 1,2-Benzenediol, 3-methyl- 0.71 0 21 Phenol, 4-ethyl-2-methoxy- 0.43 0.17 22 1,2-Benzenediol, 4-methyl- 1.56 0 23 Syringol 0 1.11 24 Eugenol 0.31 0.13 25 Phenol, 2-methoxy-4-propyl- 0.21 0.09 26 4-Ethylcatechol 0.16 0 27 Vanillin 0.45 0.30 28 Phenol, 2-methoxy-4-(1- 0.76 0.05 propenyl)-, (E)- 29 1,6-Anhydro-b-D-Glucose 3.61 4.07 30 2-Propanone, 1-(4-hydroxy-3- 0.52 0 methoxyphenyl)- 31 Syringaldehyde 0 0.50 32 Phenanthrene, 1-methyl-7- 0.003 0 (1-methylethyl)- Total 33.09 47.9 - As shown in Table 2, the softwood bark derived oil produced at Monash contains significantly less water than the oil provided by Dynamotive. The content of phenols in the softwood bark derived oil is higher than in the oil provided by Dynamotive.
- Table 3 shows the content of sugars in the oil produced by Dynamotive. The glucose quantified in this oil was derived from the hydrolysis of levoglucosan, cellobiosan and other oligo-anhydrosugars. The content of glucose (a fermentable sugar) in these oils is approximately 5.02 mass %. This concentration of sugar is suitable for fermentation. The other sugars derived from hemicelluloses (fucose, arabinose, galactose, mannose/xylose, fructose, ribose) accounted for 1.08 mass % of this oil.
-
TABLE 3 Sugars Content (mass %) Fucose 0.058 Arabinose 0.105 Galactose 0.197 Glucose 5.028 Mannose/Xylose 0.586 Fructose 0.115 Ribose 0.019 Total sugars 6.108 - Although the bulk of the phenolic compounds from bio-oil can be extracted with the ethyl acetate, small concentrations of these toxic compounds remain in the aqueous phase together with most of the sugars. The nature and the range of lethal concentrations of many of these toxic compounds was not well known. Thus, we carried out tests with model compounds to identify which of them were toxic to yeasts.
- The toxic effects of selected bio-oil compounds (acetic acid, propanoic acid, cyclopentanone, 2-furaldehyde, furfuryl alcohol, phenol, eugenol, acetol, 2-(5H)-furanone, stilbene, vanillin, syringaldehyde, o-cresol) on Saccharomyces cerevisiae were studied. The concentration of each of the compounds tested was 25, 50, 75 and 100% of the concentration found in bio-oils (CFBO) for a fast pyrolysis oil derived from Mallee which was produced at a pyrolysis temperature of 500° C. The inhibition rate estimated for the compounds studies is shown in Table 4.
-
TABLE 4 25% of 50% of 75% of 100% of No Compound CFBO CFBO CFBO CFBO 1 Acetic acid 97.75 97.75 97.96 98.24 2 Propanoic acid 97.01 97.54 97.82 98.00 3 Cyclopentanone −22.07 −5.26 −4.41 21.73 4 2-furaldehyde 7.81 7.98 11.03 95.89 5 Furfuryl alcohol 5.94 6.90 7.81 7.81 6 Phenol 76.95 96.95 97.45 97.67 7 Eugenol 97.04 97.22 96.64 97.04 8 Acetol 44.17 77.80 78.93 80.07 9 2-(5H)-Furanone 3.057 5.89 8.83 10.42 10 Stilbene 9.17 32.62 37.89 45.07 11 Vanillin 81.54 82.45 81.77 81.88 12 Syringaldehyde 71.68 79.95 81.54 81.99 13 O-cresol 2.61 14.16 23.38 31.22 14 O-xylol 5.01 5.23 5.33 5.44 15 Pyrocatechol 84.53 90.48 91.67 92.10 16 Palmitic acid 2.63 0.36 −2.02 −4.19 17 Toluene −0.72 1.00 1.66 2.09 18 Tetradecane 1.11 4.68 10.53 10.64 19 Petadecane 4.68 7.39 8.90 9.78 - As shown in Table 4, the carboxylic acids (acetic acid and propanoic acid) and the phenols (phenol, eugenol, vanillin, syringaldehyde, pyrocatechol) are the most lethal compounds inhibiting yeast growth. The furans (furaldehyde, furfuryl alcohol, 2-(5H)-furanone) and the alkanes (tetradecane, pentadecane) are also inhibitors but their inhibition rate is much lower.
- Extraction of phenols, hydrolysis, detoxification and fermentation of pyrolytic sugars were also tested. Ethyl-acetate was the solvent used for the extraction of compounds from the bio-oil. The method employed to separate the phenols is similar to the one patented by NREL for the production of resins. Briefly, blends of ethyl acetate/bio-oil with mass ratio of 1:1 were prepared. The blends were shaken for 10 minutes at 30° C. and were left to equilibrate for over 6 hours. The organic phase rich in ethyl acetate which contains most of the phenols was separated by decantation and the ethyl acetate solubilised in the aqueous phase removed with a rotary evaporator at 80° C.
- The sugars in the aqueous phase (levoglucosan, cellobionsan) were hydrolysed using H2SO4 as catalyst to produce glucose. The phenols remaining in the aqueous phase were removed by adsorption on activated carbon. An activated carbon/aqueous solution volume ratio of 1:1 was employed. The aqueous solution was left overnight at 4° C. in the refrigerator and the slurry formed was filtrated to obtain a colorless liquid. The aqueous solution containing the sugars was then neutralized to
pH 7 with solid barium hydroxide. Under these conditions the free sulfuric acid and the acetic acid present in the aqueous phase are removed as precipitated salts. - The content of sugars in the detoxified solution was quantified by Ion Exchange Chromatography and the detoxified aqueous phase rich in sugars was then fermented. Briefly, YPD media was prepared by taking 25 ml of the detoxified solution obtained in the previous step, 2 mass % yeast extract and 1% mass peptone. 10 vol of Saccharomyces cerevisiae seed culture media was then inoculated in the YPD media. The media was cultured at 30° C. and the micro-organism growth, sugar consumption and ethanol production were monitored by UV-Vis, ion exchange chromatography, and GC-FID. The initial content of glucose in the detoxified aqueous phases from the Dynamotive oil and from the oil produced in Monash University were 2.6 and 2.0 mass % respectively. Clearly the solvent extraction method should be further improved. Control solutions containing the same concentrations of glucose were also fermented.
-
FIG. 10 shows a glucose content as a function of fermentation time. Based on the consumption of glucose it appears that the fermentation process happened mainly during the first 5 hours. No major difference was observed between the behavior of the control and the solutions derived from pyrolysis oils. -
FIG. 11 shows a rate of microbial growth in solutions derived from bio-oils and in control solutions produced with glucose. As shown inFIG. 11 , most of the growth happened in the first 5 hours and that the growth in the solution derived from bio-oil was comparable with the growth obtained with the control solution prepared with glucose. Very little microbial growth was observed after the first 5 hours. -
FIG. 12 shows ethanol concentration as a function of fermentation time. High concentrations of ethanol were produced (12-16 g/L) during the first 5 hours. The production of ethanol slowed down after almost the same time that the content of glucose in the solution was depleted. The production of ethanol from the solutions derived from bio-oils was comparable to the production of ethanol from the control. The effect of any inhibitor remaining in the solution was negligible. - Fatty acids were produced from glucose using oleaginous yeasts (Cryptococcus curvatus and Rhodotorula glutinis yeasts). These yeasts were cultured for periods varying between 24 and 144 hours on a mixture rich in xylose and glucose which were derived from pyrolysis oils. The initial content of glucose in the solution was 6.8 mass %.
-
FIG. 13 shows sugar consumption and production of fatty acids as a function of fermentation time in accordance with embodiments of the technology. Microorganisms with fat content ranging from 28 to 68 mass % were obtained with the Cryptococcus curvatus. Lower fat contents (between 13 and 45 mass %) were obtained with Rhodotorula glutinis. The most important fatty acids found in Cryptococcus curvatus were: palmitic (C16:O) (20 mass %), stearic (C18:O) (20 mass %) and oleic (48 mass %) acids. A slightly different fatty acid profile was observed for the Rhodotorula glutinis: palmitic (15 mass %), stearic (20 mass %) and oleoic: (51 mass %). - From the foregoing, it will be appreciated that specific embodiments of the technology have been described herein for purposes of illustration, but that various modifications may be made without deviating from the technology. Many of the elements of one embodiment may be combined with other embodiments in addition to or in lieu of the elements of the other embodiments. Accordingly, the technology is not limited except as by the appended claims.
Claims (20)
1. A process for processing a biomass, comprising:
treating a biomass by heating the biomass at a first temperature;
thermally converting the treated biomass into a product having an oil portion and an aqueous portion via pyrolysis at a second temperature, the first temperature being lower than the second temperature; and
selecting the first temperature based on a correlation between the first temperature and a desired anhydrosugar content in the oil portion of the product.
2. The process of claim 1 wherein thermally converting includes using a synthesis gas as a carrier gas in a pyrolysis reactor.
3. The process of claim 1 , further comprising producing an oil phase in a first condenser and producing an aqueous phase in a second condenser, the first and second condensers are in a series.
4. The process of claim 1 , further comprising separating sugars from phenols in the oil phase via liquid-liquid extraction with a solvent.
5. The process of claim 1 , further comprising converting at least a fraction of sugars in the oil phase to ethanol.
6. The process of claim 1 wherein the oil phase contains sugars, and wherein the process further comprising converting at least a fraction of the sugars into lipids.
7. The process of claim 1 wherein treating a biomass includes treating a biomass by heating the biomass at a first temperature of about 200° C. to about 300° C.
8. The process of claim 1 wherein treating a biomass includes treating a biomass by heating the biomass at a first temperature of about 200° C. to about 300° C. for a period of time of about 3 minutes to about 10 hours.
9. The process of claim 1 wherein treating a biomass includes treating a biomass by heating the biomass at a first temperature of about 200° C. to about 300° C. for a period of time of about 1 minutes to about 10 hours, and wherein the first temperature is inversely related to the period of time.
10. A process for processing a biomass, comprising:
providing a biomass having a first crystallinity;
modifying a structure of cellulose in the biomass to have a second crystallinity higher than the first crystallinity; and
thermally converting the biomass with the increased crystallinity into a pyrolysis product containing anhydrosugar via pyrolysis.
11. The process of claim 10 wherein:
the first crystallinity of the biomass corresponds to a first anhydrosugar content of the pyrolysis product; and
modifying the structure of cellulose includes modifying the structure of cellulose to have a second crystallinity and/or a degree of polymerization corresponding to a second anhydrosugar content higher than the first anhydrosugar content of the pyrolysis product.
12. The process of claim 10 wherein:
the first crystallinity of the biomass corresponds to an anhydrosugar content of the pyrolysis product; and
modifying the structure of cellulose includes enhancing the anhydrosugar content of the pyrolysis product.
13. The process of claim 10 wherein modifying the structure of cellulose includes heating the biomass at a first temperature of about 200° C. to about 300° C.
14. The process of claim 10 wherein modifying the structure of cellulose includes heating the biomass at a first temperature of about 200° C. to about 300° C. for a period of time of about 1 minute to about 10 hours.
15. The process of claim 10 wherein modifying the structure of cellulose includes heating the biomass at a first temperature of about 200° C. to about 300° C. for a period of time of about 3 minutes to about 10 hours, and wherein the first temperature is inversely related to the period of time.
16. A process for processing a biomass, comprising:
heating a biomass at a first temperature;
thermally converting the heated biomass into a product via pyrolysis at a second temperature, the first temperature being lower than the second temperature; and
wherein the first temperature is selected to enhance an anhydrosugar content in the product from thermally converting the heated biomass.
17. The process of claim 16 wherein the first temperature is selected to be about 200° C. to about 300° C.
18. The process of claim 16 wherein the first temperature is selected to be about 200° C. to about 300° C., and wherein a heating period of time is also selected to enhance the anhydrosugar content in the product from thermally converting the heated biomass.
19. The process of claim 16 wherein the first temperature is selected to be about 200° C. to about 300° C., and wherein a heating period of time is also selected to enhance the anhydrosugar content in the product from thermally converting the heated biomass, the heating period of time being about 1 minute to about 10 hours.
20. The process of claim 16 wherein the first temperature is selected to be about 200° C. to about 300° C., and wherein a heating period of time is also selected to enhance the anhydrosugar content in the product from thermally converting the heated biomass, the heating period of time being about 1 minutes to about 10 hours and inversely related to the first temperature.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/717,833 US20100223839A1 (en) | 2009-03-04 | 2010-03-04 | Systems and processes for producing bio-fuels from lignocellulosic materials |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15733809P | 2009-03-04 | 2009-03-04 | |
US12/717,833 US20100223839A1 (en) | 2009-03-04 | 2010-03-04 | Systems and processes for producing bio-fuels from lignocellulosic materials |
Publications (1)
Publication Number | Publication Date |
---|---|
US20100223839A1 true US20100223839A1 (en) | 2010-09-09 |
Family
ID=42676998
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/717,833 Abandoned US20100223839A1 (en) | 2009-03-04 | 2010-03-04 | Systems and processes for producing bio-fuels from lignocellulosic materials |
Country Status (2)
Country | Link |
---|---|
US (1) | US20100223839A1 (en) |
WO (1) | WO2010102145A1 (en) |
Cited By (89)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110080255A1 (en) * | 2006-10-23 | 2011-04-07 | Borth Paul W | Bedbug detection, monitoring and control techniques |
US20110091940A1 (en) * | 2008-04-03 | 2011-04-21 | Cellulose Sciences International, Inc. | Highly disordered cellulose |
US20110177466A1 (en) * | 2009-01-21 | 2011-07-21 | Cheiky Michael C | System and method for biomass fractioning |
US20110212004A1 (en) * | 2011-03-24 | 2011-09-01 | Michael Cheiky | System for making renewable fuels |
US20110209386A1 (en) * | 2011-03-24 | 2011-09-01 | Michael Cheiky | Method for making renewable fuels |
US20110278149A1 (en) * | 2009-05-11 | 2011-11-17 | Andreas Hornung | Staged biomass pyrolysis process and apparatus |
US20110290202A1 (en) * | 2010-04-26 | 2011-12-01 | Smith Michael J | Method and apparatus for the conversion of aquatic plants into biogases and electricity |
US20120090221A1 (en) * | 2011-05-15 | 2012-04-19 | Avello Bioenergy, Inc. | Methods for integrated fast pyrolysis processing of biomass |
WO2012057986A2 (en) | 2010-10-29 | 2012-05-03 | Kior Inc. | Production of renewable bio-gasoline |
US20120108860A1 (en) * | 2010-10-29 | 2012-05-03 | Conocophillips Company | Process for producing high quality pyrolysis oil from biomass |
US8173044B1 (en) | 2011-05-09 | 2012-05-08 | Cool Planet Biofuels, Inc. | Process for biomass conversion to synthesis gas |
US20120116135A1 (en) * | 2010-11-09 | 2012-05-10 | Conocophillips Company | Heat integrated process for producing high quality pyrolysis oil from biomass |
US20120111714A1 (en) * | 2009-07-01 | 2012-05-10 | Circa Group Pty Ltd | Method for converting lignocellulosic materials into useful chemicals |
CN102476128A (en) * | 2010-11-29 | 2012-05-30 | 华中农业大学 | Method for green conversion of urban and rural household reuse into renewable energy sources |
US20120137538A1 (en) * | 2010-07-15 | 2012-06-07 | Karl Lampe | Device and method for the drying and torrefaction of at least one carbon-containing material flow in a multiple hearth furnace |
US8198493B1 (en) * | 2012-01-11 | 2012-06-12 | Earth Care Products, Inc. | High energy efficiency biomass conversion process |
US20120157726A1 (en) * | 2010-12-15 | 2012-06-21 | Air Liquide Large Industries U.S. Lp | Process For The Production Of Cellulose Based Biofuels |
WO2012094736A1 (en) | 2011-01-14 | 2012-07-19 | Dja Technologies Inc. | Production of biochar absorbent from anaerobic digestate |
US8236085B1 (en) | 2011-06-06 | 2012-08-07 | Cool Planet Biofuels, Inc. | Method for enhancing soil growth using bio-char |
US8308911B2 (en) | 2009-01-09 | 2012-11-13 | Cool Planet Biofuels, Llc | System and method for atmospheric carbon sequestration |
WO2012166771A2 (en) | 2011-05-30 | 2012-12-06 | Washington State University Research Foundation | Processing biomass using thermochemical processing and anaerobic digestion in combination |
US8367881B2 (en) | 2011-05-09 | 2013-02-05 | Cool Planet Biofuels, Inc. | Method for biomass fractioning by enhancing biomass thermal conductivity |
WO2013036694A1 (en) * | 2011-09-06 | 2013-03-14 | Johnston John C | A thermal conversion combined torrefaction and pyrolysis reactor system and method thereof |
WO2013059792A1 (en) * | 2011-10-21 | 2013-04-25 | Therma-Flite, Inc. | Gasifying system and method, and waste-treatment system and method including the same |
US8430937B2 (en) | 2011-07-25 | 2013-04-30 | Cool Planet Biofuels, Inc. | Method for producing negative carbon fuel |
US8431757B2 (en) | 2011-03-24 | 2013-04-30 | Cool Planet Biofuels, Inc. | Method for making renewable fuels |
WO2013078146A1 (en) * | 2011-11-22 | 2013-05-30 | Cool Planet Biofuels Llc | System and process for biomass conversion to renewable fuels with byproducts recycled to gasifier |
US8476480B1 (en) | 2008-08-29 | 2013-07-02 | Iowa State University Research Foundation, Inc. | Bio-oil fractionation and condensation |
US20130213489A1 (en) * | 2010-09-10 | 2013-08-22 | Thyssenkrupp Uhde Gmbh | Method and device for producing process vapor and boiler feed steam in a heatable reforming reactor for producing synthesis gas |
EP2710099A1 (en) * | 2011-05-18 | 2014-03-26 | Bioendev AB | Method for monitoring and control of torrefaction temperature |
US20140175803A1 (en) * | 2012-12-26 | 2014-06-26 | General Electric Company | Biomass conversion reactor power generation system and method |
WO2014110221A1 (en) * | 2013-01-09 | 2014-07-17 | C2O Technologies, Llc | Process for treating coal to improve recovery of condensable coal derived liquids |
ITTO20130193A1 (en) * | 2013-03-12 | 2014-09-13 | Pierluigi Martini | APPARATUS AND METHOD OF TOTAL TREATMENT OF RICE STRAW FOR ENERGETIC USE. |
WO2014164545A1 (en) * | 2013-03-12 | 2014-10-09 | Cool Planet Energy Systems, Inc. | Staged biomass fractionator |
US8951476B2 (en) | 2011-03-24 | 2015-02-10 | Cool Planet Energy Systems, Inc. | System for making renewable fuels |
CN104907321A (en) * | 2015-07-02 | 2015-09-16 | 杨先春 | Comprehensive garbage treatment method |
US9187571B2 (en) | 2008-04-03 | 2015-11-17 | Cellulose Sciences International, Inc. | Nano-deaggregated cellulose |
US9193924B2 (en) | 2011-06-16 | 2015-11-24 | Uop Llc | Methods and apparatuses for forming low-metal biomass-derived pyrolysis oil |
US9260666B2 (en) | 2011-07-25 | 2016-02-16 | Cool Planet Energy Systems, Inc. | Method for reducing the carbon footprint of a conversion process |
US9284203B2 (en) | 2012-01-23 | 2016-03-15 | Anaergia Inc. | Syngas biomethanation process and anaerobic digestion system |
US9416374B2 (en) | 2010-09-24 | 2016-08-16 | Anaergia Inc. | Method for treating lignocellulose-bearing materials |
EP2948240A4 (en) * | 2013-01-28 | 2016-09-28 | Cool Planet Energy Systems Inc | System for making renewable fuels |
US20160304800A1 (en) * | 2013-04-09 | 2016-10-20 | Dia Carbon Technologies Inc. | Torrefaction Process |
US9493380B2 (en) | 2011-06-06 | 2016-11-15 | Cool Planet Energy Systems, Inc. | Method for enhancing soil growth using bio-char |
US9493379B2 (en) | 2011-07-25 | 2016-11-15 | Cool Planet Energy Systems, Inc. | Method for the bioactivation of biochar for use as a soil amendment |
US9580665B2 (en) | 2011-05-18 | 2017-02-28 | Bioendev Ab | Countercurrent oxygen enhanced torrefaction |
US9676678B1 (en) * | 2011-06-21 | 2017-06-13 | Emerging Fuels Technology, Inc. | Renewable fuels co-processing |
US9677005B1 (en) * | 2011-06-21 | 2017-06-13 | Emerging Fuels Technology, Inc. | Integrated fuel processing with biomass oil |
US9799712B2 (en) * | 2016-01-15 | 2017-10-24 | Samsung Display Co., Ltd. | Method of manufacturing light-emitting display device with reduced pressure drying |
US9809502B2 (en) | 2011-06-06 | 2017-11-07 | Cool Planet Energy Systems, Inc. | Enhanced Biochar |
US9868964B2 (en) | 2015-02-06 | 2018-01-16 | Anaergia Inc. | Solid waste treatment with conversion to gas and anaerobic digestion |
US9879285B2 (en) | 2015-07-20 | 2018-01-30 | Anaergia Inc. | Production of biogas from organic materials |
US9890706B2 (en) * | 2012-12-28 | 2018-02-13 | Phoenix Biopower Ab | Method and plant for transferring energy from biomass raw material to at least one energy user |
US9909067B2 (en) | 2009-01-21 | 2018-03-06 | Cool Planet Energy Systems, Inc. | Staged biomass fractionator |
US9944538B2 (en) | 2013-10-25 | 2018-04-17 | Cool Planet Energy Systems, Inc. | System and method for purifying process water |
US9980912B2 (en) | 2014-10-01 | 2018-05-29 | Cool Planet Energy Systems, Inc. | Biochars for use with animals |
US10059634B2 (en) | 2011-06-06 | 2018-08-28 | Cool Planet Energy Systems, Inc. | Biochar suspended solution |
US10118870B2 (en) | 2011-06-06 | 2018-11-06 | Cool Planet Energy Systems, Inc. | Additive infused biochar |
WO2019002690A1 (en) * | 2017-06-28 | 2019-01-03 | Oy Lunawood Ltd | Method and apparatus to extract products from heat treatment process |
US10173937B2 (en) | 2011-06-06 | 2019-01-08 | Cool Planet Energy Systems, Inc. | Biochar as a microbial carrier |
US10190065B2 (en) * | 2013-03-15 | 2019-01-29 | Mark E. Koenig | Feed delivery system and method for gasifier |
IT201700092370A1 (en) * | 2017-08-09 | 2019-02-09 | Univ Degli Studi Di Bari Aldo Moro | Fast pyrolytic process with low environmental impact |
US10233129B2 (en) | 2011-06-06 | 2019-03-19 | Cool Planet Energy Systems, Inc. | Methods for application of biochar |
US10252951B2 (en) | 2011-06-06 | 2019-04-09 | Cool Planet Energy Systems, Inc. | Biochars and biochar treatment processes |
US10301228B2 (en) | 2011-06-06 | 2019-05-28 | Cool Planet Energy Systems, Inc. | Enhanced biochar |
US10322389B2 (en) | 2014-10-01 | 2019-06-18 | Cool Planet Energy Systems, Inc. | Biochar aggregate particles |
EP3388498A4 (en) * | 2015-12-08 | 2019-07-17 | University Industry Foundation, Yonsei University Wonju Campus | Method for producing bio-oil using torrefaction and fast pyrolysis process |
US10392313B2 (en) | 2011-06-06 | 2019-08-27 | Cool Planet Energy Systems, Inc. | Method for application of biochar in turf grass and landscaping environments |
EP3540032A1 (en) * | 2018-03-16 | 2019-09-18 | Wilson Bio-Chemical Limited | Processing waste into carbon char |
US10472297B2 (en) | 2014-10-01 | 2019-11-12 | Cool Planet Energy System, Inc. | Biochars for use in composting |
US10550044B2 (en) | 2011-06-06 | 2020-02-04 | Cool Planet Energy Systems, Inc. | Biochar coated seeds |
FR3086299A1 (en) * | 2018-09-26 | 2020-03-27 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | METHOD AND PLANT FOR THE PRODUCTION OF EUGENOL BY BIOMASS ROASTING FOLLOWED BY A STAGE CONDENSATION |
US10870608B1 (en) | 2014-10-01 | 2020-12-22 | Carbon Technology Holdings, LLC | Biochar encased in a biodegradable material |
US11053171B2 (en) | 2014-10-01 | 2021-07-06 | Carbon Technology Holdings, LLC | Biochars for use with animals |
US11097241B2 (en) | 2014-10-01 | 2021-08-24 | Talipot Cool Extract (Ip), Llc | Biochars, biochar extracts and biochar extracts having soluble signaling compounds and method for capturing material extracted from biochar |
US11123778B2 (en) | 2016-03-18 | 2021-09-21 | Anaergia Inc. | Solid waste processing with pyrolysis of cellulosic waste |
US11214528B2 (en) | 2011-06-06 | 2022-01-04 | Carbon Technology Holdings, LLC | Treated biochar for use in water treatment systems |
US11279894B2 (en) * | 2012-01-30 | 2022-03-22 | Aries Gasification, Llc | Universal feeder for gasification reactors |
US11279662B2 (en) | 2011-06-06 | 2022-03-22 | Carbon Technology Holdings, LLC | Method for application of biochar in turf grass and landscaping environments |
US11286507B2 (en) | 2013-07-11 | 2022-03-29 | Anaergia Inc. | Anaerobic digestion and pyrolysis system |
CN114380665A (en) * | 2022-01-26 | 2022-04-22 | 南京林业大学 | Method for converting cellulose into phenol primary product |
US11312666B2 (en) | 2011-06-06 | 2022-04-26 | Carbon Technology Holdings, LLC | Mineral solubilizing microorganism infused biochars |
US11345859B2 (en) * | 2018-06-24 | 2022-05-31 | Bioforce Tech Corporation | Hybrid pyrolysis system and method |
EP4019612A1 (en) * | 2020-12-23 | 2022-06-29 | Ingelia, S.L. | Apparatus to obtain valuable products from biomass and process thereof |
US20220204860A1 (en) * | 2019-04-15 | 2022-06-30 | Carbonzero Sagl | Continuous reactor device and process for treatment of biomass |
US11390569B2 (en) | 2011-06-06 | 2022-07-19 | Carbon Technology Holdings, LLC | Methods for application of biochar |
US11426350B1 (en) | 2014-10-01 | 2022-08-30 | Carbon Technology Holdings, LLC | Reducing the environmental impact of farming using biochar |
WO2023111376A1 (en) * | 2021-12-13 | 2023-06-22 | Greene Enterprise, S.L. | Method for valorization of waste material |
US11866329B2 (en) | 2017-12-15 | 2024-01-09 | Talipot Cool Extract (Ip), Llc | Biochars, biochar extracts and biochar extracts having soluble signaling compounds and method for capturing material extracted from biochar |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5668469B2 (en) * | 2010-12-28 | 2015-02-12 | トヨタ自動車株式会社 | Method for thermal decomposition of plant biomass |
US9035116B2 (en) * | 2012-08-07 | 2015-05-19 | Kior, Inc. | Biomass feed system including gas assist |
CN103540379B (en) * | 2013-10-31 | 2015-03-11 | 华南理工大学 | Solid fuel prepared by hydrothermal carbonization of aqueous phase component of biological oil as well as method thereof |
US10577544B2 (en) * | 2014-04-15 | 2020-03-03 | Iowa State University Research Foundation, Inc. | Low temperature, low pressure upgrading and stabilization of bio-oil or bio-oil fractions |
WO2017105817A1 (en) * | 2015-12-16 | 2017-06-22 | Exxonmobil Research And Engineering Company | Microbial fermentation of anhydrosugars to fatty acid alkyl esters |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4153514A (en) * | 1975-02-27 | 1979-05-08 | Occidental Petroleum Corporation | Pyrolysis process for solid wastes |
US4880473A (en) * | 1988-04-01 | 1989-11-14 | Canadian Patents & Development Ltd. | Process for the production of fermentable sugars from biomass |
US5223601A (en) * | 1988-12-29 | 1993-06-29 | Midwest Research Institute Ventures, Inc. | Phenolic compounds containing/neutral fractions extract and products derived therefrom from fractionated fast-pyrolysis oils |
US5395455A (en) * | 1992-03-10 | 1995-03-07 | Energy, Mines And Resources - Canada | Process for the production of anhydrosugars from lignin and cellulose containing biomass by pyrolysis |
US6485841B1 (en) * | 1998-10-30 | 2002-11-26 | Ensyn Technologies, Inc. | Bio-oil preservatives |
US20070125369A1 (en) * | 2005-02-07 | 2007-06-07 | Olson Edwin S | Process for converting anhydrosugars to glucose and other fermentable sugars |
US20080006520A1 (en) * | 2006-07-06 | 2008-01-10 | Badger Phillip C | Method and system for accomplishing flash or fast pyrolysis with carbonaceous materials |
US20090047721A1 (en) * | 2007-06-01 | 2009-02-19 | Solazyme, Inc. | Renewable Diesel and Jet Fuel from Microbial Sources |
US7572365B2 (en) * | 2002-10-11 | 2009-08-11 | Ivanhoe Energy, Inc. | Modified thermal processing of heavy hydrocarbon feedstocks |
-
2010
- 2010-03-04 US US12/717,833 patent/US20100223839A1/en not_active Abandoned
- 2010-03-04 WO PCT/US2010/026265 patent/WO2010102145A1/en active Application Filing
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4153514A (en) * | 1975-02-27 | 1979-05-08 | Occidental Petroleum Corporation | Pyrolysis process for solid wastes |
US4880473A (en) * | 1988-04-01 | 1989-11-14 | Canadian Patents & Development Ltd. | Process for the production of fermentable sugars from biomass |
US5223601A (en) * | 1988-12-29 | 1993-06-29 | Midwest Research Institute Ventures, Inc. | Phenolic compounds containing/neutral fractions extract and products derived therefrom from fractionated fast-pyrolysis oils |
US5395455A (en) * | 1992-03-10 | 1995-03-07 | Energy, Mines And Resources - Canada | Process for the production of anhydrosugars from lignin and cellulose containing biomass by pyrolysis |
US6485841B1 (en) * | 1998-10-30 | 2002-11-26 | Ensyn Technologies, Inc. | Bio-oil preservatives |
US7572365B2 (en) * | 2002-10-11 | 2009-08-11 | Ivanhoe Energy, Inc. | Modified thermal processing of heavy hydrocarbon feedstocks |
US20070125369A1 (en) * | 2005-02-07 | 2007-06-07 | Olson Edwin S | Process for converting anhydrosugars to glucose and other fermentable sugars |
US20080006520A1 (en) * | 2006-07-06 | 2008-01-10 | Badger Phillip C | Method and system for accomplishing flash or fast pyrolysis with carbonaceous materials |
US20090047721A1 (en) * | 2007-06-01 | 2009-02-19 | Solazyme, Inc. | Renewable Diesel and Jet Fuel from Microbial Sources |
Non-Patent Citations (5)
Title |
---|
Lipinsky, E.S. et al. (2002). Fuel Chemistry Division Preprints, 47(1), 408-410. * |
Molton, P.M. et al. (1977). Reaction Mechanisms in Cellulose Pyrolysis: A Literature Review, Battelle Pacific Northwest Laboratory, 178 pgs. * |
Piskorz, J. et al. (1989). Journal of Analytical and Applied Pyrolysis, 16, 127-142. * |
Puri, V.P. (1984). Biotechnology and Bioengineering, 26, 1219-1222. * |
Taylor, J.B. (1957). transactions of the Faraday Society, 53, 1198-1203. * |
Cited By (143)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8375626B2 (en) | 2006-10-23 | 2013-02-19 | Dow Agrosciences, Llc | Bedbug detection, monitoring and control techniques |
US8661728B2 (en) | 2006-10-23 | 2014-03-04 | Dow Agrosciences, Llc | Bedbug detection, monitoring and control techniques |
US8984804B2 (en) | 2006-10-23 | 2015-03-24 | Dow Agrosciences, Llc. | Bedbug detection, monitoring and control techniques |
US20110080255A1 (en) * | 2006-10-23 | 2011-04-07 | Borth Paul W | Bedbug detection, monitoring and control techniques |
US10264776B2 (en) | 2006-10-23 | 2019-04-23 | Dow Agrosciences Llc | Bedbug detection, monitoring and control techniques |
US9187571B2 (en) | 2008-04-03 | 2015-11-17 | Cellulose Sciences International, Inc. | Nano-deaggregated cellulose |
US20110091940A1 (en) * | 2008-04-03 | 2011-04-21 | Cellulose Sciences International, Inc. | Highly disordered cellulose |
US9611439B1 (en) | 2008-08-29 | 2017-04-04 | Iowa State University Research Foundation, Inc. | Bio-oil fractionation and condensation |
US8476480B1 (en) | 2008-08-29 | 2013-07-02 | Iowa State University Research Foundation, Inc. | Bio-oil fractionation and condensation |
US8308911B2 (en) | 2009-01-09 | 2012-11-13 | Cool Planet Biofuels, Llc | System and method for atmospheric carbon sequestration |
US9909067B2 (en) | 2009-01-21 | 2018-03-06 | Cool Planet Energy Systems, Inc. | Staged biomass fractionator |
US20110177466A1 (en) * | 2009-01-21 | 2011-07-21 | Cheiky Michael C | System and method for biomass fractioning |
US8293958B2 (en) | 2009-01-21 | 2012-10-23 | Cool Planet Biofuels, Inc. | System and method for biomass fractioning |
US8216430B2 (en) | 2009-01-21 | 2012-07-10 | Cool Planet Biofuels, Inc. | System and method for biomass fractioning |
US20110278149A1 (en) * | 2009-05-11 | 2011-11-17 | Andreas Hornung | Staged biomass pyrolysis process and apparatus |
US20120111714A1 (en) * | 2009-07-01 | 2012-05-10 | Circa Group Pty Ltd | Method for converting lignocellulosic materials into useful chemicals |
US9505985B2 (en) * | 2009-07-01 | 2016-11-29 | Circa Group Pty Ltd | Method for converting lignocellulosic materials into useful chemicals |
US20110290202A1 (en) * | 2010-04-26 | 2011-12-01 | Smith Michael J | Method and apparatus for the conversion of aquatic plants into biogases and electricity |
US9295205B2 (en) | 2010-04-26 | 2016-03-29 | Ssb International, Llc | System for producing a biogas |
US20120137538A1 (en) * | 2010-07-15 | 2012-06-07 | Karl Lampe | Device and method for the drying and torrefaction of at least one carbon-containing material flow in a multiple hearth furnace |
US9102876B2 (en) * | 2010-07-15 | 2015-08-11 | Thyssenkrupp Industrial Solutions Ag | Device and method for the drying and torrefaction of at least one carbon-containing material flow in a multiple hearth furnace |
US8904970B2 (en) * | 2010-09-10 | 2014-12-09 | Thyssenkrupp Uhde Gmbh | Method and device for producing process vapor and boiler feed steam in a heatable reforming reactor for producing synthesis gas |
US20130213489A1 (en) * | 2010-09-10 | 2013-08-22 | Thyssenkrupp Uhde Gmbh | Method and device for producing process vapor and boiler feed steam in a heatable reforming reactor for producing synthesis gas |
US9416374B2 (en) | 2010-09-24 | 2016-08-16 | Anaergia Inc. | Method for treating lignocellulose-bearing materials |
WO2012057986A2 (en) | 2010-10-29 | 2012-05-03 | Kior Inc. | Production of renewable bio-gasoline |
US20120108860A1 (en) * | 2010-10-29 | 2012-05-03 | Conocophillips Company | Process for producing high quality pyrolysis oil from biomass |
EP2633007A2 (en) * | 2010-10-29 | 2013-09-04 | KiOR, Inc. | Production of renewable bio-gasoline |
EP2633007A4 (en) * | 2010-10-29 | 2014-12-10 | Kior Inc | Production of renewable bio-gasoline |
US20120116135A1 (en) * | 2010-11-09 | 2012-05-10 | Conocophillips Company | Heat integrated process for producing high quality pyrolysis oil from biomass |
CN102476128A (en) * | 2010-11-29 | 2012-05-30 | 华中农业大学 | Method for green conversion of urban and rural household reuse into renewable energy sources |
US20120157726A1 (en) * | 2010-12-15 | 2012-06-21 | Air Liquide Large Industries U.S. Lp | Process For The Production Of Cellulose Based Biofuels |
WO2012094736A1 (en) | 2011-01-14 | 2012-07-19 | Dja Technologies Inc. | Production of biochar absorbent from anaerobic digestate |
US9919290B2 (en) | 2011-01-14 | 2018-03-20 | Char Technologies Inc. | Production of biochar absorbent from anaerobic digestate |
EP2663397A4 (en) * | 2011-01-14 | 2017-08-16 | Char Technologies Inc. | Production of biochar absorbent from anaerobic digestate |
US8431757B2 (en) | 2011-03-24 | 2013-04-30 | Cool Planet Biofuels, Inc. | Method for making renewable fuels |
US8951476B2 (en) | 2011-03-24 | 2015-02-10 | Cool Planet Energy Systems, Inc. | System for making renewable fuels |
US9951280B2 (en) | 2011-03-24 | 2018-04-24 | Cool Planet Energy Systems, Inc. | System and method for making renewable fuels |
US9328290B2 (en) | 2011-03-24 | 2016-05-03 | Cool Planet Energy Systems, Inc. | System and method for making renewable fuels |
US8143464B2 (en) | 2011-03-24 | 2012-03-27 | Cool Planet Biofuels, Inc. | Method for making renewable fuels |
US9403140B2 (en) | 2011-03-24 | 2016-08-02 | Cool Planet Energy Systems, Inc. | System for making renewable fuels |
US8137628B2 (en) | 2011-03-24 | 2012-03-20 | Cool Planet Biofuels, Inc. | System for making renewable fuels |
US20110209386A1 (en) * | 2011-03-24 | 2011-09-01 | Michael Cheiky | Method for making renewable fuels |
US20110212004A1 (en) * | 2011-03-24 | 2011-09-01 | Michael Cheiky | System for making renewable fuels |
US8367881B2 (en) | 2011-05-09 | 2013-02-05 | Cool Planet Biofuels, Inc. | Method for biomass fractioning by enhancing biomass thermal conductivity |
US10066167B2 (en) | 2011-05-09 | 2018-09-04 | Cool Planet Energy Systems, Inc. | Method for biomass fractioning by enhancing biomass thermal conductivity |
US8372311B2 (en) | 2011-05-09 | 2013-02-12 | Cool Planet Biofuels, Inc. | Process for biomass conversion to synthesis gas |
US9333474B2 (en) | 2011-05-09 | 2016-05-10 | Cool Planet Energy Systems, Inc. | Method for biomass fractioning by enhancing biomass thermal conductivity |
US8173044B1 (en) | 2011-05-09 | 2012-05-08 | Cool Planet Biofuels, Inc. | Process for biomass conversion to synthesis gas |
US8425633B2 (en) * | 2011-05-15 | 2013-04-23 | Avello Bioenergy, Inc. | Methods for integrated fast pyrolysis processing of biomass |
US20120090221A1 (en) * | 2011-05-15 | 2012-04-19 | Avello Bioenergy, Inc. | Methods for integrated fast pyrolysis processing of biomass |
EP2710099A1 (en) * | 2011-05-18 | 2014-03-26 | Bioendev AB | Method for monitoring and control of torrefaction temperature |
US9580665B2 (en) | 2011-05-18 | 2017-02-28 | Bioendev Ab | Countercurrent oxygen enhanced torrefaction |
EP2710099A4 (en) * | 2011-05-18 | 2015-03-11 | Bioendev Ab | Method for monitoring and control of torrefaction temperature |
US9926507B2 (en) | 2011-05-18 | 2018-03-27 | Bioendev Ab | Method for monitoring and control of torrefaction temperature |
WO2012166771A2 (en) | 2011-05-30 | 2012-12-06 | Washington State University Research Foundation | Processing biomass using thermochemical processing and anaerobic digestion in combination |
EP2739577A4 (en) * | 2011-05-30 | 2015-04-01 | Univ Washington State Res Fdn | Processing biomass using thermochemical processing and anaerobic digestion in combination |
EP2739577A2 (en) * | 2011-05-30 | 2014-06-11 | Washington State University Research Foundation | Processing biomass using thermochemical processing and anaerobic digestion in combination |
US9493380B2 (en) | 2011-06-06 | 2016-11-15 | Cool Planet Energy Systems, Inc. | Method for enhancing soil growth using bio-char |
US10023503B2 (en) | 2011-06-06 | 2018-07-17 | Cool Planet Energy Systems, Inc. | Biochars and biochar treatment processes |
US10472298B2 (en) | 2011-06-06 | 2019-11-12 | Cool Planet Energy System, Inc. | Biochar suspended solution |
US10118870B2 (en) | 2011-06-06 | 2018-11-06 | Cool Planet Energy Systems, Inc. | Additive infused biochar |
US11390569B2 (en) | 2011-06-06 | 2022-07-19 | Carbon Technology Holdings, LLC | Methods for application of biochar |
US10301228B2 (en) | 2011-06-06 | 2019-05-28 | Cool Planet Energy Systems, Inc. | Enhanced biochar |
US8236085B1 (en) | 2011-06-06 | 2012-08-07 | Cool Planet Biofuels, Inc. | Method for enhancing soil growth using bio-char |
US10273195B2 (en) | 2011-06-06 | 2019-04-30 | Cool Planet Energy Systems, Inc. | Method for the bioactivation of biochar for use as a soil amendment |
US10252951B2 (en) | 2011-06-06 | 2019-04-09 | Cool Planet Energy Systems, Inc. | Biochars and biochar treatment processes |
US10059634B2 (en) | 2011-06-06 | 2018-08-28 | Cool Planet Energy Systems, Inc. | Biochar suspended solution |
US10233129B2 (en) | 2011-06-06 | 2019-03-19 | Cool Planet Energy Systems, Inc. | Methods for application of biochar |
US11384031B2 (en) | 2011-06-06 | 2022-07-12 | Carbon Technology Holdings, LLC | Biochar as a microbial carrier |
US10550044B2 (en) | 2011-06-06 | 2020-02-04 | Cool Planet Energy Systems, Inc. | Biochar coated seeds |
US10106471B2 (en) | 2011-06-06 | 2018-10-23 | Cool Planet Energy Systems, Inc. | Biochars and biochar treatment processes |
US10556838B2 (en) | 2011-06-06 | 2020-02-11 | Cool Planet Energy Systems, Inc. | Biochars and biochar treatment processes |
US11180428B2 (en) | 2011-06-06 | 2021-11-23 | Talipot Cool Extract (Ip), Llc | Biochar suspended solution |
US8317891B1 (en) | 2011-06-06 | 2012-11-27 | Cool Planet Biofuels, Inc. | Method for enhancing soil growth using bio-char |
US10173937B2 (en) | 2011-06-06 | 2019-01-08 | Cool Planet Energy Systems, Inc. | Biochar as a microbial carrier |
US11130715B2 (en) | 2011-06-06 | 2021-09-28 | Talipot Cool Extract (Ip), Llc | Biochar coated seeds |
US10093588B2 (en) | 2011-06-06 | 2018-10-09 | Cool Planet Energy Systems, Inc. | Method for enhancing soil growth using bio-char |
US11214528B2 (en) | 2011-06-06 | 2022-01-04 | Carbon Technology Holdings, LLC | Treated biochar for use in water treatment systems |
US8317892B1 (en) | 2011-06-06 | 2012-11-27 | Cool Planet Biofuels, Inc. | Method for enhancing soil growth using bio-char |
US11312666B2 (en) | 2011-06-06 | 2022-04-26 | Carbon Technology Holdings, LLC | Mineral solubilizing microorganism infused biochars |
US9809502B2 (en) | 2011-06-06 | 2017-11-07 | Cool Planet Energy Systems, Inc. | Enhanced Biochar |
US11279662B2 (en) | 2011-06-06 | 2022-03-22 | Carbon Technology Holdings, LLC | Method for application of biochar in turf grass and landscaping environments |
US10392313B2 (en) | 2011-06-06 | 2019-08-27 | Cool Planet Energy Systems, Inc. | Method for application of biochar in turf grass and landscaping environments |
US9193924B2 (en) | 2011-06-16 | 2015-11-24 | Uop Llc | Methods and apparatuses for forming low-metal biomass-derived pyrolysis oil |
US9676678B1 (en) * | 2011-06-21 | 2017-06-13 | Emerging Fuels Technology, Inc. | Renewable fuels co-processing |
US9677005B1 (en) * | 2011-06-21 | 2017-06-13 | Emerging Fuels Technology, Inc. | Integrated fuel processing with biomass oil |
US8430937B2 (en) | 2011-07-25 | 2013-04-30 | Cool Planet Biofuels, Inc. | Method for producing negative carbon fuel |
US8568493B2 (en) | 2011-07-25 | 2013-10-29 | Cool Planet Energy Systems, Inc. | Method for producing negative carbon fuel |
US9963650B2 (en) | 2011-07-25 | 2018-05-08 | Cool Planet Energy Systems, Inc. | Method for making sequesterable biochar |
US9260666B2 (en) | 2011-07-25 | 2016-02-16 | Cool Planet Energy Systems, Inc. | Method for reducing the carbon footprint of a conversion process |
US9493379B2 (en) | 2011-07-25 | 2016-11-15 | Cool Planet Energy Systems, Inc. | Method for the bioactivation of biochar for use as a soil amendment |
US9359268B2 (en) | 2011-07-25 | 2016-06-07 | Cool Planet Energy Systems, Inc. | Method for producing negative carbon fuel |
WO2013036694A1 (en) * | 2011-09-06 | 2013-03-14 | Johnston John C | A thermal conversion combined torrefaction and pyrolysis reactor system and method thereof |
WO2013059792A1 (en) * | 2011-10-21 | 2013-04-25 | Therma-Flite, Inc. | Gasifying system and method, and waste-treatment system and method including the same |
US9446975B2 (en) | 2011-10-21 | 2016-09-20 | Therma-Flite, Inc. | Gasifying system and method |
US9873842B2 (en) | 2011-11-22 | 2018-01-23 | Cool Planet Energy Systems, Inc. | System and process for biomass conversion to renewable fuels with byproducts recycled to gasifier |
WO2013078146A1 (en) * | 2011-11-22 | 2013-05-30 | Cool Planet Biofuels Llc | System and process for biomass conversion to renewable fuels with byproducts recycled to gasifier |
CN104302766A (en) * | 2011-11-22 | 2015-01-21 | 酷星能源系统公司 | System and process for biomass conversion to renewable fuels with byproducts recycled to gasifier |
US8198493B1 (en) * | 2012-01-11 | 2012-06-12 | Earth Care Products, Inc. | High energy efficiency biomass conversion process |
US9567247B2 (en) | 2012-01-23 | 2017-02-14 | Anaergia Inc. | Syngas biomethanation process and anaerobic digestion system |
US9284203B2 (en) | 2012-01-23 | 2016-03-15 | Anaergia Inc. | Syngas biomethanation process and anaerobic digestion system |
US11279894B2 (en) * | 2012-01-30 | 2022-03-22 | Aries Gasification, Llc | Universal feeder for gasification reactors |
US20140175803A1 (en) * | 2012-12-26 | 2014-06-26 | General Electric Company | Biomass conversion reactor power generation system and method |
US9890706B2 (en) * | 2012-12-28 | 2018-02-13 | Phoenix Biopower Ab | Method and plant for transferring energy from biomass raw material to at least one energy user |
US9598646B2 (en) | 2013-01-09 | 2017-03-21 | C20 Technologies, Llc | Process for treating coal to improve recovery of condensable coal derived liquids |
WO2014110221A1 (en) * | 2013-01-09 | 2014-07-17 | C2O Technologies, Llc | Process for treating coal to improve recovery of condensable coal derived liquids |
EP2948240A4 (en) * | 2013-01-28 | 2016-09-28 | Cool Planet Energy Systems Inc | System for making renewable fuels |
ITTO20130193A1 (en) * | 2013-03-12 | 2014-09-13 | Pierluigi Martini | APPARATUS AND METHOD OF TOTAL TREATMENT OF RICE STRAW FOR ENERGETIC USE. |
WO2014164545A1 (en) * | 2013-03-12 | 2014-10-09 | Cool Planet Energy Systems, Inc. | Staged biomass fractionator |
US10190065B2 (en) * | 2013-03-15 | 2019-01-29 | Mark E. Koenig | Feed delivery system and method for gasifier |
US20160304800A1 (en) * | 2013-04-09 | 2016-10-20 | Dia Carbon Technologies Inc. | Torrefaction Process |
US11286507B2 (en) | 2013-07-11 | 2022-03-29 | Anaergia Inc. | Anaerobic digestion and pyrolysis system |
US9944538B2 (en) | 2013-10-25 | 2018-04-17 | Cool Planet Energy Systems, Inc. | System and method for purifying process water |
US10864492B2 (en) | 2014-10-01 | 2020-12-15 | Carbon Technology Holdings, LLC | Method for producing biochar aggregate particles |
US10472297B2 (en) | 2014-10-01 | 2019-11-12 | Cool Planet Energy System, Inc. | Biochars for use in composting |
US10322389B2 (en) | 2014-10-01 | 2019-06-18 | Cool Planet Energy Systems, Inc. | Biochar aggregate particles |
US11426350B1 (en) | 2014-10-01 | 2022-08-30 | Carbon Technology Holdings, LLC | Reducing the environmental impact of farming using biochar |
US11739031B2 (en) | 2014-10-01 | 2023-08-29 | Carbon Technology Holdings, LLC | Biochar encased in a biodegradable material |
US9980912B2 (en) | 2014-10-01 | 2018-05-29 | Cool Planet Energy Systems, Inc. | Biochars for use with animals |
US10870608B1 (en) | 2014-10-01 | 2020-12-22 | Carbon Technology Holdings, LLC | Biochar encased in a biodegradable material |
US11053171B2 (en) | 2014-10-01 | 2021-07-06 | Carbon Technology Holdings, LLC | Biochars for use with animals |
US11097241B2 (en) | 2014-10-01 | 2021-08-24 | Talipot Cool Extract (Ip), Llc | Biochars, biochar extracts and biochar extracts having soluble signaling compounds and method for capturing material extracted from biochar |
US11111185B2 (en) | 2014-10-01 | 2021-09-07 | Carbon Technology Holdings, LLC | Enhanced biochar |
US9868964B2 (en) | 2015-02-06 | 2018-01-16 | Anaergia Inc. | Solid waste treatment with conversion to gas and anaerobic digestion |
CN104907321A (en) * | 2015-07-02 | 2015-09-16 | 杨先春 | Comprehensive garbage treatment method |
US9879285B2 (en) | 2015-07-20 | 2018-01-30 | Anaergia Inc. | Production of biogas from organic materials |
EP3388498A4 (en) * | 2015-12-08 | 2019-07-17 | University Industry Foundation, Yonsei University Wonju Campus | Method for producing bio-oil using torrefaction and fast pyrolysis process |
US9799712B2 (en) * | 2016-01-15 | 2017-10-24 | Samsung Display Co., Ltd. | Method of manufacturing light-emitting display device with reduced pressure drying |
US11123778B2 (en) | 2016-03-18 | 2021-09-21 | Anaergia Inc. | Solid waste processing with pyrolysis of cellulosic waste |
WO2019002690A1 (en) * | 2017-06-28 | 2019-01-03 | Oy Lunawood Ltd | Method and apparatus to extract products from heat treatment process |
US11766626B2 (en) | 2017-06-28 | 2023-09-26 | Oy Lunawood Ltd | Method and apparatus to extract products from heat treatment process |
IT201700092370A1 (en) * | 2017-08-09 | 2019-02-09 | Univ Degli Studi Di Bari Aldo Moro | Fast pyrolytic process with low environmental impact |
WO2019030689A1 (en) * | 2017-08-09 | 2019-02-14 | Universita' Degli Studi Di Bari Aldo Moro | Fast pyrolytic process with low environmental impact based on controlled reforming of produced syngas |
US11866329B2 (en) | 2017-12-15 | 2024-01-09 | Talipot Cool Extract (Ip), Llc | Biochars, biochar extracts and biochar extracts having soluble signaling compounds and method for capturing material extracted from biochar |
EP3540032A1 (en) * | 2018-03-16 | 2019-09-18 | Wilson Bio-Chemical Limited | Processing waste into carbon char |
US11345859B2 (en) * | 2018-06-24 | 2022-05-31 | Bioforce Tech Corporation | Hybrid pyrolysis system and method |
EP3628654A1 (en) * | 2018-09-26 | 2020-04-01 | Commissariat à l'Energie Atomique et aux Energies Alternatives | Method and facility for producing eugenol by roasting biomass followed by staged condensation |
FR3086299A1 (en) * | 2018-09-26 | 2020-03-27 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | METHOD AND PLANT FOR THE PRODUCTION OF EUGENOL BY BIOMASS ROASTING FOLLOWED BY A STAGE CONDENSATION |
US20220204860A1 (en) * | 2019-04-15 | 2022-06-30 | Carbonzero Sagl | Continuous reactor device and process for treatment of biomass |
US11981868B2 (en) * | 2019-04-15 | 2024-05-14 | Carbonzero Sagl | Continuous reactor device and process for treatment of biomass |
EP4019612A1 (en) * | 2020-12-23 | 2022-06-29 | Ingelia, S.L. | Apparatus to obtain valuable products from biomass and process thereof |
WO2023111376A1 (en) * | 2021-12-13 | 2023-06-22 | Greene Enterprise, S.L. | Method for valorization of waste material |
CN114380665A (en) * | 2022-01-26 | 2022-04-22 | 南京林业大学 | Method for converting cellulose into phenol primary product |
Also Published As
Publication number | Publication date |
---|---|
WO2010102145A1 (en) | 2010-09-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20100223839A1 (en) | Systems and processes for producing bio-fuels from lignocellulosic materials | |
Ruan et al. | Biofuels: introduction | |
Cao et al. | Hydrothermal liquefaction of agricultural and forestry wastes: state-of-the-art review and future prospects | |
Tekin et al. | A review of hydrothermal biomass processing | |
Lian et al. | Separation, hydrolysis and fermentation of pyrolytic sugars to produce ethanol and lipids | |
Alvarez-Chavez et al. | Physical, chemical, thermal and biological pre-treatment technologies in fast pyrolysis to maximize bio-oil quality: A critical review | |
Ly et al. | Fast pyrolysis of macroalga Saccharina japonica in a bubbling fluidized-bed reactor for bio-oil production | |
Abnisa et al. | Characterization of bio-oil and bio-char from pyrolysis of palm oil wastes | |
Demirbas | Current technologies for the thermo-conversion of biomass into fuels and chemicals | |
Nanda et al. | Lignocellulosic biomass: a review of conversion technologies and fuel products | |
US20130295628A1 (en) | Processes for producing energy-dense biomass and sugars or sugar derivatives, by integrated hydrolysis and torrefaction | |
Sidi-Yacoub et al. | Characterization of lignocellulosic components in exhausted sugar beet pulp waste by TG/FTIR analysis | |
Islam et al. | Microbial conversion of pyrolytic products to biofuels: a novel and sustainable approach toward second-generation biofuels | |
WO2010033512A1 (en) | Improved process for preparing bio-oils from biomass | |
Huang et al. | Utilization of rice hull and straw | |
Balan et al. | Biochemical and thermochemical conversion of switchgrass to biofuels | |
Kumar | Sub-and supercritical water technology for biofuels | |
US20150167969A1 (en) | Processes utilizing fermentation vinasse for producing energy-dense biomass and biomass sugars | |
EP3194536B1 (en) | Method for thermal treatment of raw materials comprising lignocellulose | |
EP2673338A2 (en) | Renewable heating oil | |
Hu et al. | Energy from biomass | |
WO2015134314A1 (en) | Processes utilizing fermentation vinasse for producing energy-dense biomass and biomass sugars | |
Adeoye et al. | Sustainable Energy via Thermochemical and Biochemical Conversion of Biomass Wastes for Biofuel Production | |
Perez et al. | Integrated process of biomass thermochemical conversion to obtain pyrolytic sugars for biofuels and bioproducts | |
Oliveira et al. | From solid biowastes to liquid biofuels |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: WASHINGTON STATE UNIVERSITY, WASHINGTON Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:GARCIA-PEREZ, MANUEL;JOHNSON, ROBERT L.;LIAW, SHI-SHEN;AND OTHERS;SIGNING DATES FROM 20100315 TO 20100330;REEL/FRAME:024389/0424 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |