WO2009099684A2 - Methods and apparatus for catalytic hydrothermal gasification of biomass - Google Patents

Methods and apparatus for catalytic hydrothermal gasification of biomass Download PDF

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Publication number
WO2009099684A2
WO2009099684A2 PCT/US2009/030099 US2009030099W WO2009099684A2 WO 2009099684 A2 WO2009099684 A2 WO 2009099684A2 US 2009030099 W US2009030099 W US 2009030099W WO 2009099684 A2 WO2009099684 A2 WO 2009099684A2
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WIPO (PCT)
Prior art keywords
wet
feedstock
biomass
separation unit
catalyst
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PCT/US2009/030099
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English (en)
French (fr)
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WO2009099684A3 (en
Inventor
Douglas C. Elliott
Robert Scott Butner
Gary G. Neuenschwander
Alan H. Zacher
Todd R. Hart
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Battelle Memorial Institute
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Publication of WO2009099684A2 publication Critical patent/WO2009099684A2/en
Publication of WO2009099684A3 publication Critical patent/WO2009099684A3/en

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Classifications

    • 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
    • C10J3/72—Other features
    • C10J3/78—High-pressure apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
    • 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
    • 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
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08—Production of synthetic natural gas
    • 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
    • C10L9/086—Hydrothermal carbonization
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • 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
    • C10J2300/0916—Biomass
    • 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
    • C10J2300/0916—Biomass
    • C10J2300/0923—Sludge, e.g. from water treatment plant
    • 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
    • C10J2300/0973—Water
    • C10J2300/0979—Water as supercritical steam
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/145—Feedstock the feedstock being materials of biological origin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • Gasification of biomass by thermal methods involving pyrolysis and/or partial oxidation is known as a method to produce a synthesis gas, composed of carbon oxides and hydrogen, or a fuel gas.
  • Many of the known methods use a dry biomass feedstock with less than 10 wt % moisture.
  • much of the biomass resource contains higher levels of moisture, more typically 50 wt% and some even consist of wet biomass, or biomass in water slurries at 85 wt% moisture or higher.
  • One approach to efficiently process such wet biomass is gasification employing an active catalyst in a pressurized water environment (e.g., hydrothermal gasification).
  • the present invention includes apparatuses and methods for treating wet biomass by catalytic hydro thermal gasification that address the problem of poisoning and fouling of the catalyst, especially for long-term and/or continuous use.
  • the inorganic wastes that precipitate in the catalyst and cause plugging and poisoning can be precipitated by heating the wet biomass feedstock prior to exposure to the catalyst.
  • treatment of the wet biomass feedstock comprises heating the wet biomass with a heating unit to a temperature sufficient for organic constituents in the feedstock to decompose, for precipitates of inorganic wastes to form, for preheating the wet feedstock in preparation for subsequent separation of sulfur contaminants, or combinations thereof.
  • Treatment further comprises separating the precipitates out of the wet feedstock, removing sulfur contaminants, or both using a solids separation unit and a sulfur separation unit, respectively. Having removed much of the inorganic wastes and the sulfur that can cause poisoning and fouling, the wet biomass feedstock can be exposed to the heterogeneous catalyst for gasification.
  • biomass refers to biological material that can be used for fuel or for industrial production.
  • Exemplary biomass can include, but is not limited to, biosludge from wastewater treatment facilities, sewage sludge from municipal treatment systems, wet byproducts from bioreflnery operations, wet byproducts/residues from food processing, animal waste and waste from centralized animal raising facilities, organic chemical manufacturing wastewater streams, and industrial wastewater containing organics.
  • Biomass commonly comprises organic matter that can be treated in a continuous reactor, according to embodiments of the present invention, to yield a gas containing hydrogen or useful for hydrogen production (e.g., methane).
  • Common inorganic contaminants, which can poison and/or foul the catalyst can include, but are not limited to minerals comprising Ca, Mg, P, and/or Fe.
  • the heterogeneous catalysts comprise Ru, Ni, and/or Ni with added Na.
  • the Na can be in the form of a sodium carbonate co-catalyst.
  • the catalyst comprises Ru on a carbon support.
  • the catalyst can be configured to gasify Ih ⁇ organic constituents into a hydrogen- containing feedstock' for subsequent catalytic reformation.
  • Separation of solids from the heated wet biomass feedstock can be achieved using a solids separation unit, which can include, but is not limited to, a gravity separation unit, a hydrocyelonie separation unit, and/or a filtration unit.
  • Removal of sulfur can be achieved using a sulfur separation unit comprising, for example, an adsorbent bed with a metal or metal oxide.
  • the catalytic hydro thermal gasification occurs at conditions in which water is below its critical point (i.e., sub-critical), in a particular embodiment, the wet biomass feedstock is heated to at least 300 0 C. In another embodiment, a catalytic reactor containing the heterogeneous catalyst is heated to a temperature between 250 0 C and 374 0 C. The pressure in the catalytic reactor can be up to 23 MPa. In a preferred embodiment the catalytic reactor is operated at temperatures between 340 0 C and 360 0 C and pressures between 18 MPa and 21 MPa.
  • FIG. 1 is a diagram depicting system for hydrothcrmal gasification of biomass according to one embodiment of the present invention.
  • the wet biomass feedstock typically comprises at least two types of solids that can clog, plug, and/or poison the catalyst including organic matter and mineral materials.
  • proper preheating of the biomass feedstock can transform the solid organic matter to liquid and/or gas, both of which can pass into the catalytic reactor without causing plugging and/or poisoning.
  • char can be a major product at sub-critical conditions.
  • the present invention also calls for sub-critical operating conditions and provides approaches for the minerals to be precipitated and separated from the stream while allowing the liquefied biomass organics to pass on to the catalytic reactor. With the solids separated, a sulfur scrubber bed could also be used without plugging, as well as the catalytic bed for gasification.
  • a more stable nickel catalyst was used and was effective (97.7% COD reduction @ 2.3 LHSV) but lost activity (71.2% COD reduction @ 2.0 LHSV) after several hours.
  • Analysis of the catalyst showed deposits of biomass-derived minerals on the catalyst such as hydroxylapatite (Ca 5 (PO ⁇ )OH) and nickel subsulfid ⁇ (Ni 3 S 2 ).
  • apatite and nickel subsuifide but also iron phosphate, ammonium iron sulfate, potassium alurainosiiicate, calcium carbonate, calcium magnesium sulfate, and anorrhoelasc, an alkali silicoaiuminate. All of these precipitates were attributed to components in the biomass feedstock. Furthermore, in tubular-reactor-only configurations, biomass slurry pumping difficulties became evident. Processing of slurries of ground potato or apple peels were short-lived because of pump failures and plugging of solids at the front end of the catalytic bed. The plugging appeared to be primarily organic solids produced from partially pyrolyzed biomass. These short-lived tests verified the high activity (95.4% COD reduction @ 2.67 LHSV) of the ruthenium stabilized nickel catalyst for biomass gasification.
  • a continuous-flow reactor system comprises a wet biomass feedstock heater, a sulfur removal unit, a solids separation unit, and a catalytic reactor.
  • FIG. 1 One particular system similar to the one illustrated in Fig. 1 was based on a throughput of 0.5-10 Ib of slurry or solution per hour and was typically operated over a range of 1 to 3 liter/hour. These operating parameters are not to be construed as limitations to the present invention, but are rather descriptive by way of example.
  • Slimy feeding to the pressurized system was accomplished using a syringe pump having a large-bore valve package that controls the feeding from one cylinder or the other.
  • the valve package comprised four 3/8-inch air-actuated (6000 psi rated) ball valves with 3/8- inch stainless steel (SS) tubing connections. Oversize caps were installed on the barrels that accommodate 3/8-inch NPT fittings.
  • the large bore head, valve, and tubing allowed suctioning and pumping of the viscous slurries while still allowing the pump to operate at 3500 psi max. All valves and valve trim (except the pressure-control valve) were made of SS. The feeding rates were measured directly by the screw drive of the positive displacement syringe pump.
  • the preheater was a 1 -liter 316 SS vessel that functioned as a continuous- flow, stirred-tank reactor in which the feedstock was brought to the reaction temperature.
  • the organics in the biomass were pyrolyzed and liquefied while inorganic components, such as calcium phosphates, formed and precipitated as solids.
  • the catalytic reactor was constructed of 304 SS and had an inner diameter of one inch with a length of 72 inches.
  • the reactor had boltcd-closurc cndeaps with metal o-rings on each end.
  • Catalyst pellets were supported in the reactor on a circle of fine screen.
  • the reactor furnace was a 6-kWe resistance heater split into three separately controllable zones. The pressure was controlled with a dome-loaded diaphragm backpressure regulator.
  • a solid separations unit was placed in the process line between the preheater and the reactor to capture and remove the solids before they reached the catalyst bed, where, in previous tests, they have collected and caused flow plugging.
  • a sulfur scrubber trap incorporated a chemical trap for reduced sulfur forms.
  • the sulfur components reacted with the trap material to form insoluble sulfide, which prevented their passing into the catalyst bed where they could react with the metal of the catalyst and destroy its catalytic capability.
  • the mineral recovery system recovered a solid with 91 % ash content and which accounted for less than 1% of the carbon in the feedstock. Phosphate in the feedstock at about 2700 ppm was found to be absent, ⁇ lppm, following the processing.
  • Phosphate in the feedstock at about 940 ppm was found to be absent, ⁇ lppm, following the processing. Sulfate was also present in the feed at 35 ppm but was found in the range of 2 to 10 ppm in the effluent.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Processing Of Solid Wastes (AREA)
  • Treatment Of Sludge (AREA)
  • Catalysts (AREA)
PCT/US2009/030099 2008-01-31 2009-01-05 Methods and apparatus for catalytic hydrothermal gasification of biomass WO2009099684A2 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US2497008P 2008-01-31 2008-01-31
US61/024,970 2008-01-31
US12/339,876 US8241605B2 (en) 2008-01-31 2008-12-19 Methods and apparatus for catalytic hydrothermal gasification of biomass
US12/339,876 2008-12-19

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WO2012167793A2 (en) 2011-06-10 2012-12-13 Steeper Energy Aps Process and apparatus for producing liquid hydrocarbon
WO2012167794A2 (en) 2011-06-10 2012-12-13 Steeper Energy Aps Process and apparatus for producing liquid hydrocarbons
US8519203B2 (en) 2010-02-17 2013-08-27 Uop Llc Low oxygen biomass-derived pyrolysis oils and methods for producing the same
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US8961743B2 (en) 2007-11-20 2015-02-24 Ensyn Renewables, Inc. Rapid thermal conversion of biomass
US9044727B2 (en) 2011-09-22 2015-06-02 Ensyn Renewables, Inc. Apparatuses and methods for controlling heat for rapid thermal processing of carbonaceous material
US9102889B2 (en) 2011-12-12 2015-08-11 Ensyn Renewables, Inc. Fluidized catalytic cracker riser quench system
US9127208B2 (en) 2006-04-03 2015-09-08 Pharmatherm Chemicals, Inc. Thermal extraction method and product
US9347005B2 (en) 2011-09-13 2016-05-24 Ensyn Renewables, Inc. Methods and apparatuses for rapid thermal processing of carbonaceous material
US9422478B2 (en) 2010-07-15 2016-08-23 Ensyn Renewables, Inc. Char-handling processes in a pyrolysis system
US9441887B2 (en) 2011-02-22 2016-09-13 Ensyn Renewables, Inc. Heat removal and recovery in biomass pyrolysis
US9670413B2 (en) 2012-06-28 2017-06-06 Ensyn Renewables, Inc. Methods and apparatuses for thermally converting biomass
US9951278B2 (en) 2010-05-20 2018-04-24 Ensyn Renewables, Inc. Processes for controlling afterburn in a reheater and for controlling loss of entrained solid particles in combustion product flue gas
US9982199B2 (en) 2012-08-30 2018-05-29 Steeper Energy Aps Method for preparing start up of process and equipment for producing liquid hydrocarbons
US10005962B2 (en) 2012-08-30 2018-06-26 Steeper Energy Aps Method for preparing shut down of process and equipment for producing liquid hydrocarbons
US10041667B2 (en) 2011-09-22 2018-08-07 Ensyn Renewables, Inc. Apparatuses for controlling heat for rapid thermal processing of carbonaceous material and methods for the same
US10087373B2 (en) 2012-08-30 2018-10-02 Steeper Energy Aps Method for controlling cleaning of an apparatus for producing liquid hydrocarbons
US10337726B2 (en) 2015-08-21 2019-07-02 Ensyn Renewables, Inc. Liquid biomass heating system
US10400176B2 (en) 2016-12-29 2019-09-03 Ensyn Renewables, Inc. Demetallization of liquid biomass
US10400175B2 (en) 2011-09-22 2019-09-03 Ensyn Renewables, Inc. Apparatuses and methods for controlling heat for rapid thermal processing of carbonaceous material
US10428276B2 (en) 2014-05-05 2019-10-01 Steeper Energy Aps Feed mixture for producing hydrocarbons
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US9404063B2 (en) 2013-11-06 2016-08-02 Battelle Memorial Institute System and process for efficient separation of biocrudes and water in a hydrothermal liquefaction system
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