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WO2015081104A1 - Récupération de composés organiques à partir de la phase aqueuse d'une pyrolyse catalytique de biomasse et leur valorisation - Google Patents

Récupération de composés organiques à partir de la phase aqueuse d'une pyrolyse catalytique de biomasse et leur valorisation Download PDF

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Publication number
WO2015081104A1
WO2015081104A1 PCT/US2014/067421 US2014067421W WO2015081104A1 WO 2015081104 A1 WO2015081104 A1 WO 2015081104A1 US 2014067421 W US2014067421 W US 2014067421W WO 2015081104 A1 WO2015081104 A1 WO 2015081104A1
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Prior art keywords
group
water
metals
organic compounds
aqueous stream
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PCT/US2014/067421
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English (en)
Inventor
Maria Magdalena Ramirez-Corredores
Leslie May
Christopher PARADISE
Nicholas KENT
Xiaowei TONG
Rocio Maria Banda
Royce ROEMISCH
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Inaeris Technologies LLC
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Kior Inc
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Priority claimed from US14/090,801 external-priority patent/US20140221693A1/en
Application filed by Kior Inc filed Critical Kior Inc
Publication of WO2015081104A1 publication Critical patent/WO2015081104A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
    • C07C37/82—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by solid-liquid treatment; by chemisorption
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/79—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
    • C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves

Definitions

  • Embodiments of the invention relate generally to an improved method for recovering organics from an aqueous phase. More particularly, embodiments of the invention relate to a method including one or more removal zones/stages employing sorbents or extractants for removal of organics from such aqueous phase and to methods of recovering such organics after removal. Embodiments of the invention also relate to methods for converting the lighter portion of the recovered organics to heavier organics.
  • renewable energy sources have become increasingly important.
  • the development of renewable fuel sources provides a means for reducing the dependence on fossil fuels. Accordingly, many different areas of renewable fuel research are currently being explored and developed.
  • biomass With its low cost and wide availability, biomass has increasingly been emphasized as an ideal feedstock in renewable fuel research. Consequently, many different conversion processes have been developed that use biomass as a feedstock to produce useful biofuels and/or specialty chemicals.
  • Existing biomass conversion processes include, for example, combustion, gasification, slow pyrolysis, fast pyrolysis, thermocatalytic pyrolysis, liquefaction, and enzymatic conversion.
  • One of the useful products that may be derived from the aforementioned biomass conversion processes is a liquid product commonly referred to as "bio-oil.” Bio-oil may be processed into transportation fuels, hydrocarbon chemicals, and/or specialty chemicals.
  • the water-soluble organic compounds contain heavy oxygenated compounds and light oxygenated compounds having 5 or less carbon atoms.
  • Such light oxygenated compounds having 5 or less carbon atoms only possess green chemicals value, but no value at all for fuels production (fuel value).
  • trying to subject these light oxygenated compounds to hydrodeoxygenation for fuels production wastes hydrotreater capacity and valuable hydrogen, since only light gases can be produced.
  • reactions such as ketonization, etherification or esterification of these light oxygenated compounds will also render products of no fuel value.
  • a method for recovering a water-soluble complex mixture of organic compounds from an aqueous stream including:
  • removed quantity B comprises light oxygenated compounds and heavy oxygenated compounds; wherein the light oxygenated compounds are separated from the removed quantity B in step c); and wherein a reactor feed comprises the light oxygenated compounds and is charged to a basic catalyzed reactor containing a basic catalyst for conversion of the light oxygenated compounds to heavier oxygenated compounds.
  • a method for recovering a water-soluble complex mixture of organic compounds from an aqueous stream includes:
  • the recovered quantity comprises light oxygenated compounds and heavy oxygenated compounds; and wherein a reactor feed comprises the recovered quantity and is charged to a basic catalyzed reactor containing a basic catalyst for conversion of the light oxygenated compounds to heavier oxygenated compounds prior to combination with the bio-oil stream.
  • FIG. 1 is a schematic view of a two-stage sorption method/system for carrying out a specific embodiment of the invention.
  • FIG. 1 a is a schematic view of a two-stage sorption method/system including up to two additional optional stages for carrying out specific embodiments of the invention.
  • FIG. 1 b is a schematic view of a two-stage sorption method/system including up to two additional optional stages for carrying out specific embodiments of the invention.
  • FIG. 1 c is a schematic view of a two-stage sorption method/system including up to two additional optional stages for carrying out specific embodiments of the invention.
  • FIG. 2 is a schematic view of a sorption method/system including a bio- oil/water separator for carrying out specific embodiments of the invention.
  • FIG. 3 is a schematic view of a method/system for recovering sorbed quantities from a removal zone in accordance with an embodiment of the invention.
  • FIG. 4 is a schematic view of a method/system for recovering sorbed quantities from a removal zone in accordance with an embodiment of the invention.
  • FIG. 5 is a schematic view of a method/system for recovering sorbed quantities from a removal zone in accordance with an embodiment of the invention.
  • FIG. 6 is a graph depicting thermograms for various granulated activated carbon samples.
  • FIG. 7 is a schematic view of a method/system for reacting recovered quantities from a removal zone(s) in accordance with an embodiment of the invention.
  • FIG. 8 is a schematic view of a method/system for reacting recovered quantities from a removal zone(s), which includes a separator, in accordance with an embodiment of the invention.
  • FIG. 9 is a schematic view of a method/system for reacting recovered quantities from a removal zone(s), which includes a separator, in accordance with an embodiment of the invention.
  • FIG. 10 is a schematic view of a method/system for removing, recovering and reacting oxygenated compounds contained in an aqueous stream in accordance with an embodiment of the invention.
  • FIG. 11 is a graph depicting Nuclear Magnetic Resonance spectra of a light oxygenated compound feed and the reaction product resulting from reacting such feed with a basic catalyst.
  • FIG. 12 presents a visual comparison of samples of the light oxygenated compound feed and the resulting reaction product of FIG. 11.
  • pyrolysis processes in particular flash pyrolysis processes, are generally recognized as offering the most promising routes to the conversion of solid biomass materials to liquid products, generally referred to as bio-oil or bio-crude.
  • these processes produce gaseous reaction products and solid reaction products.
  • Gaseous reaction products comprise carbon dioxide, carbon monoxide, and relatively minor amounts of hydrogen, methane, and ethylene.
  • the solid reaction products comprise coke and char.
  • the pyrolysis process should provide a relatively fast heating rate of the biomass feedstock. Lately, the focus has been on ablative reactors, cyclone reactors, and fluidized reactors to provide the fast heating rates. Fluidized reactors include both fluidized stationary bed reactors and transport reactors.
  • Transport reactors provide heat to the reactor feed by injecting hot particulate heat carrier material into the reaction zone. This technique provides rapid heating of the feedstock. The fluidization of the feedstock ensures an even heat distribution within the mixing zone of the reactor.
  • the biomass to be pyrolyzed is generally ground to a small particle size in order to optimize pyrolysis.
  • the biomass may be ground in a grinder or a mill until the desired particle size is achieved.
  • an aqueous stream is produced as a part of the reaction products.
  • this aqueous stream is usually emulsified with the organic portion (bio-oil) of the reaction products.
  • the aqueous stream is only separable from the organic portion of the reaction products upon breaking the emulsion by some further treatment, such as hydrotreatment or de-oxygenation, of the organic components of the reaction products.
  • the aqueous and bio-oil streams form into two separate phases which are separable by methods including, but not limited to, gravity separation and centrifugation.
  • the bio-oil phase is often more dense than the aqueous phase, causing the aqueous phase to rest on top of the bio-oil phase.
  • the density of either the aqueous phase or bio-oil phase can be adjusted.
  • the aqueous stream can contain up to 10 or up to 15 wt% of a water-soluble complex mixture of organic compounds. This amount of organic compounds can account for up to 30 wt% of the total organics yield from the biomass.
  • the water-soluble complex mixture of organic compounds contained in the aqueous phase include phenols, catechols, aromatics, aldehydes, ketones, carboxylic acids, furans, indenols, and naphthols. Their relative proportions increase with increasing polarity of the compound.
  • a method 10 for recovering at least a portion of the water-soluble complex mixture of organic compounds from the aqueous stream comprises, consists of, or consists essentially of:
  • At least a portion of the removed quantity A can be recovered from the removal zone A forming a recovered quantity A and at least a portion of the removed quantity B can be recovered from the removal zone B forming a recovered quantity B.
  • Sorbent B can be selected from the group consisting of polymeric microreticular sorbent resins, zeolite-based adsorbents, clay-based adsorbents, activated carbon-based sorbents, and mixtures thereof.
  • the polymeric microreticular sorbent resins can be selected from the group consisting of Amberlite, Osorb, Amberlyst, Super adsorbent, and mixtures thereof;
  • the zeolite-based adsorbents can be selected from the group consisting of X-Faujasite, Y-Faujasite, ZSM-5, zeolite-A, and mixtures thereof;
  • the clay-based adsorbents can be selected from the group consisting of kaolin, bentonite, chlorite, perovskite, smectite, organoclays and mixtures thereof;
  • the activated carbon-based sorbents can be selected from the group consisting of microporous activated carbon, mesoporous activated carbon, carbon molecular sieves, carbon microbeads, carbon powder, granular activated carbon, and mixtures thereof.
  • the aqueous stream can optionally be passed to a removal zone C prior to being passed to removal zone A.
  • removal zone C at least a portion of the water-soluble complex mixture of organic compounds can be removed from the aqueous stream forming a removed quantity C comprising water-soluble organic compounds. At least a portion of the removed quantity C can be removed from the removal zone C forming recovered quantity C.
  • Removal zone C can comprise a sorbent C selected from the group consisting of zeolite-based adsorbents (as described above), clay-based adsorbents, (as described above), and mixtures thereof, which sorbs at least a portion of the water-soluble complex mixture of organic compounds from the aqueous stream through contact with sorbent C forming the removed quantity C.
  • a sorbent C selected from the group consisting of zeolite-based adsorbents (as described above), clay-based adsorbents, (as described above), and mixtures thereof, which sorbs at least a portion of the water-soluble complex mixture of organic compounds from the aqueous stream through contact with sorbent C forming the removed quantity C.
  • the aqueous stream can optionally be passed from removal zone C to a removal zone D comprising a super absorbent polymer for removal of at least a portion of the water from the aqueous stream through contact with the super absorbent polymer and yielding a stream of recovered quantity D comprising concentrated water-soluble organic compounds.
  • the stream of recovered quantity D can then be passed to removal zone A as at least part of the aqueous stream.
  • the super absorbent polymer in removal zone D can be regenerated by taking removal zone D offline and heating at a temperature between about 50°C and about 90°C under an inert gas flow having a GHSV of at least about 0.5h "1 , thereby removing the water.
  • Removal zone C can comprise an extraction zone wherein the aqueous stream is contacted with a solvent selected from the group consisting of i) renewable gasoline, ii) toluene, iii) xylene, iv) oxygenated solvents selected from the group consisting of methanol, ethanol, isopropanol, acetone, methylbutyl ketone, tetrahydrofuran, ethyl acetate, and v) mixtures thereof for extractive removal of at least a portion of the water-soluble complex mixture of organic compounds from the aqueous stream forming the removed quantity C.
  • a solvent selected from the group consisting of i) renewable gasoline, ii) toluene, iii) xylene, iv) oxygenated solvents selected from the group consisting of methanol, ethanol, isopropanol, acetone, methylbutyl ketone, tetrahydrofuran, ethyl acetate
  • the aqueous stream can optionally be passed from removal zone A to a removal zone E comprising a super absorbent polymer prior to being passed to removal zone B. At least a portion of the water from the aqueous stream can be removed in removal zone E through contact with the super absorbent polymer and yielding a stream of recovered quantity E comprising concentrated water-soluble organic compounds. The stream of recovered quantity E can then be passed from removal zone E to removal zone B as at least part of the aqueous stream.
  • the super absorbent polymer in removal zone E can be regenerated by taking removal zone E offline and heating at a temperature between about 50°C and about 90°C under an inert gas flow having a GHSV of at least about 0.5h "1 , thereby removing the water.
  • the aqueous stream can optionally be passed to a removal zone F comprising a zeolite-based adsorbent prior to being passed to removal zone A. At least a portion of the water-soluble complex mixture of organic compounds are sorbed from the aqueous stream through contact with the zeolite-based adsorbent forming a removed quantity F comprising water- soluble organic compounds. At least a portion of the removed quantity F can be removed from the removal zone F forming recovered quantity F.
  • the aqueous stream can optionally be passed from removal zone B to a removal zone G comprising a super absorbent polymer. At least a portion of the water from the aqueous stream can be removed in removal zone G through contact with the super absorbent polymer and yielding a stream of recovered quantity G comprising concentrated water-soluble organic compounds. Also, the super absorbent polymer in removal zone G can be regenerated by taking removal zone G offline and heating at a temperature between about 50°C and about 90°C under an inert gas flow having a GHSV of at least about 0.5h '1 , thereby removing the water.
  • the aqueous stream can optionally be passed to a removal zone H comprising a sorbent H prior to being passed to removal zone A.
  • Sorbent H can be selected from the group consisting of zeolite-based adsorbents, clay-based adsorbents, and mixtures thereof. At least a portion of the water-soluble organic compounds from the aqueous stream can be sorbed in removal zone H through contact with the sorbent H forming a removed quantity H comprising water-soluble organic compounds. At least a portion of the removed quantity H can be removed from the removal zone H forming recovered quantity H.
  • a bio-oil/water stream comprising a water-soluble complex mixture of organic compounds, water-insoluble organic compounds, and water is separated into a bio-oil stream comprising water-insoluble organic compounds and into the aqueous stream.
  • the recovered quantities (recovered from the aqueous stream) described above can be combined with the bio-oil stream.
  • a method 20 for recovering a water-soluble complex mixture of organic compounds from an aqueous stream comprises, consists of, or consists essentially of:
  • At least a portion of the removed quantity can be recovered from the activated carbon-based sorbent forming a recovered quantity, which can be combined with the bio-oil stream.
  • aqueous stream, and intermediate streams described above can be charged to the removal zones in either an upflow or a downflow mode.
  • the method of recovering the removed quantities from the sorbent materials can be any of the methods well known in the art, such as thermal desorption, thermal expansion (under vacuum) or chemical displacement.
  • a method 30 for recovering removed quantities from a removal zone is described below with reference to FIG. 3.
  • the sorbent in a removal zone 300 is selected from the group consisting of at least one of the polymeric microreticular sorbent resins, at least one of the activated carbon-based sorbents, and mixtures thereof
  • the recovery of the removed quantities as variously described above is carried out by chemical displacement at temperatures in the range of about 20°C to about 200°C or about 30°C to about 150°C or about 40°C to about 100°C using a regenerant (solvent) selected from the group consisting of i) renewable gasoline, ii) toluene, iii) xylene, iv) an oxygenated solvent selected from the group consisting of methanol, ethanol, isopropanol, acetone, methylbutyl ketone, methylisobutyl ketone, tetrahydrofuran, ethyl acetate
  • the regenerant is charged to the removal zone displacing the removed quantity from the sorbent, and the removed quantity is recovered forming a recovered quantity.
  • the regenerant can then be displaced from the sorbent by any suitable manner in order to prepare the removal zone for further removal of water-soluble organic compounds from the aqueous stream, once put back on-line.
  • a method 40 for recovering removed quantities from a removal zone is described below with reference to FIG. 4.
  • the sorbent in the removal zone is selected from the group consisting of at least one of the zeolite-based adsorbents, at least one of the clay-based adsorbents, at least one of the activated carbon-based sorbents, and mixtures thereof
  • the recovery of the removed quantities as variously described above is carried out by thermal desorption in accordance with the following.
  • the sorbent in the removal zone is heated to a temperature in the range of from about 20°C to about 200°C or about 50°C to about 150°C or about 60°C to about 130°C, by introduction of a heated regenerant, which can be an inert gas r to the removal zone at pressures slightly above atmospheric pressure.
  • a heated regenerant which can be an inert gas r to the removal zone at pressures slightly above atmospheric pressure.
  • a first effluent is removed from the removal zone and is partially condensed in a first condenser at a temperature in the range of from about 20°C to about 50°C, for a period of time between about 0.2 to about 6 hours or about 0.5 to about 4 hours, followed by passing the first effluent to a second condenser wherein the first effluent is further partially condensed at a temperature in the range of from about - 150°C to about -30°C or about -100°C to about -40°C for a period of time between about 0.2 to about 6 hours or about 0.5 to about 4 hours, forming a first recovered quantity.
  • the sorbent is heated to a temperature in the range of from about 130°C to about 500°C or about 150°C to about 400°C or about 200°C to about 350°C, under at least a partial vacuum and for a period of time between about 0.2 to about 6 hours or about 0.5 to about 4 hours.
  • the vacuum can be up to about 0.01 or up to about 0.1 or up to about 1 torr.
  • a second effluent is removed from the removal zone and is passed to a third condenser wherein the second effluent is partially condensed at a temperature in the range of from about -150°C to about -30°C or about -100°C to about -40°C, forming a second recovered quantity.
  • Condensed water can be drawn off from each of the first, second, and third condensers.
  • a method 50 for recovering removed quantities from a removal zone is described below with reference to FIG. 5.
  • the sorbent in the removal zone is selected from the group consisting of at least one of the activated carbon-based sorbents
  • the recovery of the removed quantity is carried out by chemical displacement using a regenerant which is a supercritical solvent selected from the group consisting of supercritical C0 2 , supercritical propane, supercritical butane, supercritical toluene, supercritical xylene, and mixtures thereof.
  • the regenerant is charged to the removal zone displacing the removed quantity from the sorbent, and the removed quantity is recovered forming a recovered quantity.
  • the regenerant can then be displaced from the sorbent by any suitable manner in order to prepare the removal zone for further removal of water-soluble organic compounds from the aqueous stream, once put back on-line.
  • regenerant streams described above can be charged to the removal zones for recovery of the recovered quantities in either an upflow or a downflow mode.
  • Each of the recovered quantities described above can comprise, consist of, or consist essentially of light oxygenated compounds and heavy oxygenated compounds.
  • the light oxygenated compounds can comprise, consist of, or consist essentially of compounds selected from the group consisting of ketones, aldehydes and carboxylic acids, but can also include other light oxygenated compounds. Typically, such light oxygenated compounds contain 5 or less carbon atoms, or between 2 and 5 carbon atoms.
  • the heavy oxygenated compounds can comprise, consist of, or consist essentially of phenols, methoxy-substituted aromatics, anhydrosugars, benzofurans, and diols.
  • the polymeric microreticular sorbent resins described above, with the exception of the Superadsorbent resin, are more selective for the removal of the light oxygenated compounds than for the heavy oxygenated compounds from the aqueous stream. More particularly, the polymeric microreticular sorbent resins remove 50%, or 30%, or 20% more, by weight, of the light oxygenated compounds as compared to the heavy oxygenated compounds from the aqueous stream.
  • the Superadsorbent resin is highly selective towards water.
  • the zeolite-based adsorbents described above are more selective for the removal of the heavy oxygenated compounds than for the light oxygenated compounds from the aqueous stream. More particularly, the zeolite-based adsorbents remove 50%, or 30%, or 20% more, by weight, of the heavy oxygenated compounds as compared to the light oxygenated compounds from the aqueous stream.
  • the clay-based adsorbents and the activated carbon-based sorbents remove both light and heavy oxygenated compounds, and do not selectively remove one over the other.
  • a reactor feed can comprise, consist of, or consist essentially of a component selected from the group consisting of any of the recovered quantities A - H described herein (and the "recovered quantity" from any of the other embodiments), or separated light oxygenate compound portions thereof, and combinations thereof.
  • the reactor feed can comprise light oxygenated compounds and can be charged to a basic catalyzed reactor containing a basic catalyst for conversion of the light oxygenated compounds to heavier oxygenated compounds.
  • the basic catalyst can comprise, consist of, or consist essentially of a material selected from the group consisting of: the oxides, mixed oxides, hydroxides and mixed hydroxides of alkaline metals, alkaline earth metals, Group MB metals, and Group 1MB metals; mixed oxides between Group IIIA or Group IVA metals with at least one element selected from the group consisting of alkaline metals, alkaline earth metals, Group MB metals, and Group 1MB metals; mixed hydroxides between Group IIIA or Group IVA metals with at least one element selected from the group consisting of alkaline metals, alkaline earth metals, Group MB metals, and Group 1MB metals; and mixtures thereof.
  • the basic catalyst can be a solid basic catalyst or a liquid basic catalyst.
  • the solid basic catalysts are used in a heterogeneous phase, while the liquid basic catalysts are used in a homogeneous liquid phase.
  • the liquid basic catalysts comprise, consist of, or consist essentially of aqueous solutions of the basic catalysts, and mixtures thereof.
  • Non-limiting examples of solid basic catalysts are Na 2 0, K 2 0, MgO, CaO, SrO, BaO, Zr0 2 , Ti0 2 , CeO, mixed oxides thereof such as MgO-Zr0 2 , CeO-Zr0 2 , Ti0 2 -Zr0 2 , MgO-Ti0 2 , the corresponding solid hydroxides, other mixed oxides such as MgO-AI 2 03, MgO-Si0 2 , CaO-AI 2 0 3 , CaO-Si0 2 and mixtures thereof.
  • Process conditions vary with the type of catalyst and reactor.
  • the heterogeneous phase reactions can be carried out in a fixed bed reactor at relatively mild conditions, such as temperatures less than about: 450°C, or 400°C, or 350°C; pressures less than about: 20 atm, or 10 atm, or 5 atm; and liquid hourly space velocities (LHSV) less than about: 30 h "1 , or 20 h "1 , or 10 h "1 .
  • LHSV liquid hourly space velocities
  • the homogeneous liquid phase reactions can be carried out in a fixed bed reactor in countercurrent flow or in a batch reactor (continuous, semi-continuous or discontinuous), under similar conditions.
  • a method 70 for upgrading the above described recovered quantities is described below with reference to FIG. 7.
  • Any of the above described recovered quantities, or portions thereof, which comprise, consist of, or consist essentially of light oxygenated compounds can optionally be used alone or in any combination in this embodiment as the reactor feed which is charged to the Basic Catalyzed Reactor for contact with the basic catalyst described above. At least a portion of the light oxygenated compounds in the reactor feed are converted to heavier oxygenated compounds in the Basic Catalyzed Reactor, the effluent of which is charged to the Bio-oil Storage. The contents of the Bio-oil Storage vessel can then be deoxygenated to form fuel- range hydrocarbons.
  • a method 80 for upgrading the above described recovered quantities is described below with reference to FIG. 8.
  • Any of the above described recovered quantities, or portions thereof, which comprise, consist of, or consist essentially of oxygenated compounds selected from the group consisting of light oxygenated compounds, heavy oxygenated compounds, and combinations thereof, can be used alone or in any combination in this embodiment as the reactor feed.
  • the reactor feed either: 1 ) at least a portion of the reactor feed is charged directly to the Basic Catalyzed Reactor for contact with the basic catalyst described above; or 2) at least a portion of the reactor feed is charged to a Separator for separation into a light stream comprising, consisting of, or consisting essentially of light oxygenated compounds and into a heavy stream comprising, consisting of, or consisting essentially of heavy oxygenated compounds; wherein the heavy stream is charged to the Bio-oil Storage and the light stream is charged to the Basic catalyzed reactor; or 3) both 1 ) and 2).
  • At least a portion of the light oxygenated compounds are converted to heavier oxygenated compounds in the Basic Catalyzed Reactor, the effluent of which is charged to the Bio-oil Storage.
  • the contents of the Bio-oil Storage vessel can then be deoxygenated to form fuel-range hydrocarbons.
  • a method 90 for upgrading a recovered quantity which has been recovered using chemical displacement and which comprises, consists of, or consists essentially of light oxygenated compounds and regenerant (chemical displacing solvent), is described below with reference to FIG. 9.
  • Any such recovered quantity(ies) can be used as the reactor feed.
  • At least a portion of the reactor feed is charged to a Separator for separation into a light stream comprising, consisting of, or consisting essentially of light oxygenated compounds and into a heavy stream comprising, consisting of, or consisting essentially of the regenerant (solvent); wherein the heavy stream is charged to the Regenerant Storage and the light stream is charged to the Basic Catalyzed Reactor.
  • At least a portion of the light oxygenated compounds are converted to heavier oxygenated compounds in the Basic Catalyzed Reactor, the effluent of which is charged to the Bio-oil Storage.
  • the contents of the Bio-oil Storage vessel can then be deoxygenated to form fuel-range hydrocarbons; and the regenerant can be recycled for use in recovering recovered quantities.
  • a method 100 or removing at least a portion of the water-soluble complex mixture of organic compounds (comprising, consisting of, or consisting essentially of light oxygenated compounds and heavy oxygenated compounds) from the aqueous stream, and recovering and upgrading the removed quantities from removal zones A and B comprises, consists of, or consists essentially of the process described below with reference to FIG. 10.
  • aqueous stream comprising, consisting of, or consisting essentially of the water-soluble complex mixture of organic compounds to removal zone A for contact with sorbent A, as described above, for removal of at least a portion of the water-soluble complex mixture of organic compounds from the aqueous stream forming a removed quantity A comprising heavy oxygenated compounds, and optionally light oxygenated compounds; and b) passing the aqueous stream from the removal zone A to removal zone B for contact with sorbent B contained therein, as described above, for removal of at least a portion of the water-soluble complex mixture of organic compounds from the aqueous stream forming a treated water stream and a removed quantity B comprising light oxygenated compounds and heavy oxygenated compounds.
  • At least a portion of removed quantity A contained in removal zone A is removed by chemical displacement in accordance with the process described in FIG. 3 by passing a Regenerant A selected from the group consisting of i) renewable gasoline, ii) toluene, iii) xylene, iv) an oxygenated solvent selected from the group consisting of methanol, ethanol, isopropanol, acetone, methylbutyl ketone, methylisobutyl ketone, tetrahydrofuran, ethyl acetate, and v) mixtures thereof, to removal zone A.
  • the removed quantity A is then recovered using the Separator forming a recovered quantity A.
  • the recovered quantity A becomes a part of a reactor feed which is charged to a Basic Catalyzed Reactor for conversion of any optionally present light oxygenate compounds
  • the recovered quantity A is charged to a Bio-oil Storage vessel
  • a portion of the recovered quantity A becomes a part of a reactor feed and is charged to a Basic Catalyzed Reactor for conversion of any optionally present light oxygenate compounds and a portion of the recovered quantity A is charged to a Bio-oil Storage vessel.
  • At least a portion of the removed quantity B contained in removal zone B can be removed by thermal desorption in accordance with the following: i) removed quantity B in the removal zone B is heated to a temperature in the range of from about 20°C to about 200°C or about 50°C to about 150°C or about 60°C to about 130°C, by introduction of a heated regenerant, which can be an inert gas, to the removal zone B at pressures slightly above atmospheric pressure.
  • a heated regenerant which can be an inert gas
  • a first effluent is removed from the removal zone B and is partially condensed in a first condenser at a temperature in the range of from about 20°C to about 50°C, for a period of time between about 0.2 to about 6 hours or about 0.5 to about 4 hours, followed by passing the first effluent to a second condenser wherein the first effluent is further partially condensed at a temperature in the range of from about -150°C to about -30°C or about -100°C to about -40°C for a period of time between about 0.2 to about 6 hours or about 0.5 to about 4 hours, forming a first recovered quantity.
  • the first recovered quantity comprises light oxygenated compounds and optionally heavy oxygenated compounds.
  • the first recovered quantity is then charged, as at least a part of the reactor feed, to the Basic Catalyzed Reactor. At least a portion of the light oxygenated compounds are converted to heavier oxygenated compounds in the Basic Catalyzed Reactor. The heavier oxygenated compounds from the Basic Catalyzed Reactor are charged to the Bio-oil Storage.
  • removed quantity B is heated to a temperature in the range of from about 130°C to about 500°C or about 150°C to about 400°C or about 200°C to about 350°C, under at least a partial vacuum and for a period of time between about 0.2 to about 6 hours or about 0.5 to about 4 hours.
  • the vacuum can be up to about 0.01 or up to about 0.1 or up to about 1 torr.
  • a second effluent is removed from the removal zone B and is passed to a third condenser wherein the second effluent is partially condensed at a temperature in the range of from about -150°C to about -30°C or about -100°C to about -40°C, forming a second recovered quantity comprising heavy oxygenated compounds, and optionally light organic compounds.
  • the second recovered quantity is charged to the Bio-oil Storage.
  • the contents of the Bio-oil Storage can then be deoxygenated to form fuel-range hydrocarbons.
  • condensed water can be drawn off from each of the first, second, and third condensers and combined with the treated water.
  • thermograms were obtained for samples of the spent GAC, the vacuum regenerated GAC from the 120°C run, fresh GAC, and a fresh GAC made damp with Dl water (damp GAC). The thermograms are shown in FIG. 6. As can be seen in FIG. 6, the weight loss for the spent GAC confirm the efficiency of thermal regeneration shown in Table 1 , and that of the vacuum regenerated GAC was very low and similar to that of the fresh GAC, indicating vacuum regeneration is very effective at removing these water-soluble organic compounds from spent GAC.
  • Example 2 A model aqueous solution was prepared containing 0.5 wt% phenol and about 1 wt% catechol. About 50 g quantity of this solution was charged at a flow rate of 1ml/min to a vessel containing about 10 g of a mixture of sorbent resins referred to generally as Amberlite XAD (75% of the resin with product designation Amberlite XAD 761 and 25% of the resin with product designation Amberlite XAD 1600) which are manufactured by the Rohm and Haas company. The resulting spent sorbent resin mixture contained 0.16 g of phenol and 0.45 g of catechol. The spent sorbent resin mixture was subjected to desorption by extraction with about 8 ml ethanol.
  • Amberlite XAD 75% of the resin with product designation Amberlite XAD 761 and 25% of the resin with product designation Amberlite XAD 1600
  • Table 2 shows the wt% removal from the model solution, the wt% desorption from the sorbent resin mixture, and the total overall recovery.
  • the data in Table 2 show that the Amberlite XAD resins are effective in removing phenol and catechol from an aqueous stream, and that such absorbed components can be effectively removed by chemical displacement with a suitable solvent from such resins.
  • aqueous streams containing from about 7 to about 14 wt% water-soluble organic compounds were separated from reaction products resulting from the thermocatalytic conversion of southern yellow pine wood particles.
  • the aqueous streams were then contacted with various sorbents for removal of water-soluble organic compounds, or in the case of Super Absorbent Polymer (SAP) the removal of water resulting in a concentrating effect of the water-soluble organic compounds.
  • SAP Super Absorbent Polymer
  • Table 3 shows the selectivities for these sorbents in the removal of specific water-soluble organic compounds.
  • the removal %'s for each sorbent is based on the amounts of the subject organics contained in the feed to that in the treated water.
  • the data show that NaX zeolite is very effective in removing heavier compounds, Osorb resin is effective in removing phenolics, and that Amberlyst 21 resin is effective in removing acidic compounds.
  • Tables 4a, 4b, and 4c below show the total removal of water-soluble organic compounds from such aqueous streams described above resulting from the serial contact of the aqueous streams with different sequences and combinations of sorbents.
  • Table 4a the arrangement used in Run C demonstrated a very selective separation, and in consideration of the selectivities of the sorbents used (shown in Table 3), leaving most of the heavy compounds on the zeolite sorbent, most of the hydroxylic compounds on the Amberlyst sorbent and produced a concentrated ketones and aldehydes stream.
  • the removal wt% for ketones and aldehydes in Run C is negative due to the manner in which the removal %'s are calculated, that is:
  • Table 5 shows the total removal and total recovery percentages of water-soluble organic compounds from an aqueous stream as described above resulting from the contact of the aqueous stream, in a column containing a commercial granulated activated carbon (GAC) manufactured by Norit Inc. and having product designation GAC300.
  • GAC commercial granulated activated carbon
  • the data in Table 5 shows that microporous GAC is effective in removing substantially all of the organics present and is selective for the recovery of the light organic compounds from an aqueous stream.
  • the data also shows that such absorbed light components can be effectively removed from the GAC by thermal desorption.
  • Catechol 100 0 Total for heavies
  • Table 6 below shows the total removal and total recovery percentages of water-soluble organic compounds from an aqueous stream as described above resulting from the contact of the aqueous stream, in a column, with: 1) a mixture of sorbent resins referred to generally as Amberlite XAD (75% of the resin with product designation Amberlite XAD 761 and 25% of the resin with product designation Amberlite XAD 1600) which are manufactured by the Rohm and Haas company, followed by contact with: 2) a commercial granulated activated carbon (GAC) manufactured by Norit Inc. and having product designation GAC300. The bottom 25 vol% of the column was packed with the GAC and the top 75 vol% of the column was packed with the Amberlite XAD resin mixture.
  • Amberlite XAD 75% of the resin with product designation Amberlite XAD 761 and 25% of the resin with product designation Amberlite XAD 1600
  • GAC300 commercial granulated activated carbon
  • the adsorber column was loaded in the downflow mode.
  • the spent adsorbents bed was subjected to desorption for recovery of organic compounds by extraction with ethanol in the upflow mode.
  • Such recovery method was expected to be effective with regard to organics recovery from the Amberlite XAD sorbent, but have only minimal effectiveness in organics recovery from the GAC.
  • the data in Table 6 shows that the use of a two-stage system including Amberlite XAD resins and GAC is effective in removing and recovering organic compounds, including phenol and catechol, from an aqueous stream, and that such absorbed heavy components can be effectively removed from the Amberlite XAD by chemical displacement with a suitable solvent.
  • the light compounds contained in the GAC can be recovered from the GAC by thermal desorption, as described in Examples 1 and 5.
  • a biomass feedstock of Southern Yellow Pine wood particles were thermocatalytically converted to a reaction product containing a bio-oil phase and an aqueous phase.
  • the aqueous phase was obtained by gravity separation from the bio-oil phase.
  • a stream of recovered light oxygenated compounds was obtained from treating the aqueous phase by first contacting with a mixture of Amberlite XAD resins followed by contact with GAC, in the same way as that described in Examples 5 and 6 above.
  • the GAC was subjected to two-stage thermal desorption in accordance with Example 5, and the effluent resulting from the first desorption are the recovered light oxygenated compounds.
  • the concentration of the recovered light oxygenated compounds from the first desorption is presented in Table 7. Table 7
  • a 1 ml quantity of the recovered light oxygenated compounds was allowed to react, at 27°C and 1 atm, in the presence of 80 mg of a solid NaOH pearl catalyst forming a reaction product.
  • a sample of the recovered light oxygenated compounds feed and a sample of the reaction product were subjected to testing by Nuclear Magnetic Resonance (NMR).
  • NMR Nuclear Magnetic Resonance
  • the H-NMR spectrum of the reaction product is compared to that of the recovered light oxygenated compounds feed in FIG. 11.
  • NMR is commonly used to assess changes in composition resulting from treatment by various means. Functional groups of interest give signals in different regions of the NMR spectrum. Carbonyls typically appear between 170 and 210 in 13 C NMR, while peaks in the 60-80 region are assigned to carbons singly bonded to oxygen.
  • FIG. 12 presents a visual comparison of the recovered light oxygenated compounds feed and the reaction product.
  • the recovered light oxygenated compounds feed was a mostly transparent homogeneous liquid, whereas the reaction product clearly shows an oil phase floating on top of an aqueous phase. This serves as confirmation that the homogeneous recovered light oxygenated compounds in the feed are converted, at least in part, to heavier oxygenated compounds which float on top of an aqueous phase.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention porte sur un procédé de récupération d'un mélange complexe et hydrosoluble de composés organiques provenant d'un courant aqueux par extraction et/ou mise en contact du courant aqueux avec un ou plusieurs sorbants choisis dans le groupe constitué par les résines sorbantes, microporeuses et polymères, les adsorbants à base de zéolite, les adsorbants à base d'argile, les sorbants à base de charbon actif et les mélanges de ces derniers ; ledit procédé comprenant des techniques de récupération et de valorisation des composés organiques éliminés.
PCT/US2014/067421 2013-11-26 2014-11-25 Récupération de composés organiques à partir de la phase aqueuse d'une pyrolyse catalytique de biomasse et leur valorisation Ceased WO2015081104A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4563568A1 (fr) 2023-11-28 2025-06-04 TotalEnergies OneTech Procédé et installation de production d'additifs pour carburant à partir d'un flux aqueux issu de la conversion de biomasse en huile

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2585491A (en) * 1949-04-14 1952-02-12 Sun Oil Co Continuous adsorption process
US20080312476A1 (en) * 2007-06-15 2008-12-18 Mccall Michael J Production of Chemicals from Pyrolysis Oil
US20110147313A1 (en) * 2008-06-06 2011-06-23 Eni S.P.A. Process for the treatment of the aqueous stream coming from the fischer-tropsch reaction by means of ion exchange resins
US20120156742A1 (en) * 2010-12-20 2012-06-21 Shell Oil Company Process to produce biofuels from biomass
US20130090487A1 (en) * 2010-04-15 2013-04-11 Eni S.P.A. Process for the production of bio-oil from municipal solid waste

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2585491A (en) * 1949-04-14 1952-02-12 Sun Oil Co Continuous adsorption process
US20080312476A1 (en) * 2007-06-15 2008-12-18 Mccall Michael J Production of Chemicals from Pyrolysis Oil
US20110147313A1 (en) * 2008-06-06 2011-06-23 Eni S.P.A. Process for the treatment of the aqueous stream coming from the fischer-tropsch reaction by means of ion exchange resins
US20130090487A1 (en) * 2010-04-15 2013-04-11 Eni S.P.A. Process for the production of bio-oil from municipal solid waste
US20120156742A1 (en) * 2010-12-20 2012-06-21 Shell Oil Company Process to produce biofuels from biomass

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4563568A1 (fr) 2023-11-28 2025-06-04 TotalEnergies OneTech Procédé et installation de production d'additifs pour carburant à partir d'un flux aqueux issu de la conversion de biomasse en huile
WO2025114328A1 (fr) 2023-11-28 2025-06-05 Totalenergies Onetech Procédé et installation de production d'additifs pour carburants à partir d'un flux aqueux issu de la conversion de biomasse en huile

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