WO2014182499A1 - Procédé de valorisation de produits dérivés d'une biomasse, par utilisation d'une extraction liquide-liquide - Google Patents

Procédé de valorisation de produits dérivés d'une biomasse, par utilisation d'une extraction liquide-liquide Download PDF

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Publication number
WO2014182499A1
WO2014182499A1 PCT/US2014/035804 US2014035804W WO2014182499A1 WO 2014182499 A1 WO2014182499 A1 WO 2014182499A1 US 2014035804 W US2014035804 W US 2014035804W WO 2014182499 A1 WO2014182499 A1 WO 2014182499A1
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WIPO (PCT)
Prior art keywords
mixture
extraction
water
oil
organics
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PCT/US2014/035804
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English (en)
Inventor
Vicente Sanchez
Brent Moore
Ed SMITH
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Kior, Inc.
Priority date (The priority date 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 date listed.)
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Publication date
Priority claimed from US13/889,105 external-priority patent/US9387415B2/en
Application filed by Kior, Inc. filed Critical Kior, Inc.
Priority to EP14794254.4A priority Critical patent/EP2994209A4/fr
Priority to CA2911456A priority patent/CA2911456C/fr
Publication of WO2014182499A1 publication Critical patent/WO2014182499A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B1/00—Production of fats or fatty oils from raw materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0492—Applications, solvents used

Definitions

  • the invention relates generally to the alteration of the ratio of the specific gravities of the oil and water phases resulting from the conversion of biomass to liquid products, which can further include the removal of metals and/or the modification of the conductivity, and more particularly to an effective means to reduce the level of solids contained in the oil phase.
  • the invention also relates to using liquid-liquid extraction to partition desirable carbon containing compounds into the oil phase and undesirable carbon containing compounds into the water phase.
  • the product stream can contain both an oil phase and a water phase (containing both water present in the biomass prior to conversion, and water produced during the conversion process).
  • Pyrolysis in particular flash pyrolysis, has been proposed as one such process for converting solid biomass material to liquid products. Pyrolysis in general refers to a process in which a feedstock is heated in an oxygen-poor or oxygen-free atmosphere. If solid biomass is used as the feedstock of a pyrolysis process, the process produces gaseous, liquid, and solid products.
  • the oil phase has a higher specific gravity than the water phase, resulting in the oil phase settling to the bottom of a settling vessel, and emulsions can also form between the oil and water phases.
  • any solids present in the reaction products also settle into the oil phase, which can cause issues in downstream processing of the oil, and can be difficult and expensive to remove.
  • undesirable carbon containing compounds such as aldehydes and carboxylic acids can be present in the liquid product and such are not easily upgradable to transportation fuels.
  • undesirable carbon containing compounds can be present in the oil phase while desirable carbon containing compounds can be present in the water phase, thus lowering the yield of high quality bio-oil for upgrading to fuels.
  • desirable carbon containing compounds can be transferred from the oil phase to the water phase and desirable carbon containing compounds are transferred from the water phase to the oil phase.
  • such process can additionally comprise:
  • such process can additionally comprise:
  • such process can additionally comprise:
  • such process can additionally comprise:
  • At least one specific gravity modifier comprising a diluent, a water-soluble compound, a water soluble co-solvent, and combinations thereof, with the first mixture, thereby forming the second oil phase and the second aqueous phase.
  • such process can additionally comprise: allowing the second mixture to settle, thereby forming an upper layer containing the second oil phase and a lower layer containing the second aqueous phase, wherein the first oil phase contains solids, and following the settling, the second oil phase in the upper layer contains less solids than the first oil phase.
  • such process can additionally comprise:
  • the conductivity modifier can have a TAN lower than the TAN of the first mixture, and wherein the quantity of conductivity modifier is sufficient such that the electrical conductivity of the second mixture is lower than the electrical conductivity of the first mixture.
  • first and/or second oil phases further contain metals
  • a process comprising: contacting either the first and/or second mixtures with specific acids for removal of at least a portion of the metals from either or both of the first and second oil phases.
  • organics A comprising compounds selected from the group consisting of i) aldehydes, ii) ketones having from 3 to 4 carbon atoms per molecule, iii) carboxylic acids having from 2 to 3 carbon atoms per molecule, and iv) combinations thereof, and organics B comprising compounds having at least four carbon atoms per molecule, thereby forming a second mixture comprising an extract and a raffinate, wherein the organics B are substantially free of: i) aldehydes, ii) ketones having from 3 to 4 carbon atoms per molecule, and iii) carboxylic acids having from 2 to 3 carbon atoms per molecule , wherein the extract and the raffinate are immiscible, the extract comprises substantially all of the extraction solvent and substantially all of the organics B, the raffinate comprises substantially all of the water and substantially all of the organics A, and where
  • the biomass material useful in the current invention can be any biomass capable of being converted to liquid and gaseous hydrocarbons.
  • solid biomass materials comprising a cellulosic material, in particular lignocellulosic materials, because of the abundant availability of such materials, and their low cost.
  • the solid biomass feed can comprise components selected from the group consisting of lignin, cellulose, hemicelluloses, and combinations thereof.
  • suitable solid biomass materials include forestry wastes, such as wood chips and saw dust; agricultural waste, such as straw, corn stover, sugar cane bagasse, municipal waste, in particular yard waste, paper, and card board; energy crops such as switch grass, coppice, eucalyptus; and aquatic materials such as algae; and the like.
  • the biomass can be converted, by any suitable means, to reaction products comprising, at least in part, a first mixture comprising, consisting of, or consisting essentially of water and biomass derived carbon containing compounds which can include organics A comprising carbon containing compounds selected from the group consisting of i) aldehydes, ii) ketones having from 3 to 4 carbon atoms per molecule, iii) carboxylic acids having from 2 to 3 carbon atoms per molecule, and iv) combinations thereof, and organics B comprising carbon containing compounds having at least four carbon atoms per molecule.
  • organics A comprising carbon containing compounds selected from the group consisting of i) aldehydes, ii) ketones having from 3 to 4 carbon atoms per molecule, iii) carboxylic acids having from 2 to 3 carbon atoms per molecule, and iv) combinations thereof
  • organics B comprising carbon containing compounds having at least four carbon atoms per molecule.
  • the carbon containing compounds of the organics B can be selected from the group consisting of ketones, furans, phenols, catechols, aromatics hydrocarbons (such as, but not limited to, alkyl benzenes and naphthalenes), indenols, indanols, naphthalenos.benzofurans, and combinations thereof.
  • the first mixture can also comprise i) a first oil phase (also referred to as bio-oil) comprising, consisting of, or consisting essentially of at least a portion of the biomass derived carbon containing compounds and at least a portion of the water and ii) a first aqueous phase (also referred to as process water) comprising, consisting of, or consisting essentially of at least a portion of the water and at least a portion of the biomass derived carbon containing compounds.
  • the first oil phase (or bio-oil) of the reaction products can comprise at least about 8 wt% water.
  • the first oil phase and the first aqueous phase can be immiscible.
  • the biomass conversion can be by a method including, but not limited to, fast pyrolysis, catalytic pyrolysis, and hydrothermal conversion, each at elevated temperatures.
  • the temperatures can range from 300 to 1000 C, or 400 to 700 C.
  • the first mixture can have a Total Acid Number (TAN) of at least about 2, or at least about 3, or at least about 10, or at least about 20, or at least about 30.
  • TAN Total Acid Number
  • the biomass feed can be charged to a reaction zone along with a heat carrier material and/or a catalyst for mixture with the biomass feed and to transfer heat thereto.
  • Useful catalysts for this process include those containing catalytic acidity and preferably containing zeolite.
  • the biomass feed can be converted to reaction products comprising, consisting of, or consisting essentially of: the first mixture described above, and optionally light gases and/or char.
  • the reaction products can be removed from the reaction zone and the first mixture condensed therefrom.
  • the first mixture can also comprise, consist of, or consist essentially of a first oil phase comprising, consisting of, or consisting essentially of biomass derived carbon containing compounds, and a first aqueous phase comprising, consisting of, or consisting essentially of water, and solids.
  • the solids can include dissolved or suspended solids and can be catalyst fines, char, unreacted biomass and ash.
  • the first oil phase can comprise at least a portion of the biomass derived carbon containing compounds and at least a portion of the water.
  • the first aqueous phase can comprise at least a portion of the water and at least a portion of the biomass derived carbon containing compounds and at least a portion of the solids.
  • the ratio of the specific gravities of the first oil phase to the first aqueous phase can be greater than 1.0, greater than about 1 .05, or greater than about 1.1.
  • the specific gravity of at least one of the first oil phase and the first aqueous phase can be modified, thereby resulting in a second mixture having a second oil phase and a second aqueous phase, wherein the ratio of the specific gravities of the second oil phase to the second aqueous phase (SGR2) is less than 1.0, preferably less than about 0.99, and more preferably less than about 0.97.
  • the modification of the specific gravity of at least one of the first oil phase and the first aqueous phase can include adding at least one specific gravity modifier to the mixture, thereby forming the second mixture.
  • a diluent can be combined with the first oil phase, as at least a portion of the specific gravity modifier, thereby forming the second oil phase, resulting in the specific gravity of the second oil phase being lower than the specific gravity of the first oil phase. More particularly, the specific gravity of the second oil phase is less than 1 .0.
  • the diluent preferably has a specific gravity less than about 0.97.
  • the diluent can be selected from the group consisting of: light cycle oil, naphtha, toluene, methyl isobutyl ketone, reformate, a bio- oil fraction having a specific gravity lower than the specific gravity of the first oil phase, a hydrotreated bio-oil fraction having a specific gravity lower than the specific gravity of the first oil phase, and combinations thereof.
  • the bio-oil fraction can be obtained as a fraction of the first oil phase following the specific gravity modification step.
  • the hydrotreated bio-oil fraction can optionally be obtained as a fraction of the first oil phase following hydrotreatment of the first oil phase.
  • the ratio by volume of the diluent to the first oil phase can be in the range of from about 0.6:1 to about 2.4: 1 , and more preferably from about 0.6:1 to about 1 : 1 .
  • the ratio by volume of the diluent to first oil phase can be in the range of from about 0.05: 1 to about 1 :1 , or from about 0.05:1 to about 0.2: 1.
  • the modification of the specific gravity of at least one of the first oil phase and the first aqueous phase can also include combining a water-soluble compound, as at least a portion of the specific gravity modifier (alone or in addition to the use of a diluent as a specific gravity modifier), with the first aqueous phase, thereby forming the second aqueous phase, and wherein the specific gravity of the second aqueous phase is higher than the specific gravity of the first aqueous phase.
  • the specific gravity of the second aqueous phase ends up being greater than about 1.05.
  • the water-soluble compound can be selected from the group consisting of NaCI, gCI 2 , KCI, KBr, Na 2 S0 4 , NaHC0 3 , NaOH, KOH, NH OH, alkyl amines, pyridines, quinolines, H 2 S, ammonia, ammonium compounds including: nitrates, sulfides, carbonates (such as ammonium bicarbonate), hydroxides, acetates, chlorides, bromides, iodides, and sulfates, and combinations thereof.
  • the water-soluble compound can be added as a solid and dissolved into the first aqueous phase, and can also, alternatively, be added in the form of a water-soluble compound solution.
  • the water-soluble compound is preferably ammonium bicarbonate, NaCI, or MgCI 2 .
  • the water-soluble compound is preferably combined with the first aqueous phase in a quantity sufficient to result in a specific gravity of the second aqueous phase which is greater than about 1.05.
  • the modification of the specific gravity of at least one of the first oil phase and the first aqueous phase can also include combining a water-soluble co-solvent, as at least a portion of the specific gravity modifier (alone or in addition to the use of one or both of the diluent or water-soluble compound as specific gravity modifiers), with the first aqueous phase, thereby forming the second aqueous phase, and wherein the specific gravity of the second aqueous phase is higher than the specific gravity of the first aqueous phase.
  • the water soluble co-solvent can be a glycol, and more preferably, is selected from the group consisting of ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, and combinations thereof.
  • the resulting specific gravity of the second aqueous phase is preferably greater than about 1.05.
  • the at least one specific gravity modifier added to the first mixture can also be selected from the group consisting of a light cycle oil, naphtha, toluene, methyl isobutyl ketone, reformate, a bio-oil fraction having a specific gravity lower than the specific gravity of said first oil phase, a hydrotreated bio-oil fraction having a specific gravity lower than the specific gravity of said first oil phase, NaCI, MgCI 2 , KCI, KBr, Na 2 S0 , NaHC0 3 , NaOH, KOH, NH OH, alkyl amines, pyridines, quinolines, H 2 S, ammonia, ammonium compounds including: nitrates, sulfides, carbonates (such as ammonium bicarbonate), hydroxides, acetates, chlorides, bromides, iodides, and sulfates, a glycol, and combinations thereof.
  • a light cycle oil naphtha, toluene, methyl iso
  • the second mixture is preferably allowed to settle in a settling vessel, thereby forming an upper layer containing the second oil phase and a lower layer containing the second aqueous phase.
  • the first oil phase can contain solids, which can be present in an amount of at least about 100, or about 1000, or about 3,000 ppmw.
  • the solids can include, but are not limited to, organic and inorganic components, which can include solid catalyst material.
  • the second oil phase in the upper layer contains less solids than the first oil phase; and can contain less than about 25, or about 10, or about 5 wt% of the solids contained in the first oil phase; and preferably contains less than about 80 ppmw solids.
  • a diluent is used as at least one specific gravity modifier
  • at least a portion of the second oil phase in the upper layer can be passed to a separator for recovery of at least a portion of the diluent, resulting in a recovered diluent.
  • At least a portion of the recovered diluent can be recycled for use as at least a portion of the diluent.
  • At least a portion of the second oil phase can be passed to a separator for recovery of at least one bio-oil fraction from the second oil phase.
  • At least one of the bio-oil fractions can be utilized, as at least a portion of the diluent.
  • a diluent when used as at least one specific gravity modifier, at least a portion of the second oil phase can be passed to a hydrotreater for at least partial hydrotreating, thereby forming a hydrotreated stream, and at least a portion of the hydrotreated stream can be passed to a separator for separation into at least one hydrotreated bio-oil fraction. At least one of the hydrotreated bio-oil fractions can be utilized as at least a portion of the diluent.
  • a quantity of a conductivity modifier can also be added to the first mixture thereby forming the second mixture, wherein the quantity of the conductivity modifier is sufficient such that the electrical conductivity of the second mixture is lower than the electrical conductivity of the first mixture.
  • the first mixture can have an electrical conductivity of at least about 900,000, or at least about 950,000 nano Siemens per meter (nS/m); and the second mixture preferably has an electrical conductivity less than about 800,000 or less than about 500,000 nS/m.
  • the conductivity modifier can have a TAN lower than the TAN of the first mixture, and preferably has a TAN at least about 2 units lower than the TAN of the first mixture.
  • the electrical conductivity of the second mixture is preferably less than about 75%, more preferably less than about 50%, and even more preferably less than about 25% of the electrical conductivity of the first mixture.
  • the conductivity modifier can be selected from the group consisting of an aqueous solution, a fraction separated from the biomass derived carbon containing compounds, a fraction separated from the biomass derived carbon containing compounds following hydrotreatment of the biomass derived carbon containing compounds, and combinations thereof.
  • the conductivity modifier can comprise an aqueous solution having a pH greater than 7 or greater than about 9.
  • the aqueous solution can comprise a base selected from the group consisting of NaOH, KOH, NH 4 OH, alkyl amines, pyridines, quinolines, ammonia, ammonium compounds including: nitrates, sulfides, carbonates, hydroxides, acetates, chlorides, bromides, iodides, and sulfates, and combinations thereof, and is preferably ammonium bicarbonate or ammonium hydroxide or a combination thereof.
  • bases can be added separately or simultaneously as a pre-mixed solution. If added separately, they can be added at different process conditions including different temperature and different pressures. Buffers may also be used to more tightly control pH.
  • the first mixture and/or the resulting second mixture can be in the form of an emulsion comprising a portion of the biomass derived carbon containing compounds and a portion of the water.
  • the second mixture including the conductivity modifier described above, can be subjected to electrostatic dehydration, resulting in at least a partial breaking of the emulsion, and freeing from the emulsion at least 75%, or at least 90%, or at least 95% of the biomass derived carbon containing compounds contained in the emulsion or at least 50%, or at least 70%, or at least 95% of the water contained in the emulsion.
  • the second mixture following electrostatic dehydration, preferably has an electrical conductivity less than about 250,000 nS/m.
  • the electrostatic dehydration is preferably performed in a desalter vessel.
  • a demulsifier compound can be added to the first mixture, along with the conductivity modifier, thereby forming the second mixture which is then subjected to the electrostatic dehydration.
  • the demulsifier can be an alkoxylate derived from a poly amine.
  • first and second oil phases can each further comprise metals, which can be selected from the group consisting of Al, Ca, Mg, Si, Fe, and combinations thereof. At least a portion of these metals can be removed from either the first oil phase or the second oil phase, or both, into either the first or second aqueous phases by contact of either or both of the first mixture and the second mixture with certain acids. If metals are removed from the first oil phase into the first aqueous phase by contact with such acid(s), the conductivity modifier can then optionally be added to form the second mixture, having a reduced electrical conductivity, as described above.
  • metals can be selected from the group consisting of Al, Ca, Mg, Si, Fe, and combinations thereof. At least a portion of these metals can be removed from either the first oil phase or the second oil phase, or both, into either the first or second aqueous phases by contact of either or both of the first mixture and the second mixture with certain acids. If metals are removed from the first oil phase into the first aqueous phase by contact with such acid
  • the removal of at least a portion of the metals can also take place from the second oil phase into the second aqueous phase following addition of the conductivity modifier, and also optionally, before or after the electrostatic dehydration of the second mixture to at least partially break the emulsion, as described above.
  • the acid can be selected from the group consisting of sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, glycolic acid, aminocarboxylic acids, hydroxo- carboxylic acids, dibasic carboxylic acids, monobasic carboxylic acids, carbonic acid, alpha- hydroxy carboxylic acids, and their salts, and combinations thereof.
  • the acid also preferably has a pH less than about 5.
  • the acid and metal interaction can include, but is not limited to, a process selected from the group consisting of: chemically binding at least a portion of the metals; removing at least a portion of the metals from the first and or second oil phases; or combinations thereof.
  • the first mixture can be contacted with an extraction solvent thereby forming a second mixture comprising an extract and a raffinate, wherein the extract and raffinate are immiscible.
  • the organics B described above can be substantially free of i) aldehydes, ii) ketones having from 3 to 4 carbon atoms per molecule, and iii) carboxylic acids having from 2 to 3 carbon atoms per molecule.
  • substantially free as used herein means less than 5, or 3, or 2, or 1 , or 0.5, or 0.1 wt%.
  • the extract can comprise substantially all of the extraction solvent and substantially all of the organics B, and the raffinate can comprise substantially all of the water and substantially all of the organics A.
  • substantially all as used herein means at least 85, or 90, or 95, or 98, or 100 wt%.
  • the extraction solvent can have a dipole moment greater than about 1.0 or greater than about 2.0 or greater than about 4.0 debye; a density less than about 1.0 or less than about 0.9 or less than about 0.8; a water solubility at 20°C of less than about 2.5 or less than about 2.2 or less than about 2.0 g/100 ml of water; and a boiling point in the range of from about 90 to about 300 °F or from about 200 to about 270 °F or from about 200 to about 260 °F.
  • the extraction solvent can be substantially unreactive when exposed to acidic aqueous media and substantially thermally stable at temperatures up to about 500°F.
  • the extraction solvent can comprise a member selected from the group consisting of methyl isobutyl ketone, cyclopentyl-methyl-ether, and combinations thereof.
  • the second mixture can then be separated thereby forming an intermediate product stream comprising at least a portion of, or substantially all of, the extract and a waste water stream comprising substantially all of the raffinate.
  • At least a portion of the extraction solvent can be removed from the intermediate product stream forming a recovered extraction solvent and a bio-oil product, and the recovered extraction solvent can be recycled as at least a part of the extraction solvent contacted with the first mixture, as described above.
  • the viscosity of the second mixture is lower than the viscosity of the first mixture making it easier to filter.
  • the second mixture can be filtered to remove at least a portion of the solids therefrom prior to the separation of the second mixture.
  • the partition coefficients of the organics A for the extract and the raffinate can each be less than about 1.0 or less than about 0.7
  • the partition coefficients of the organics B for the extract and the raffinate can each be greater than about 1.0 or greater than about 2.0.
  • the bio-oil product can comprise less than about 1.0 or less than about 0.8 or less than about 0.5 wt% of the organics A, and can comprise less than about 1 or less than about 0.5 wt% water.
  • the waste water stream separated from the second mixture can comprise less than about 0.1 or less than about 0.05 wt% of the organics B.
  • the first aqueous phase can be separated from the reaction products described above to form the first mixture, or the reaction products can be used as the first mixture.
  • the first mixture can be counter-currently or cross-currently contacted with the extraction solvent.
  • the contacting of the first mixture with the extraction solvent can be in a manner such that the second mixture is formed as a static mixture, with separation of the second mixture by decanting.
  • the first mixture can be contacted with the extraction solvent thereby forming an extraction mixture comprising an extraction oil phase and an extraction aqueous phase.
  • Substantially all of the organics A present in the first oil phase can be partitioned from the first oil phase to the first aqueous phase and substantially all of the organics B present in the first aqueous phase can be partitioned from the first aqueous phase to the first oil phase, thereby forming the extraction oil phase comprising, consisting of, or consisting essentially of substantially all of the organics B and substantially all of the extraction solvent and the extraction aqueous phase comprising, consisting of, or consisting essentially of substantially all of the water and substantially all of the organics A.
  • the extraction oil phase and the extraction aqueous phase can be immiscible.
  • the extraction mixture can be separated thereby forming an intermediate product stream described above comprising at least a portion of, or substantially all of, the extraction oil phase and a waste water stream comprising substantially all of the extraction aqueous phase.
  • At least a portion of the extraction solvent can be removed from the intermediate product stream forming a recovered extraction solvent and a bio-oil product, and the recovered extraction solvent can be recycled as at least a part of the extraction solvent contacted with the first mixture, as described above.
  • the viscosity of the extraction mixture is lower than the viscosity of the first mixture making it easier to filter.
  • the extraction mixture can further comprise solids and can be filtered to remove at least a portion of such solids therefrom prior to the separation of the extraction mixture.
  • the partition coefficients of the organics A for the extraction oil phase and the extraction aqueous phase can each be less than about 1.0 or less than about 0.7
  • the partition coefficients of the organics B for the extraction oil phase and the extraction aqueous phase can each be greater than about 1.0 or greater than about 2.0.
  • the bio-oil product can comprise less than about 1.0 or less than about 0.8 or less than about 0.5 wt% of the organics A, and can comprise less than about 1 or less than about 0.5 wt% water. Having a lower water content in the bio-oil product aids in any subsequent hydrodeoxygenation by both allowing increased volume throughput in the unit and increased hydrodeoxygenation activity due to an equilibrium shift (given that water is a product of hydrodeoxygenation).
  • the waste water stream separated from the extraction mixture can comprise less than about 0.1 or less than about 0.05 wt% of the organics B.
  • the first aqueous phase can be separated from the reaction products described above to form the first mixture, or the reaction products can be used as the first mixture.
  • the first mixture can be counter-currently or cross-currently contacted with the extraction solvent.
  • the contacting of the first mixture with the extraction solvent can be in a manner such that the second mixture is formed as a static mixture, with separation of the second mixture by decanting.
  • a product mixture produced from the thermo-catalytic pyrolysis of southern yellow pine wood chips was collected and allowed to settle.
  • the organic phase (raw bio-oil) for the product mixture settled to a position below the water phase.
  • a 45 ml. quantity of the raw bio-oil, separated from the product mixture was mixed with a 45 ml. quantity of an un-hydrotreated bio-naphtha fraction of the bio-oil (bio-naphtha).
  • a 10 ml. quantity of process water separated from the product mixture was also added to the raw bio- oil and bio-naphtha.
  • a total of twenty four (24) 100 ml. samples were prepared in this way.
  • the resulting samples were each mixed for around 20 seconds and placed in a 140 F water bath for around 1 hour. Upon settling, the organic phase (blended bio-oil) layer for each sample was flipped and on top, with the water phase on the bottom of the containers. The blended bio-oil for each sample was then extracted and all extracted blended bio-oils combined in one container. The container was then mixed for around 20 seconds and an aliquot was tested for filterable solids through a 0.2 ⁇ PVDF membrane filter. A sample of the raw bio-oil separated from the product mixture was also tested for filterable solids through a 0.2 ⁇ PVDF membrane filter.
  • the amount of solids in the blended (flipped) bio- oil was about 610 ppm (with 1220 ppm attributed to the raw bio-oil portion), compared to about 3,558 ppm for the un-flipped raw bio-oil.
  • the solids content in the bio-oil drops significantly once the oil and water layers are flipped. This provides substantial benefits for downstream processing of the bio-oil, such as hydrotreatment, and significantly reduces the cost of any subsequently required solids removal.
  • a product mixture produced from the thermo-catalytic pyrolysis of southern yellow pine wood chips was collected and allowed to settle.
  • the organic phase (raw bio-oil) for the product mixture settled to a position below the water phase.
  • a 100 ml. quantity of the raw bio-oil, separated from the product mixture was mixed with a 100 ml. quantity of an un-hydrotreated bio-naphtha fraction of the raw bio-oil.
  • the 200 ml. bio- oil/bio-naphtha mixture was split into four samples. Each of the four samples was combined with 50 ml. quantities of process water separated from the product mixture. Three different demulsifier additives were added to three of the samples.
  • the four samples were each mixed for around 20 seconds and placed in a 140 F water bath for around 30 minutes.
  • the organic phase (blended bio-oil) layer for each sample was flipped and on top, with the water phase on the bottom of the containers.
  • the blended bio-oil for each sample was then extracted.
  • Each of the four extracted blended bio-oils were mixed for around 20 seconds, and aliquots of each were tested for filterable solids through a 0.2 pm PVDF membrane filter.
  • the amount of solids contained in the three blended (flipped) bio-oil samples including desalter additives were about 205, 193, and 400 ppm; and the amount of solids contained in the blended (flipped) bio-oil sample not including a desalter additive was about 492 ppm.
  • the desalter additives used were from Champion Technologies and designated as XZ-1677, Code 80 and EC-1 -C, respectively.
  • a product mixture produced from the thermo-catalytic pyrolysis of southern yellow pine wood chips was collected and allowed to settle.
  • the organic phase (raw bio-oil) for the product mixture settled to a position below the water phase.
  • a quantity of the total product mixture was mixed with a quantity of a Light Cycle Oil (LCO) obtained from a crude oil refinery.
  • LCO Light Cycle Oil
  • the product mixture/LCO mixture was vigorously mixed for around 30 seconds.
  • the product mixture/LCO mixture was then centrifuged to separate out the blended bio-oil.
  • the blended bio-oil, as well as a sample of the raw bio-oil from the product mixture were then tested for ash content.
  • the ash content of the blended bio-oil was only about 0.007 wt%, compared to about 0.146 wt% for the control raw bio-oil.
  • a product mixture produced from the thermo-catalytic pyrolysis of southern yellow pine wood chips was collected and allowed to settle.
  • the organic phase (raw bio-oil, pH of about 4.5) for the product mixture settled to a position below the product water phase (pH of about 4-5).
  • Three separate quantities of the total product mixture were mixed with quantities of LCO sufficient such that the resulting organic phases of the mixtures contained about 5 wt%, about 10 wt%, and about 20 wt% LCO, respectively.
  • the density of the product water portions of the three mixtures were also modified by adding NaCI such that the resulting product water for each mixture contained about 2M NaCI.
  • the organic phase (blended bio-oil) layer was flipped and on top, with the 2M NaCI product water phase on the bottom of the container.
  • the density of the bio-oil vs. percent of LCO added is shown in Table 1 below.
  • a product mixture produced from the thermo-catalytic pyrolysis of southern yellow pine wood chips was collected and allowed to settle.
  • the organic phase (raw bio-oil, pH of about 4.5, density of about 1 .095) for the product mixture settled to a position below the product water phase.
  • Six separate quantities of the bio-oil (separated from the product water) were mixed with quantities of distilled water (pH of about 7).
  • NaCI was added to five of the bio-oil/water mixtures such that the distilled water portions separately contained about 1 M NaCI, about 2M NaCI, about 3M NaCI, about 4M NaCI, and about 5M NaCI, respectively.
  • the organic phase (blended bio-oil) layer was clearly flipped and on top, with the water phase on the bottom of the container.
  • the layers were mostly, but not completely, flipped, and the layers were not flipped for the 1 M NaCI mixture.
  • a product mixture produced from the thermo-catalytic pyrolysis of southern yellow pine wood chips was collected and allowed to settle.
  • the organic phase (raw bio-oil, pH of about 4.5, density of about 1.095) for the product mixture settled to a position below the product water phase.
  • Six separate quantities of the bio-oil (separated from the product water) were mixed with quantities of distilled water (pH of about 7).
  • MgCI 2 was added to five of the bio-oil/water mixtures such that the distilled water portions separately contained about 1 M MgCI 2 , about 2M MgCI 2 , about 3M MgCI 2 , about 4M MgCI 2 , and about 5M MgCI 2 , respectively.
  • the organic phase (blended bio-oil) layer was clearly flipped and on top, with the water phase on the bottom of the container.
  • the layers were partially flipped, and the layers were not flipped for the 1 M MgCI 2 mixture.
  • a product mixture produced from the thermo-catalytic pyrolysis of southern yellow pine wood chips was collected and allowed to settle.
  • the organic phase (raw bio-oil, pH of about 4.5, density of about 1 .085) for the product mixture settled to a position below the product water phase (pH ⁇ 4-5).
  • the product mixture was separated into six quantities. NaCI was added to five of the product mixture samples such that those five product water portions separately contained about 1 M NaCI, about 2M NaCI, about 3M NaCI, about 4M NaCI, and about 5M NaCI, respectively.
  • the organic phase layer was clearly flipped and on top, with the product water phase on the bottom of the container.
  • a product mixture produced from the thermo-catalytic pyrolysis of southern yellow pine wood chips was collected and allowed to settle.
  • the organic phase (raw bio-oil) for the product mixture settled to a position below the water phase, and had a TAN of 6.1 .
  • a 20.1 gram quantity of ammonium bicarbonate was combined with an 82 gram quantity of process water separated from the product mixture to form a modified water solution containing about 19.7 wt% ammonium bicarbonate.
  • a 19.9 gram quantity of the modified water solution was combined with 91 grams of the raw bio-oil separated from the product mixture.
  • the organic phase (raw bio-oil) layer was flipped and on top, with the modified water phase on the bottom of the container.
  • Raw bio-oil was separated from a product mixture produced from the thermo-catalytic pyrolysis of southern yellow pine wood chips.
  • the raw bio-oil had a TAN of 6.1 ; 3.2 vol% water (determined by the Karl Fischer titration method); and 5,000 ppm solids.
  • a quantity of the raw bio-oil was blended with a quantity of a bio-naphtha fraction separated from the raw bio-oil by distillation to form a 50/50 blend (by volume).
  • the 50/50 blend contained about 4.0 wt% BS&W (basic sediment and water).
  • a quantity of the 50/50 blend was centrifuged, removing a major portion of the free water and solids, amounting to about 3 wt%, resulting in a centrifuged blend containing about 1.0 wt% BS&W.
  • a quantity of the centrifuged blend was then neutralized with a 3 wt% NaOH aqueous solution to reduce the TAN to about 0 (no TAN measurable).
  • the neutralized blend was also treated at 2.5 kV/inch AC electricity following addition of 100 ppm of a demulsifier obtained from Croda, commercially available under the trade name Croda D510.
  • the resulting neutralized blend contained about 0 wt% (trace) BS&W.
  • Each of the 50/50 blend, the centrifuged blend, and the neutralized blend were tested for conductivity at various temperatures. Results of such tests are shown in Table 2 below.
  • Raw bio-oil was separated from a product mixture produced from the thermo-catalytic pyrolysis of southern yellow pine wood chips.
  • a quantity of the raw bio-oil was blended with a quantity of an un-hydrotreated bio-naphtha fraction of the raw bio-oil to form a 50/50 blend (by volume), which was then stirred for 1 hour at 300 RPM.
  • an 80 ml quantity of the blend was mixed with 20 ml of an aqueous acid solution, and blended for 15 seconds.
  • the aqueous acid solutions were prepared by mixing the acids into process water produced in the thermo-catalytic pyrolysis of the wood chips.
  • one of the tested samples was prepared using process water without added acid.
  • a product mixture produced from the thermo-catalytic pyrolysis of southern yellow pine wood chips was collected and allowed to settle into an oil phase and a process water phase.
  • the process water phase was separated from the oil phase.
  • the process water phase was then extracted with MIBK and produced a raffinate and an extract.
  • MIBK was then separated (by distillation) from the extract which formed recovered MIBK and a residue which was not solid but an oily liquid material.
  • the results for the process water extraction are shown in Table 5 below.
  • the recovered MIBK quantity was 35.9 grams less than the amount of MIBK added to the process water. It is assumed that most of the overall mass loss of 21 .30 g was from MIBK.
  • the wt% yield of organics from the organics present in the initial process water portion of the total product mixture is calculated to be: 100 x (176.7g residue - 98.9 g organics in process oil - 16.7 g MIBK in residue) / (205 g organics in the process water) ⁇ 30 wt%.
  • Thermal stability of the bio-oil product is an extremely important processing parameter, since changes in the chemical and physical composition by thermal stress may create chemical changes (polymerization), viscosity changes and plugging issues (solids formation) in the upgrading units (such as hydrotreating units).
  • a high oxygen product mixture produced from the thermo-catalytic pyrolysis of southern yellow pine wood chips was collected and allowed to settle, and a bio-oil stream was obtained. Also, a portion of the total product mixture was then extracted with MIBK and produced a raffinate and an extract. MIBK was then separated (by distillation) from the extract which formed recovered MIBK and a residue which was not solid but an oily liquid material.
  • the resulting bio-oil stream and residue were separately subjected to a thermal stability study by heating the extracted oil in autoclave tubes, purged with Argon gas and immersed in a heated oil bath for 1 hr and 5 hrs, which is a more than typical residence time in heat exchangers and separation tanks.
  • Table 7 shows results from the thermal stability test of the bio-oil stream and the residue.
  • the % viscosity change for the MIBK produced residue is significantly lower than that for the bio-oil stream. This demonstrates a significant increase in stability for the residue over that for the typical bio-oil stream which has not been subjected to extraction.
  • the initial viscosity of the residue is higher than that for the bio-oil stream due to the substantial absence of water and light (C1 -C4) carbon containing compounds which are removed during the MIBK extraction.
  • a product mixture produced from the thermo-catalytic pyrolysis of southern yellow pine wood chips was collected.
  • the total product mixture was then extracted with MIBK and produced a raffinate and an extract.
  • MIBK was then separated (by distillation) from the extract which formed recovered MIBK and a residue which was not solid but an oily liquid material.
  • the extract was then subjected to spinning/band distillation for separation of the residue from the MIBK.
  • Table 8 The results of such distillation demonstrate that substantially all of the MIBK is removable from the extract.
  • a product mixture produced from the thermo-catalytic pyrolysis of southern yellow pine wood chips was collected.
  • the total product mixture was then extracted with MIBK and produced a raffinate 1 and an extract.
  • MIBK was then separated (by distillation) from the extract which formed recovered MIBK and a residue which was not solid but an oily liquid material.
  • the resulting raffinate 1 was then subjected to an extraction with MIBK to form a raffinate 2.
  • the resulting raffinate 2 was then subjected to an extraction with MIBK to form a raffinate 3.
  • the resulting raffinate 3 was then subjected to an extraction with MIBK to form a raffinate 4.
  • a product mixture produced from the thermo-catalytic pyrolysis of southern yellow pine wood chips was collected.
  • the total product mixture was then extracted with MIBK and produced a raffinate 1 and an extract.
  • the resulting raffinate 1 was then subjected to an extraction with MIBK to form a raffinate 2.
  • the resulting raffinate 2 was then subjected to an extraction with MIBK to form a raffinate 3.
  • Each of the extractions were at a volume ratio of MIBK to water of 25 : 75.
  • (+/-)-1 -lndanol >6 >5
  • a low oxygen product mixture produced from the thermo-catalytic pyrolysis of southern yellow pine wood chips was collected.
  • the total product mixture was then extracted with MI BK and produced a raffinate and an extract.
  • MIBK was then separated (by distillation) from the extract which formed recovered MIBK and a residue which was not solid but an oily liquid material.
  • Concentrations of volatile organic components were measured using GC/MS for the product mixture and for the raffinate. Also, % C was also determined for such components.
  • the results for the C1 -C4 volatile organic components are shown in Table 1 1 below, and the results for the C5+ volatile organic components are shown in Tables 12A and 12B below .
  • the total carbon content of the product mixture was analyzed and found to be 3.78 wt% C. By subtraction, the total amount of carbon from non-volatile organic components was 0.37 wt%.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Extraction Or Liquid Replacement (AREA)

Abstract

L'invention porte sur un procédé pour altérer le rapport entre les densités de la phase huileuse et de la phase aqueuse résultant de la conversion d'une biomasse en produits liquides, la réduction de la conductivité et de métaux du mélange produit, dont chacune peut aider à l'enlèvement des matières solides contenues dans la phase huileuse ; et un procédé d'extraction liquide-liquide pour partager les composés contenant du carbone souhaitable dans la phase huileuse et les composés contenant du carbone indésirable dans la phase aqueuse.
PCT/US2014/035804 2013-05-07 2014-04-29 Procédé de valorisation de produits dérivés d'une biomasse, par utilisation d'une extraction liquide-liquide WO2014182499A1 (fr)

Priority Applications (2)

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CA2911456A CA2911456C (fr) 2013-05-07 2014-04-29 Procede de valorisation de produits derives d'une biomasse, par utilisation d'une extraction liquide-liquide

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WO2018013575A1 (fr) * 2016-07-11 2018-01-18 Inaeris Technologies, Llc Procédé de valorisation de produits dérivés d'une biomasse par extraction liquide-liquide
US10427069B2 (en) 2011-08-18 2019-10-01 Inaeris Technologies, Llc Process for upgrading biomass derived products using liquid-liquid extraction
EP3494201B1 (fr) 2016-08-05 2021-03-31 Neste Oyj Purification d'une matière première par traitement thermique

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WO2000071494A1 (fr) * 1999-05-24 2000-11-30 James W. Bunger And Associates, Inc. Procede d'amelioration de la valeur des ressources naturelles d'hydrocarbures
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Publication number Priority date Publication date Assignee Title
US10427069B2 (en) 2011-08-18 2019-10-01 Inaeris Technologies, Llc Process for upgrading biomass derived products using liquid-liquid extraction
WO2018013575A1 (fr) * 2016-07-11 2018-01-18 Inaeris Technologies, Llc Procédé de valorisation de produits dérivés d'une biomasse par extraction liquide-liquide
EP3481524A4 (fr) * 2016-07-11 2020-05-13 Inaeris Technologies, LLC. Procédé de valorisation de produits dérivés d'une biomasse par extraction liquide-liquide
EP3494201B1 (fr) 2016-08-05 2021-03-31 Neste Oyj Purification d'une matière première par traitement thermique

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CA2911456A1 (fr) 2014-11-13
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EP2994209A1 (fr) 2016-03-16

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