Patent Grant
10427069
1. Field
The present disclosure 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 presently disclosed and/or claimed 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.
2. Description of the Related Art
In the conversion of biomass to liquid products, 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. It is often the case that 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. As a result, 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.
Thus, there is a need for an improved system whereby the solids content of biomass derived oil is reduced.
In addition, 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. Such 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. Thus, there is also a need for an improved system whereby undesirable carbon containing compounds are transferred from the oil phase to the water phase and desirable carbon containing compounds are transferred from the water phase to the oil phase.
In accordance with an embodiment of the present disclosure, a process is provided comprising:
In accordance with another embodiment of the present disclosure, such process can additionally comprise:
In accordance with another embodiment of the present disclosure, such process can additionally comprise:
In accordance with another embodiment of the present disclosure, such process can additionally comprise:
In accordance with another embodiment of the present disclosure, such process can additionally comprise:
In accordance with another embodiment of the present disclosure, such process can additionally comprise:
In accordance with another embodiment of the present dislcosure, such process can additionally comprise:
In accordance with another embodiment of the present disclosure, wherein the first and/or second oil phases further contain metals, a process is provided comprising:
In accordance with another embodiment of the present disclosure, a method is provided comprising:
In accordance with another embodiment of the present disclosure, a method is provided comprising:
The biomass material useful in the presently disclosed and/or claimed invention can be any biomass capable of being converted to liquid and gaseous hydrocarbons.
Preferred are 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. Examples of 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. 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 6, or at least about 7, or 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.
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.
Specific Gravity Modification
The ratio of the specific gravities of the first oil phase to the first aqueous phase (SGR1) 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 6:1, or from about 0.6:1 to about 4:1, or from about 0.6:1 to about 2.4:1, or from about 0.6:1 to about 1:1. When light cycle oil is used as the diluent, 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. Preferably, 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 NaCl, MgCl2, KCl, KBr, Na2SO4, NaHCO3, NaOH, KOH, NH4OH, alkyl amines, pyridines, quinolines, H2S, 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, NaCl, or MgCl2. 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.
More generally, 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, NaCl, MgCl2, KCl, KBr, Na2SO4, NaHCO3, NaOH, KOH, NH4OH, alkyl amines, pyridines, quinolines, H2S, ammonia, ammonium compounds including: nitrates, sulfides, carbonates (such as ammonium bicarbonate), hydroxides, acetates, chlorides, bromides, iodides, and sulfates, a glycol, and combinations thereof.
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. Following the settling of the second mixture, 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.
When 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.
Additionally, when a diluent is used as at least one specific gravity modifier, 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.
Further, when a diluent is 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.
Conductivity Modification
Alternatively, 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. In one embodiment, 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, NH4OH, 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. Combinations of 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.
In addition, at least a portion of 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. Also, 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. Also, 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.
Acid Treatment
In addition, the 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. 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.
Liquid-Liquid Extraction
Alternatively, 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. The term “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. The term “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. Also, 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. In addition, 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, and 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 10, or less than about 7, or less than about 5, or less than about 4, or less than about 3, or less than about 2, or 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 5, or less than about 3, or less than about 2, or 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 second mixture can comprise less than about 0.5, or less than about 0.4, or less than about 0.3, or less than about 0.2, or less than about 0.1 or less than about 0.05 wt % of the organics B.
The first aqueous phase (process water) 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. Also, 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.
In accordance with another embodiment, 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. In addition, 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, and 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 10, or less than about 7, or less than about 5, or less than about 4, or less than about 3, or less than about 2, or 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 5, or less than about 4, or less than about 3, or less than about 2, or 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 0.5, or less than about 0.4, or less than about 0.3, or less than about 0.2, or less than about 0.1 or less than about 0.05 wt % of the organics B.
The first aqueous phase (process water) 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. Also, 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.
Methyl Isobutyl Ketone Extraction Process for Recovering Bio-Oil Product
In another aspect, the present disclosure is directed to a method comprising: (a) providing a first mixture comprising reaction products produced from catalytic conversion of biomass (as described above), wherein said reaction products comprise water and biomass derived carbon containing compounds; (b) contacting said first mixture with an extraction solvent comprising, consisting of, or consisting essentially of methyl isobutyl ketone, thereby forming an extraction mixture comprising an extraction oil phase and an extraction aqueous phase; wherein the extraction oil phase has a specific gravity less than 1.0 and the extraction aqueous phase has a specific gravity equal to or greater than 1.0; and (c) separating the extraction oil phase and the extraction aqueous phase.
The biomass conversion can comprise, for example but without limitation, fast pyrolysis, catalytic pyrolysis, and/or 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.
In one embodiment, the biomass conversion can be by catalytic pyrolysis at a temperature ranging from 400° C. to 700° C.
In one embodiment, the extraction mixture further comprises solids and at least a portion of the solids are removed from the extraction mixture by filtration prior to step b). In another embodiment, at least one of the extraction oil phase and the extraction aqueous phase comprises solids and at least a portion of the solids are removed from at least one of the extraction oil phase and the extraction aqueous phase by filtration after step c).
Separating the extraction oil phase and extraction aqueous phase can comprise feeding the extraction mixture to, for example but without limitation, a decanter, filter, filter press, centrifuge, decanter centrifuge, an inverting filter centrifuge, and combinations thereof.
In one embodiment, the method further comprises separating at least a portion of the extraction solvent from the extraction oil phase to produce a bio-oil product substantially free of the extraction solvent. In one embodiment, the step of separating at least a portion of the extraction solvent from the extraction oil phase comprises feeding the extraction oil phase to an extraction solvent recovery system comprising one or more distillation columns
In one embodiment, at least a portion of the separated extraction solvent is recycled as at least a part of the extraction solvent in step b).
The following examples are provided to further illustrate the presently disclosed and/or claimed inventive concept(s) and are not to be considered as unduly limiting the scope of the presently disclosed and/or claimed inventive concept(s).
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 μm 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 μm 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.
As can be seen from the data above, 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 μm 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. 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.
As can be seen from the data above, the ash content in the bio-oil drops significantly once the oil and water layers are flipped.
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 NaCl such that the resulting product water for each mixture contained about 2 M NaCl. For each of the mixtures, the organic phase (blended bio-oil) layer was flipped and on top, with the 2 M NaCl 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). NaCl was added to five of the bio-oil/water mixtures such that the distilled water portions separately contained about 1 M NaCl, about 2 M NaCl, about 3 M NaCl, about 4 M NaCl, and about 5 M NaCl, respectively. For each of the 3 M, 4 M, and 5 M NaCl mixtures, the organic phase (blended bio-oil) layer was clearly flipped and on top, with the water phase on the bottom of the container. For the 2 M NaCl mixture, the layers were mostly, but not completely, flipped, and the layers were not flipped for the 1 M NaCl 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). MgCl2 was added to five of the bio-oil/water mixtures such that the distilled water portions separately contained about 1M MgCl2, about 2 M MgCl2, about 3 M MgCl2, about 4 M MgCl2, and about 5 M MgCl2, respectively. For each of the 3 M, 4 M, and 5 M MgCl2 mixtures, the organic phase (blended bio-oil) layer was clearly flipped and on top, with the water phase on the bottom of the container. For the 2 M MgCl2 mixture, the layers were partially flipped, and the layers were not flipped for the 1 M MgCl2 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. NaCl was added to five of the product mixture samples such that those five product water portions separately contained about 1 M NaCl, about 2 M NaCl, about 3 M NaCl, about 4 M NaCl, and about 5 M NaCl, respectively. For each of the 3 M, 4 M, and 5 M NaCl mixtures, 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). For maximum dehydration, 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.
As can be seen from the data in Table 2, the addition of a neutralizing base to the bio-oil/bio-naphtha blend, along with electrostatic treatment, results in a significant decrease in conductivity. Thus, rather than leading to an expected increase in conductivity, it was unexpectedly found that the addition of a base to the system actually reduced the conductivity.
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. For each of the acid treatment tests, 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. As a control, one of the tested samples was prepared using process water without added acid. The samples were placed in a 140 F water bath for 30 minutes. The samples were then filtered through a 0.2 μm PVDF membrane filter and tested for metals using inductively coupled plasma mass spectrometry (ICP-MS). The metals content results are shown in Table 3 below.
As can be seen from the test results in Table 3, contacting bio-oil, which contains metals, with an aqueous acid solution including the above acids results in a substantial lowering of the wt % of dissolved metals in the resulting treated bio-oil.
Parameters of potential extraction solvents were evaluated for use in liquid-liquid extraction of bio-oil/water mixtures. Table 4 below sets out certain properties of four different solvents. As can be seen in Table 4, methyl isobutyl ketone (MIBK) and cyclopentyl methyl ether (CPME) have desirable properties for such liquid-liquid extraction, however, the use of cyclopentyl methyl ether is less desirable due to its high cost.
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. Assuming 21 g of MIBK were lost due to volatility, that leaves about 14.9 g of MIBK to account for. With a water solubility of 1.8 g/100 ml, the amount of MIBK in the raffinate is calculated as follows:
(749.3 g water)×(1 ml/g)×(1.8 g MIBK/100 ml water) ˜13.5 g MIBK. This leaves ˜1.4 g MIBK (14.9 g-13.5 g) in the residue.
As can be seen from the results in Table 5, a significant quantity of carbon containing compounds can be removed from the process water by extraction with MIBK and substantially all of the MIBK is recoverable from the process. Further quantities of MIBK can easily be recovered from the raffinate and/or the residue. Also, the wt % yield of residue from the organics present in the initial process water is calculated to be: 100×(94.1 g-1.4 g MIBK)/(229.2 g organics in the process water) ˜40 wt %.
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 results for the total product mixture extraction are shown in Table 6 below. The recovered MIBK quantity was 78.9 grams less than the amount of MIBK added to the process water. It is assumed that most of the overall mass loss of 50.9 g was from MIBK. Assuming 50 g of MIBK were lost due to volatility, that leaves about 28.9 g of MIBK to account for. With a water solubility of 1.8 g/100 ml, the amount of MIBK in the raffinate is calculated as follows:
(677.5 g water)×(1 ml/g)×(1.8 g MIBK/100 ml water) ˜12.2 g MIBK. This leaves ˜16.7 g MIBK (28.9 g-12.2 g) in the residue.
As can be seen from the results in Table 6, a significant quantity of carbon containing compounds can be removed from the total product mixture by extraction with MIBK and substantially all of the MIBK is recoverable from the process. Further quantities of MIBK can easily be recovered from the raffinate and/or the residue. Also, 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×(176.7 g 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.
As can be seen from Table 7, 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. The results of such distillation are shown in Table 8 below. The results in Table 8 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. The results of the extractions are shown in Table 9 below which shows that the low molecular weight oxygenate compounds (C1-C4) such as formaldehyde, acetaldehyde, butanone, acetic and propanoic acids and hydroxypropanone, are very soluble in water so they tend to stay in the water after MIBK extraction. This is preferred since hydrotreating such compounds would form C1-C4 alkanes that would end up in the gas phase. This would result in hydrogen consumption without the benefit of increasing renewable fuel yield.
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. Tables 10A-10C show partition coefficients for various components between the MIBK extract and the water which were calculated for raffinates 1 and 3 in accordance with the following: Kd=[wt %]MIBK Extract/[wt %]Raffinate. Values indicated as “>6” or “>5” are due to limits of detection of the GC/MS Analysis. The calculated Kd values demonstrate that the lighter components such as formaldehyde, acetaldehyde, acetic acid and 1-hydroxy-2-propanone preferentially stay with the water (raffinate).
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 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. 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 11 below, and the results for the C5+ volatile organic components are shown in Tables 12A and 12B below . In addition, 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 %.
As can be seen in Tables 11, 12A and 12B the data show that extraction of a biomass derived product mixture with MIBK is effective in removing C5+ volatile organic components from water. Specifically, while the product mixture contained 2.12 wt % C from C5+ organic volatiles, the raffinate contained at or near 0 wt % C from C5+ organic volatiles showing clear partitioning from the water phase to the oil phase. Also, the wt % C from C1-C4 volatile organic components is concentrated in the raffinate at 2.93 wt % as compared to only 1.29 wt % in the initial product mixture.
In a continuous process, a first mixture was produced from the catalytic conversion of Southern Yellow Pine at temperatures between 530° C. and 580° C. wherein said first mixture comprises raw bio-oil and product water. This mixture was sampled, separated into an aqueous phase (“first mixture water phase”) and an organic phase (“first mixture raw bio-oil phase”) by centrifuge, and then each phase was analyzed. MIBK was continuously added to the first mixture to form a second mixture, targeting a volumetric ratio of the MIBK to the raw bio-oil ranging from 0.75 to 3. The second mixture was passed through a static mixer and fed into a decanting vessel where the lighter organic/MIBK phase (“second mixture oil/MIBK phase”) was separated from the heavier aqueous phase (“second mixture aqueous phase”). Both phases were continuously removed from the vessel and samples were taken.
Each of the four phases (i.e., the first mixture raw bio-oil phase, first mixture water phase, second mixture organic/MIBK phase, and second mixture water phase) were analyzed by quantitative GC-MS to determine the amount of Organics A and Organics B in each sample. They were also analyzed by Karl-Fischer titration to determine the amount of water in each sample. Element analysis by LECO Corporation (St. Joseph, Mich.) was used to determine the carbon, hydrogen, and nitrogen in each sample; and oxygen was determined by the difference. Using the wet basis oxygen and the Karl-Fischer moisture results, a dry basis oxygen level for the oil was calculated. The amounts of solids in the organic phases were determined by filtration. The following are the completed measurements and balances for five runs, each of which is presented in one of Tables 13-17.
Additionally, hydrocarbon phases (i.e., second mixture organic/MIBK phases) produced in the same manner as the samples in Tables 13-17 were fed to a packed bed distillation tower for recovery of the MIBK and water removal prior to hydrotreating. The distillation column separated nearly all of the MIBK from the hydrocarbon phases, thereby producing a bio-oil product comprising only about 5 wt % water and substantially free of MIBK.
While the technology has been particularly shown and described with reference to specific embodiments, it should be understood by those skilled in the art that various changes in form and detail may be made without departing from the spirit and scope of the technology as defined by the appended claims.
The present application is a continuation-in-part of U.S. Ser. No. 13/889,105, filed May 7, 2013; which is a continuation-in-part of U.S. Ser. No. 13/212,861, filed Aug. 18, 2011, and issued on Apr. 19, 2016 as U.S. Pat. No. 9,315,739; the entire contents of each of which is hereby expressly incorporated herein by reference.
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| Number | Date | Country | |
|---|---|---|---|
| 20160317947 A1 | Nov 2016 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 13889105 | May 2013 | US |
| Child | 15207134 | US | |
| Parent | 13212861 | Aug 2011 | US |
| Child | 13889105 | US |
