Process for upgrading biomass derived products using liquid-liquid extraction
View Patent ↗Disclosed is a process for the alteration of the ratio of the specific gravities of the oil and water phases resulting from the conversion of biomass to liquid products, the reduction of the conductivity and of metals of the product mixture, which each can aid in the removal of solids contained in the oil phase; and a liquid-liquid extraction method for partitioning desirable carbon containing compounds into the oil phase and undesirable carbon containing compounds into the water phase.
1. A method comprising:
a) contacting an extraction solvent with a first mixture, thereby forming a second mixture comprising an extract and a raffinate,
wherein said first mixture comprises process water separated from reaction products comprising bio-oil and said process water produced from catalytic conversion of biomass at temperatures ranging from 300° C. to 1000° C., and wherein said process water comprises water and biomass derived carbon containing compounds including organics A and organics B, and further wherein:
said organics A comprise 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,
said organics B comprise compounds having at least four carbon atoms per molecule wherein said 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,
said extract and said raffinate are immiscible,
said extract comprises substantially all of said extraction solvent and substantially all of said organics B,
said raffinate comprises substantially all of said water and substantially all of said organics A, and
said extraction solvent has a dipole moment greater than about 1.0 debye, a density less than about 1.0, a water solubility at 20° C. of less than about 2.5 g/100 ml of water, and a boiling point in the range of from about 90 to about 300° F.;
b) separating said second mixture thereby forming an intermediate product stream comprising at least a portion of said extract and a waste water stream comprising substantially all of said raffinate, wherein said wastewater stream comprises less than about 0.1 wt % of said organics B; and
c) removing at least a portion of said extraction solvent from said intermediate product stream forming a recovered extraction solvent and a bio-oil product.
2. The method of claim 1 wherein the viscosity of said second mixture is lower than the viscosity of said first mixture, wherein said second mixture further comprises solids, and wherein at least a portion of said solids are removed from said second mixture by filtration prior to said step b).
3. The method of claim 1 wherein the partition coefficients of said organics A for said extract and said raffinate are each less than about 1.0, and wherein the partition coefficients of said organics B for said extract and said raffinate are each greater than about 1.0.
4. The method of claim 1 wherein said recovered extraction solvent is recycled as at least a part of said extraction solvent in step a).
5. The method of claim 1 wherein said bio-oil product comprises less than about 1.0 wt % of said organics A.
6. The method of claim 1 wherein said bio-oil of said reaction products comprises at least about 8 wt % water and wherein said bio-oil product comprises less than about 1 wt % water.
7. The method of claim 1 wherein said carbon containing compounds of said organics B are selected from the group consisting of ketones, furans, phenols, catechols, aromatic hydrocarbons, indenols, indanols, naphthalenos, benzofurans, and combinations thereof.
8. The method of claim 1 wherein said extraction solvent comprises a member selected from the group consisting of methyl isobutyl ketone, cyclopentyl methyl ether, and combinations thereof.
9. The method of claim 1 wherein said extraction solvent comprises methyl isobutyl ketone.
10. The method of claim 1 wherein said intermediate product stream comprises substantially all of said extract.
11. The method of claim 1 wherein said first mixture is counter-currently contacted with said extraction solvent in step a).
12. The method of claim 1 wherein said first mixture is cross-currently contacted with said extraction solvent in step a).
13. The method of claim 1 wherein the contacting of said first mixture with said extraction solvent in step a) forms a static mixture, and wherein the separation of said second mixture in step b) is by decanting.
14. The method of claim 1 wherein said extraction solvent is substantially unreactive when exposed to acidic aqueous media and is substantially thermally stable at temperatures up to about 500° F.
15. The method of claim 1 wherein said extraction solvent comprises cyclopentyl methyl ether.
16. A method comprising:
a) providing a first mixture comprising reaction products produced from catalytic conversion of biomass at temperatures ranging from 300° C. to 1000° C., said reaction products comprising water and biomass derived carbon containing compounds including organics A and organics B, wherein:
said organics A comprise 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
said organics B comprise carbon containing compounds having at least four carbon atoms per molecule, wherein said organics B are substantially free of said organics A, and
wherein said first mixture includes i) a first oil phase comprising at least a portion of said biomass derived carbon containing compounds and at least a portion of said water and ii) a first aqueous phase comprising at least a portion of said water and at least a portion of said biomass derived carbon containing compounds, wherein said first oil phase and said first aqueous phase are immiscible;
b) contacting said first mixture with an extraction solvent thereby forming an extraction mixture comprising an extraction oil phase and an extraction aqueous phase; wherein:
substantially all of said organics A present in said first oil phase are partitioned from said first oil phase to said first aqueous phase and substantially all of said organics B present in said first aqueous phase are partitioned from said first aqueous phase to said first oil phase, thereby forming (I) said extraction oil phase comprising substantially all of said organics B and substantially all of said extraction solvent, and (II) said extraction aqueous phase comprising substantially all of said water and substantially all of said organics A,
said extraction oil phase and said extraction aqueous phase are immiscible, and
said extraction solvent has a dipole moment greater than about 1.0 debye, a density less than about 1.0, a water solubility at 20° C. of less than about 2.5 g/100 ml of water, and a boiling point in the range of from about 90 to about 300° F.; and
c) separating said extraction mixture thereby forming an intermediate product stream comprising at least a portion of said extraction oil phase and a waste water stream comprising substantially all of said extraction aqueous phase, wherein said waste water stream comprises less than about 0.1 wt % of said organics B.
17. The method of claim 16 wherein at least a portion of said extraction solvent is removed from said intermediate product stream forming a recovered extraction solvent and a bio-oil product.
18. The method of claim 17 wherein said recovered extraction solvent is recycled as at least a part of said extraction solvent in step b).
19. The method of claim 17 wherein said bio-oil product comprises less than about 1.0 wt % of said organics A.
20. The method of claim 17 wherein said first oil phase comprises at least about 8 wt % water and wherein said bio-oil product comprises less than about 1 wt % water.
21. The method of claim 16 wherein the viscosity of said extraction mixture is lower than the viscosity of said first mixture, wherein said extraction mixture further comprises solids, and wherein at least a portion of said solids are removed from said extraction mixture by filtration prior to said step c).
22. The method of claim 16 wherein the partition coefficients of said organics A for said extraction oil phase and said extraction aqueous phase are each less than about 1, and wherein the partition coefficients of said organics B for said extraction oil phase and said extraction aqueous phase are each greater than about 1.
23. The method of claim 16 wherein said carbon containing compounds of said organics B are selected from the group consisting of Ketones, Furans, Phenols, Catechols, Aromatics hydrocarbons, Indenols, Indanols, Naphthalenos, Benzofurans, and combinations thereof.
24. The method of claim 16 wherein said extraction solvent comprises a member selected from the group consisting of methyl isobutyl ketone, cyclopentyl methyl ether, and combinations thereof.
25. The method of claim 16 wherein said extraction solvent comprises methyl isobutyl ketone.
26. The method of claim 16 wherein said intermediate product stream comprises substantially all of said extraction oil phase.
27. The method of claim 16 wherein said first mixture is counter-currently contacted with said extraction solvent in step b).
28. The method of claim 16 wherein said first mixture is cross-currently contacted with said extraction solvent in step b).
29. The method of claim 16 wherein the contacting of said first mixture with said extraction solvent in step b) forms a static mixture, and wherein the separation of said extraction mixture in step c) is by decanting.
30. The method of claim 16 wherein said extraction solvent is substantially unreactive when exposed to acidic aqueous media and is substantially thermally stable at temperatures up to about 500° F.
31. The method of claim 16 wherein said extraction solvent comprises cyclopentyl methyl ether.