Process of generating a renewable biofuel from a hydrotreated stream of condensed oxygenates
View Patent ↗A renewable fuel may be obtained from a bio-oil containing C 3 -C 5 oxygenates. In a first step, the bio-oil is subjected to a condensation reaction in which the oxygenates undergo a carbon-carbon bond forming reaction to produce a stream containing C 6 + oxygenates. In a second step, the stream is hydrotreated to produce C 6 + hydrocarbons.
1. A process for producing a renewable biofuel from a liquid bio-oil or liquid pyrolysis oil, the process comprising:
(a) introducing effluent from a biomass conversion unit into a separator and separating from the effluent a liquid bio-oil or pyrolysis oil;
(b) subjecting carbonyl containing oxygenates within the separated liquid bio-oil or pyrolysis oil to a carbon-carbon bond forming condensation reaction in a condensation reactor to form C 6 + enriched condensates, wherein the carbonyl containing oxygenates are selected from the group consisting of C 3 oxygenates, C 4 oxygenates and C 5 oxygenates and mixtures thereof and further wherein the C 3 , C 4 and C 5 oxygenates are selected from the group consisting of carboxylic acids, carboxylic acid esters, ketones and aldehydes;
(c) contacting the bio-oil or pyrolysis oil containing condensates of step (b) with hydrogen and hydrotreating the C 6 + condensates to form a hydrotreated bio-oil or pyrolysis oil comprising C 6 + enriched hydrocarbons; and
(d) removing the hydrotreated bio-oil or pyrolysis oil comprising C 6 + enriched hydrocarbons from the hydrotreater and fractionating the hydrotreated bio-oil or pyrolysis oil comprising C 6 + enriched hydrocarbons to obtain a C 6 + renewable biofuel.
2. The process of claim 1 , wherein the condensation reactor in step (b) is a distillation column.
3. The process of claim 2 , wherein condensation in the distillation column occurs in the presence of a heterogeneous acid catalyst.
4. The process of claim 3 , wherein the heterogeneous acid catalyst is selected from the group consisting of organic sulfonic acids; perfluoroalkylsulfonic acids; zeolites; sulfated transition metal oxides, and perfluorinated ion exchange polymers containing pendant sulfonic acid, carboxylic acid, or sulfonic acid groups; sulfonated copolymers of styrene and divinylbenzene; sulfated silicas, aluminas, titania and/or zirconia; and amorphous SiAl and mixtures thereof.
5. The process of claim 4 , wherein the heterogeneous acid catalyst is selected from the group consisting of ZSM-type zeolites, zeolite beta, sulfonated fluoropolymers or copolymers, sulfated zirconia and amorphous SiAl.
6. The process of claim 5 , wherein the heterogeneous catalyst is a zeolite beta.
7. The process of claim 3 , wherein the heterogeneous acid catalyst is located in the distillation column at a pre-determined location within the distillation column.
8. The process of claim 1 , wherein the carbon-carbon bond forming condensation reaction is a Diels-Alder reaction.
9. The process of claim 8 , wherein the condensation reactor is a distillation column.
10. The process of claim 1 , wherein the C 6 + enriched condensates are prepared in step (b) by an aldol condensation reaction.
11. The process of claim 1 , wherein the C 6 + enriched condensates are prepared in step (b) by a Michael addition reaction.
12. The process of claim 1 , wherein the C 6 + enriched condensates are prepared in step (b) by a Robinson annulation reaction.
13. The process of claim 1 , wherein the ketones are methyl vinyl ketone and ethyl vinyl ketone.
14. The process of claim 1 , wherein the C 6 + enriched hydrocarbons of step (c) are separated into a naphtha fraction containing predominately C 5 through C 10 hydrocarbons and a hydrocarbon fraction containing C 10 + hydrocarbons.
15. A process for enhancing the yield of either hydrotreated bio-oil from a liquid bio-oil stream or hydrotreated pyrolysis oil from a liquid pyrolysis stream, the liquid bio-oil stream or liquid pyrolysis stream containing oxygenates selected from the group consisting of C 3 oxygenates, C 4 oxygenates and C 5 oxygenates and mixtures thereof wherein the C 3 , C 4 and C 5 oxygenates are selected from the group consisting of carboxylic acids, carboxylic acid esters, ketones and aldehydes, the process comprising:
(a) subjecting the C 3 , C 4 and C 5 oxygenates within the liquid bio-oil stream or liquid pyrolysis stream to a carbon-carbon bond forming condensation reaction in a condensation reactor to produce C 6 + oxygenates;
(b) removing the C 6 + oxygenates from the condensation reactor and introducing them to a hydrotreater; and
(c) hydrotreating the C 6 + oxygenates to render C 6 + enriched hydrocarbons, wherein the amount of oxygen removed from the C 6 + oxygenates in the hydrotreater is from 90 to about 99.99%.
16. A process for producing a renewable biofuel from a hydrotreated bio-oil, the process comprising:
(a) feeding a liquid bio-oil stream to a distillation column;
(b) subjecting lower carbon oxygenates in the liquid bio-oil stream to a carbon-carbon bond forming condensation reaction in the distillation column and forming C 6 + oxygenates from the lower carbon oxygenates, wherein the lower carbon oxygenates are selected from the group consisting of C 3 oxygenates, C 4 oxygenates and C 5 oxygenates and mixtures thereof and further wherein the C 3 , C 4 and C 5 oxygenates are selected from the group consisting of carboxylic acids, carboxylic acid esters, ketones and aldehydes;
(c) removing the C 6 + oxygenates from the distillation column and introducing them into a hydrotreater;
(d) hydrotreating the C 6 + oxygenates in the hydrotreater to render C 6 + enriched hydrocarbons; and
(e) subjecting the C 6 + enriched hydrocarbons to fractionation to render a 180° F.-420° F. naphtha and at least one hydrocarbon fraction having a boiling point less than 180° F.
17. A process for producing a renewable biofuel from biomass, the process comprising:
(a) separating a predominately organic liquid bio-oil phase from treated biomass, wherein the organic liquid bio-oil phase comprises oxygenates selected from the group consisting of C 3 oxygenates, C 4 oxygenates and C 5 oxygenates and further wherein the C 3 , C 4 and C 5 oxygenates are selected from the group consisting of carboxylic acids, carboxylic acid esters, ketones and aldehydes;
(b) forming C 6 + oxygenates through a carbon-carbon bond forming reaction from the C 3 oxygenates, C 4 oxygenates and C 5 oxygenates in the organic liquid bio-oil phase;
(c) introducing the C 6 + oxygenates into a hydrotreater and hydrotreating the C 6 + oxygenates in the hydrotreater to produce C 6 + enriched hydrocarbons; and
(d) subjecting the C 6 + enriched hydrocarbons to fractionation to render separate hydrocarbon fractions containing (i) C 5 to C 10 hydrocarbons and (ii) C 10 + hydrocarbons.
18. The process of claim 17 , wherein the hydrotreater has a catalytic bed.
19. The process of claim 17 , wherein transportation fuels are prepared from the separated hydrocarbon fractions of step (d).
20. The process of claim 17 , wherein the C 3 oxygenates, C 4 oxygenates and C 5 oxygenates include methyl vinyl ketone and ethyl vinyl ketone.
21. The process of claim 17 , wherein the C 6 + oxygenates of step (b) are prepared through an aldol condensation reaction, a Diels-Alder reaction, a Michael addition, or a Robinson annulations reaction or a mixture thereof.
22. The process of claim 17 , wherein the C 6 + oxygenates of step (b) are prepared through a Diels-Alder reaction.
23. The process of claim 1 , further comprising recovering solids from the effluent in step (a), regenerating the recovered solids and then introducing the regenerated solids into the biomass conversion unit.
24. The process of claim 1 , further comprising recovering solids from the effluent in step (a), regenerating the recovered solids, introducing the regenerated solids to a biomass feedstream and then introducing the biomass feedstream into the biomass conversion unit.