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 liquid bio-oil or liquid pyrolysis oil, the process comprising:
(a) subjecting a liquid bio-oil or pyrolysis oil feedstream containing carbonyl oxygenates to a carbon-carbon bond forming condensation reaction to form C 6 + enriched condensates, wherein the carbon-carbon bond forming condensation reaction comprises an enol or enolate addition to a carbonyl compound, and wherein the oxygenates are selected from the group consisting of C 3 oxygenates, C 4 oxygenates, C 5 oxygenates and mixtures thereof and further wherein the C 3 oxygenates, C 4 oxygenates and C 5 oxygenates are selected from the group consisting of carboxylic acids, carboxylic acid esters, ketones and aldehydes;
(b) contacting the bio-oil or pyrolysis oil containing condensates of step (a) with hydrogen and hydrotreating the condensates to form a hydrotreated bio-oil or pyrolysis oil comprising C 6 + hydrocarbons; and
(c) fractionating the hydrotreated bio-oil or pyrolysis oil to obtain a C 6 + renewable biofuel,
wherein the condensation reaction in step (a) and the hydrotreating in step (b) occurs in a single reactor.
2. The process of claim 1 , wherein prior to step (a):
(i) biomass is converted in a biomass conversion reactor into gaseous, liquid and solid components;
(ii) the gaseous components and solid components are separated from the liquid components;
(iii) the liquid components are separated into an aqueous phase and an organic stream containing C 3 -C 5 oxygenates; and
(iv) the aqueous phase is then separated into another organic stream containing C 3 -C 5 oxygenates.
3. The process of claim 1 , wherein the condensation reaction is an aldol condensation.
4. The process of claim 1 , wherein the renewable biofuel is produced from liquid bio-oil.
5. A process for producing a renewable biofuel from a liquid bio-oil or pyrolysis oil, the process comprising:
(a) subjecting a liquid bio-oil or pyrolysis oil feedstream to a separation in a fractionator to produce a stream having the boiling point of naphtha;
(b) subjecting the naphtha stream and at least a portion of the liquid bio-oil or pyrolysis oil containing carbonyl oxygenates to a carbon-carbon bond forming condensation reaction to form C 6 + enriched condensates, wherein the oxygenates are selected from the group consisting of C 3 oxygenates, C 4 oxygenates and C 5 oxygenates and mixtures thereof;
(c) contacting the bio-oil or pyrolysis oil containing condensates of step (a) with hydrogen and hydrotreating the condensates to form a hydrotreated feedstream; and
(d) fractionating the hydrotreated feedstream to obtain a C 6 + biofuel,
wherein the carbon-carbon forming condensation reaction in step (a) and the hydrotreating in step (b) occurs in a single reactor.
6. The process of claim 5 , wherein prior to step (a):
(i) biomass is converted in a biomass conversion reactor into gaseous, liquid and solid components;
(ii) the gaseous components and solid components are separated from the liquid components;
(iii) the liquid components are separated into an aqueous phase and an organic stream containing C 3 -C 5 oxygenates; and
(iv) the aqueous phase is then separated into another organic stream containing C 3 -C 5 oxygenates.
7. The process of claim 5 , wherein condensation occurs in the single reactor in the presence of a heterogeneous acid catalyst.
8. The process of claim 7 , 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.
9. The process of claim 8 , 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.
10. The process of claim 7 , wherein the heterogeneous catalyst is a zeolite beta.
11. The process of claim 5 , wherein condensation occurs in the presence of a basic catalyst selected from the group consisting of alkaline oxides, alkaline earth metal oxides, Group IIB oxides and Groups IIIB oxides and mixtures thereof.
12. The process of claim 11 , wherein the basic catalyst is selected from the group consisting of MgO, CaO, SrO, BaO, ZrO 2 , TiO 2 , CeO and mixtures thereof.
13. The process of claim 11 , wherein the basic catalyst is a supported catalyst.
14. The process of claim 5 , wherein the C 3 oxygenates, C 4 oxygenates and C 5 oxygenates are selected from the group consisting of carboxylic acids, carboxylic acid esters, ketones and aldehydes.
15. The process of claim 14 , wherein the ketones are methyl vinyl ketone and ethyl vinyl ketone.
16. A process for producing a renewable biofuel from a liquid bio-oil or pyrolysis oil, the process comprising:
(a) subjecting a liquid bio-oil or pyrolysis oil feedstream to a separation in a fractionator to produce a stream having the boiling point of naphtha;
(b) subjecting the naphtha stream and at least a portion of a liquid bio-oil or pyrolysis oil stream containing carbonyl oxygenates to a carbon-carbon bond forming condensation reaction in a catalytic distillation column to form C 6 + enriched condensates, wherein the oxygenates are selected from the group consisting of C 3 oxygenates, C 4 oxygenates and C 5 oxygenates and mixtures thereof;
(c) contacting the bio-oil or pyrolysis oil containing condensates of step (a) with hydrogen and hydrotreating the condensates to form a hydrotreated feedstream; and
(d) fractionating the hydrotreated bio-oil or pyrolysis oil to obtain a C 6 + renewable biofuel,
wherein the condensation reaction in step (a) and the hydrotreating in step (b) occurs in the distillation column.
17. The process of claim 16 , wherein the feedstream containing carbonyl oxygenates originates from an aqueous stream removed from a solids separator.
18. The process of claim 16 , wherein prior to step (a):
(i) biomass is converted in a biomass conversion reactor into gaseous, liquid and solid components;
(ii) the gaseous components and solid components are separated from the liquid components;
(iii) the liquid components are separated into an aqueous phase and an organic stream containing C 3 -C 5 oxygenates; and
(iv) the aqueous phase is then separated into another organic stream containing C 3 -C 5 oxygenates.
19. The process of claim 16 , wherein the feedstream containing carbonyl oxygenates originates from an aqueous stream removed from a solids separator.
20. The process of claim 16 , wherein condensation occurs in a presence of a heterogeneous acid catalyst.
21. The process of claim 16 , wherein the carbon-carbon bond forming condensation reaction is a Diels-Alder reaction, a Michael addition reaction or a Robinson annulation reaction.
22. The process of claim 16 , wherein the carbon-carbon bond forming condensation reaction is an aldol condensation.
23. The process of claim 16 , wherein the C 3 oxygenates, C 4 oxygenates and C 5 oxygenates are selected from the group consisting of carboxylic acids, carboxylic acid esters, ketones and aldehydes.
24. A process for producing a renewable biofuel from liquid pyrolysis oil, the process comprising:
(a) subjecting a liquid pyrolysis oil feedstream containing carbonyl oxygenates to a carbon-carbon bond forming condensation reaction to form C 6 + enriched condensates, wherein the oxygenates are selected from the group consisting of C 3 oxygenates, C 4 oxygenates, 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;
(b) contacting the pyrolysis oil containing condensates of step (a) with hydrogen and hydrotreating the condensates to form a hydrotreated bio-oil comprising C 6 + hydrocarbons; and
(c) fractionating the hydrotreated pyrolysis oil to obtain a C 6 + renewable biofuel,
wherein the condensation reaction in step (a) and the hydrotreating in step (b) occurs in the same reactor.
25. The process of claim 24 , wherein prior to step (a):
(i) biomass is converted in a biomass conversion reactor into gaseous, liquid and solid components;
(ii) the gaseous components and solid components are separated from the liquid components;
(iii) the liquid components are separated into an aqueous phase and an organic stream containing C 3 -C 5 oxygenates; and
(iv) the aqueous phase is then separated into another organic stream containing C 3 -C 5 oxygenates.