Hydrocarbons from pyrolysis oil
View Patent ↗Described is a process for converting pyrolysis oil obtained by pyrolysis of biomass into fuel range hydrocarbon by alcoholysis of pyrolysis oil with subsequent hydrotreatment. A straightforward methodology to prepare upgradeable pyrolysis oil via alcoholysis. A method hydrotreating technology for oxygen removal and hydrocarbon production. The resulting hydrocarbon products are 100% fungible with conventional transportation fuels.
1. A process for converting pyrolysis oil to a hydrocarbon fuel, comprising:
a) reacting a pyrolysis oil with a feed comprising one or more alcohol species in a reactor to form a product mixture comprising an alcoholysis product;
b) contacting the alcoholysis product with a hydrotreating catalyst in the presence of hydrogen in a reaction zone under reaction conditions sufficient to convert at least a portion of said alcoholysis product into one or more fuel range hydrocarbon products.
2. The process of claim 1 , wherein the product mixture of step (a) additionally comprises solid residue, and an un-reacted quantity of the one or more alcohol species.
3. The process of claim 1 , further comprising a step prior to step (a) for pyrolyzing a biomass to form the pyrolysis oil of step (a).
4. The process of claim 1 , wherein the reacting of step (a) is performed at a temperature between about 150° C. and about 500° C.; a pressure between about 500 psig and about 4000 psig; and for a duration of between 2 min and 240 minutes.
5. The process of claim 1 , wherein the reacting of step (a) is performed at a temperature between 250° C. and about 500° C.; a pressure of between 1500 psig and about 4000 psig; and for a duration of between 15 min and 120 min.
6. The process of claim 1 , wherein the reaction conditions of step (b) comprise a temperature of between about 120° C. and about 450° C., and a pressure of between about 500 psig and about 3500 psig.
7. The process of claim 1 , wherein the reaction conditions of step (b) comprise a temperature of between about 150° C. and about 350° C., and a pressure of between about 800 psig and about 1500 psig.
8. The process of claim 1 , wherein the contacting of step (b) is first performed at a temperature of between about 120° C. and 200° C., followed by contacting at a higher temperature of between about 200° C. and about 450° C.
9. The process of claim 2 , further comprising a separation step wherein the solid residue is separated out from the product mixture using a separator, the separation step being performed by filtration, extraction, decantation, centrifugation and any combination thereof, and wherein said separator is selected from the group consisting of a gas-liquid, liquid-liquid, three-phase, horizontal, vertical, tubular, rotary, turbine, centrifugal and any combination thereof.
10. The process of claim 2 , further comprising a step for recovering the un-reacted quantity of the one or more alcohol species from the product mixture of step (a), and recycling at least a portion of the un-reacted quantity as feed for step (a).
11. The process of claim 1 , wherein the reacting of step (a) occurs in the presence of a catalyst, wherein the catalyst is selected from the group consisting of alumina, hafnia, titania, zirconia, and mixtures thereof.
12. The process of claim 1 , wherein the reacting of step (a) occurs in the presence of a solid catalyst, wherein the catalyst is selected from the group consisting of alumina, silica-alumina, hafnia, titania, zirconia and mixtures thereof.
13. The process of claim 1 , wherein the feed comprises one or more C1-C30 alcohols.
14. The process of claim 1 , wherein the feed is selected from the group comprising methanol, ethanol, butanol, tetrahydrofurfuryl alcohol, ethylene glycol, propylene glycol, glycerol, fatty alcohols and mixtures thereof.
15. The process of claim 1 , wherein the feed is formed from biomass through fermentation processes.
16. The process of claim 1 , wherein the mass ratio of the pyrolysis oil to the feed is 0.05 to 10.
17. The process of claim 1 , wherein the hydrotreating catalyst is selected from the group consisting of cobalt (Co), molybdenum (Mo), nickel (Ni), titanium (Ti), tungsten (W), zinc (Zn), antimony (Sb), bismuth (Bi), cerium (Ce), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), manganese (Mn), rhenium (Re), iron (Fe), platinum (Pt), iridium (Ir), palladium (Pd), osmium (Os), rhodium (Rh), ruthenium (Ru), nickel, copper impregnated zinc oxide (Cu/ZnO), copper impregnated chromium oxide (Cu/Cr), nickel aluminum oxide (Ni/Al 2 O 3 ), palladium aluminum oxide (Pd/Al 2 O 3 ), cobalt molybdenum (CoMo), nickel molybdenum (NiMo), nickel molybdenum tungsten (NiMoW), sulfided cobalt molybdenum (CoMo), sulfided nickel molybdenum (NiMo), metal carbides, or any combinations thereof.
18. The process of claim 1 , wherein the contacting of step (b) is performed in the presence of a high boiling point hydrocarbon solvent in addition to said hydrogen, to produce one or more fuel range hydrocarbon products and excess hydrocarbon solvent.
19. The process of claim 18 , wherein the high boiling point hydrocarbon solvent is selected from the group consisting of diesel oil, atmospheric gas oil, vacuum gas oil, cracked stock gas oils such as light cycle oil, heavy cycle oil, fluid catalytic cracking decant oil, coker gas oil, thermal cracking distillate, visbreaking distillate, other refinery stream comprising predominantly C11-C25 hydrocarbons and any mixtures thereof.
20. The process of claim 18 , wherein the excess hydrocarbon solvent is separated from the one or more fuel range hydrocarbons product and recycled as at least a portion of the high boiling point hydrocarbon solvent used in step (b).