Pyrolysis oil upgrading to gasoline range liquids
View Patent ↗Described is a method for converting biomass derived pyrolysis oil (bio-oil) into materials that will be more useful for transportation fuels including the following two steps: 1) solubilizing and extracting bio-oil oxygenates, and 2) zeolite catalyzed hydrogenation of the oxygenates into renewable fuel range materials.
1. A method to convert biomass derived pyrolysis oil into fuel range hydrocarbons comprising:
a) providing a bio-oil feedstream comprising pyrolyzed biomass,
b) mixing the bio-oil feedstream with an aqueous feedstream,
c) separating an aqueous extract comprising oxygenates from the bio-oil feedstream and aqueous feedstream mixture,
d) reacting the aqueous extract with hydrogen in the presence of a catalyst to generate a stabilized aqueous extract, and
e) reacting the aqueous extract with a hydrogen donor feedstream in the presence of a zeolite catalyst to generate a renewable fuel comprising hydrocarbons.
2. The method of claim 1 , wherein said pyrolysis oil is selected from the group consisting of a pyrolysis product of plant fiber, lignins, wood, wood byproducts, miscanthus, switchgrass, hemp, corn, poplar, willow, sorghum, sugarcane, tree byproducts, leaves, eucalyptus, palm, pulping liquor, paper, plant byproducts, plant oils, plant solids, grasses, agricultural byproducts, yard-waste, garbage, municipal waste, biologically derived manufacturing waste, animal byproducts, animal waste, bacterial solids, algal solids and combinations thereof.
3. The method of claim 1 , wherein said aqueous feedstream comprises a member of the group consisting of de-ionized water, tap water, filtered water, salt water, brackish water, acidic water, basic water, pH neutral water, buffered water, waste water, heated water, chilled water, process water and combinations thereof.
4. The method of claim 1 , wherein said aqueous extract is modified in a manner comprising at least one of dehydrated, diluted, pH balanced, buffered, pre-treated and combinations thereof, prior to reacting the stabilized aqueous feedstream with the hydrogen donor.
5. The method of claim 1 , wherein the hydrogenation catalyst is selected from the group consisting of ruthenium on carbon, platinum on silica-alumina, and supported or unsupported nickel.
6. The method of claim 1 , wherein said hydrogen donor comprises a hydrocarbon selected from the group consisting of methane, ethane, propane, butane, pentane, hexane, octane, methanol, ethanol, propanol, isopropanol and combinations thereof.
7. The method of claim 1 , wherein said hydrogenation catalyst comprises a metal selected from platinum, palladium, ruthenium, rhenium, nickel, cobalt, molybdenum, tungsten, copper, zinc, and combinations thereof.
8. The method of claim 1 , wherein said hydrogenation catalyst comprises a member of the group consisting of silica, alumina, silica-alumina, carbon, ceria, titania, zeolite and combinations thereof.
9. The method of claim 1 , wherein said catalyst comprises a zeolite catalyst selected from the group consisting of ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-35, ZSM-38 and combinations thereof.
10. The method of claim 1 , wherein said zeolite catalyst is modified by a member of the group consisting of zinc, phosphorous, boron and combinations thereof.
11. The method of claim 1 , wherein said renewable fuel is selected from a member of the group consisting of light gases, gasoline range hydrocarbons, diesel range hydrocarbons, light oils, vacuum oil, kerosene, jet fuel, naphthenes, paraffins and mixtures thereof.
12. A system to convert biomass derived pyrolysis oil (bio-oil) into fuel range hydrocarbons comprising:
a) a bio-oil feedstream comprising pyrolyzed biomass,
b) an aqueous feedstream,
c) a mixer/separator configured to receive and mix the bio-oil feedstream and the aqueous feedstream then separate an aqueous extract comprising oxygenates,
d) a first reactor operatively connected to the mixer/separator and configured to receive the aqueous extract, the first reactor containing a hydrogenation catalyst and configured to stabilize the aqueous extract via mild hydrogenation to produce a stabilized aqueous extract,
e) a second reactor that is operatively connected to receive the stabilized aqueous extract from the first reactor, the second reactor containing a zeolite catalyst and configured to react the stabilized aqueous extract and a hydrogen donor with the zeolite catalyst to generate a renewable fuel comprising hydrocarbons.
13. The system of claim 12 , wherein said bio-oil comprises a member of the group consisting of the pyrolysis product of plant fiber, lignins, wood, wood byproducts, miscanthus, switchgrass, hemp, corn, poplar, willow, sorghum, sugarcane, tree byproducts, leaves, eucalyptus, palm, pulping liquor, paper, plant byproducts, plant oils, plant solids, grasses, agricultural byproducts, yard-waste, garbage, municipal waste, biologically derived manufacturing waste, animal byproducts, animal waste, bacterial solids, algal solids, and combinations thereof.
14. The system of claim 12 , wherein said aqueous feedstream comprises a member of the group consisting of de-ionized water, tap water, filtered water, salt water, brackish water, acidic water, basic water, pH neutral water, buffered water, waste water, heated water, chilled water, process water, and combinations thereof.
15. The system of claim 12 , wherein the hydrogenation catalyst comprises a member of the group consisting of ruthenium on carbon, platinum on silica-alumina, and supported or unsupported nickel.
16. The system of claim 12 , wherein said hydrogen donor comprises a hydrocarbon selected from the group consisting of methane, ethane, propane, butane, pentane, hexane, octane, methanol, ethanol, propanol, isopropanol, and combinations thereof.
17. The system of claim 12 , wherein said hydrogenation catalyst comprises a metal selected from the group consisting of platinum, palladium, ruthenium, rhenium, nickel, cobalt, molybdenum, tungsten, copper, zinc and combinations thereof.
18. The system of claim 12 , wherein said hydrotreating catalyst comprises a support selected from the group consisting of silica, alumina, silica-alumina, carbon, ceria, titania, zeolite and combinations thereof.
19. The system of claim 12 , wherein said zeolite catalyst comprises a member selected from the group consisting of ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-35, ZSM-38 and combinations thereof.
20. The system of claim 12 , wherein said zeolite catalyst is modified by a member selected from the list consisting of zinc, phosphorous, boron and combinations thereof.
21. The system of claim 12 , wherein said renewable fuel comprises a member selected from the group consisting of light gases, gasoline range hydrocarbons, diesel range hydrocarbons, light oils, vacuum oil, kerosene, jet fuel, naphthenes, paraffins, and mixtures thereof.