# US 2013/0152454 A1 · Methods for deoxygenating biomass-derived pyrolysis oil > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2013/0152454 A1 - Document ID: US20130152454A1 - Status: Published application - Kind: A1 - Application number: 13/326,050 - Filed: 2011-12-14 - Published: 2013-06-20 - Earliest claimed: 2011-12-14 - Assignees: Uop LLC - Inventors: Lance Awender Baird; Timothy A. Brandvold; Francis Stephen Lupton - Web page: https://patentgrep.com/patent/US20130152454A1 ## CPC - C10G 3/42: {Catalytic treatment} - C10G 3/50: {in the presence of hydrogen, hydrogen donors or hydrogen generating compounds} - C10G 3/45: {containing iron group metals or compounds thereof} - C10G 2300/1011: Biomass - C10G 2300/4006: Temperature - C10G 2300/4081: Recycling aspects - Y02E 50/10: Biofuels, e.g. bio-diesel - Y02P 30/20: using bio-feedstock - C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES - Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS ## Abstract Methods for deoxygenating a biomass-derived pyrolysis oil are provided. In an embodiment, a method for deoxygenating a biomass-derived pyrolysis oil comprises the steps of combining a biomass-derived pyrolysis oil stream with a heated low-oxygen-pyoil diluent recycle stream to form a heated diluted pyoil feed stream. The heated diluted pyoil feed stream has a feed temperature of about 150° C. or greater. The heated diluted pyoil feed stream is contacted with a first deoxygenating catalyst in the presence of hydrogen at first hydroprocessing conditions effective to form a low-oxygen biomass-derived pyrolysis oil effluent. ## Claims ### Claim 1 A method for deoxygenating a biomass-derived pyrolysis oil, the method comprising the steps of: combining a biomass-derived pyrolysis oil stream with a heated low-oxygen-pyoil diluent recycle stream to form a heated diluted pyoil feed stream that has a feed temperature of about 150° C. or greater; and contacting the heated diluted pyoil feed stream with a first deoxygenating catalyst in the presence of hydrogen at first hydroprocessing conditions effective to form a low-oxygen biomass-derived pyrolysis oil effluent. ### Claim 2 (depends on 1) The method of claim 1, wherein the step of contacting comprises contacting the heated diluted pyoil feed stream with the first deoxygenating catalyst at the first hydroprocessing conditions that include a reaction temperature of about the feed temperature. ### Claim 3 (depends on 1) The method of claim 1, wherein the step of contacting comprises contacting the heated diluted pyoil feed stream with the first deoxygenating catalyst at the first hydroprocessing conditions that include a reaction temperature of from about 150 to about 400° C. ### Claim 4 (depends on 1) The method of claim 1, wherein the step of combining comprises forming the heated diluted pyoil feed stream at the feed temperature of from about 150 to about 400° C. ### Claim 5 (depends on 1) The method of claim 1, wherein the step of combining comprises introducing the heated low-oxygen-pyoil diluent recycle stream to the biomass-derived pyrolysis oil stream that has a temperature of from about 15 to about 100° C. ### Claim 6 (depends on 1) The method of claim 1, wherein the step of combining comprises introducing the heated low-oxygen-pyoil diluent recycle stream that has a temperature of from about 200 to about 450° C. to the biomass-derived pyrolysis oil stream. ### Claim 7 (depends on 1) The method of claim 1, wherein the step of combining comprises combining the biomass-derived pyrolysis oil stream with the heated low-oxygen-pyoil diluent recycle stream at a predetermined recycle ratio of from about 1:1 to about 10:1, wherein the predetermined recycle ratio is defined by a recycle mass flow rate of the heated low-oxygen-pyoil diluent recycle stream to a pyoil mass flow rate of the biomass-derived pyrolysis oil stream. ### Claim 8 (depends on 1) The method of claim 1, wherein the step of contacting comprises contacting the first deoxygenating catalyst with the heated diluted pyoil feed stream at the first hydroprocessing conditions that include a reactor pressure of from about 2 to about 20 MPa gauge. ### Claim 9 (depends on 1) The method of claim 1, wherein the step of contacting comprises contacting the first deoxygenating catalyst with the heated diluted pyoil feed stream at the first hydroprocessing conditions that include a liquid hourly space velocity on a basis of volume of the biomass-derived pyrolysis oil stream per volume of catalyst of from about 0.5 to about 1 hr−1. ### Claim 10 (depends on 1) The method of claim 1, wherein the step of contacting comprises partially deoxygenating the heated diluted pyoil feed stream to form the low-oxygen biomass-derived pyrolysis oil effluent that comprises a hydroprocessed organic phase that has a residual oxygen content of from about 5 to about 25 wt. % of the hydroprocessed organic phase. ### Claim 11 (depends on 1) The method of claim 1, wherein the step of contacting comprises partially deoxygenating the heated diluted pyoil feed stream to form the low-oxygen biomass-derived pyrolysis oil effluent that comprises a hydroprocessed organic phase that has a residual oxygen content of from about 5 to about 15 wt. % of the hydroprocessed organic phase. ### Claim 12 (depends on 1) The method of claim 1, wherein the step of contacting comprises contacting the heated diluted pyoil feed stream with the first deoxygenating catalyst by a residence time of about 60 seconds or less, wherein the residence time is defined by a time from when the biomass-derived pyrolysis oil stream is combined with the heated low-oxygen-pyoil diluent recycle stream to when the heated diluted pyoil feed stream initially contacts the first deoxygenating catalyst. ### Claim 13 (depends on 1) The method of claim 1, further comprising the steps of: removing water from and separating the low-oxygen biomass-derived pyrolysis oil effluent to form a water-depleted low-oxygen-pyoil recycle stream; and advancing and heating the water-depleted low-oxygen-pyoil recycle stream to replenish the heated low-oxygen-pyoil diluent recycle stream. ### Claim 14 (depends on 1) The method of claim 1, further comprising the steps of: removing water from and separating the low-oxygen biomass-derived pyrolysis oil effluent to form a water-depleted low-oxygen-pyoil intermediate stream; and contacting the water-depleted low-oxygen-pyoil intermediate stream with a second deoxygenating catalyst in the presence of hydrogen at second hydroprocessing conditions effective to form an ultralow-oxygen biomass-derived pyrolysis oil effluent. ### Claim 15 (depends on 14) The method of claim 14, wherein the step of contacting the water-depleted low-oxygen-pyoil intermediate stream comprises forming the ultralow-oxygen biomass-derived pyrolysis oil effluent that comprises a second hydroprocessed organic phase that has a residual oxygen content of about 1 wt. % or less of the second hydroprocessed organic phase. ### Claim 16 A method for deoxygenating a biomass-derived pyrolysis oil, the method comprising the steps of: combining a biomass-derived pyrolysis oil stream that has an initial temperature of about 100° C. or less with a heated low-oxygen-pyoil diluent recycle stream to form a heated diluted pyoil feed stream that has a feed temperature of about 150° C. or greater; and introducing the heated diluted pyoil feed stream to a hydroprocessing reactor that contains a deoxygenating catalyst in the presence of hydrogen including contacting the heated diluted pyoil feed stream with the deoxygenating catalyst at hydroprocessing conditions that include a reaction temperature of about the feed temperature effective to partially deoxygenate the heated diluted pyoil feed stream and form a low-oxygen biomass-derived pyrolysis oil effluent. ### Claim 17 (depends on 16) The method of claim 16, wherein the step of introducing comprises contacting the heated diluted pyoil feed stream with the deoxygenating catalyst by a residence time of about 60 seconds or less, wherein the residence time is defined by a time from when the biomass-derived pyrolysis oil stream is combined with the heated low-oxygen-pyoil diluent recycle stream to when the heated diluted pyoil feed stream initially contacts the deoxygenating catalyst. ### Claim 18 (depends on 16) The method of claim 16, further comprising the steps of: introducing the low-oxygen biomass-derived pyrolysis oil effluent to a separation zone to remove water from and separate the low-oxygen biomass-derived pyrolysis oil effluent to form a water-depleted low-oxygen-pyoil recycle stream; and advancing the water-depleted low-oxygen-pyoil recycle stream through a heater to heat the water-depleted low-oxygen-pyoil recycle stream to a recycle temperature of from about 200 to about 450° C. to replenish the heated low-oxygen-pyoil diluent recycle stream. ### Claim 19 A method for deoxygenating a biomass-derived pyrolysis oil, the method comprising the steps of: combining a biomass-derived pyrolysis oil stream with a heated low-oxygen-pyoil diluent recycle stream to form a heated diluted pyoil feed stream that has a feed temperature of about 150° C. or greater, wherein the biomass-derived pyrolysis oil stream comprises a first organic phase that has a first residual oxygen content of about 10 wt. % or greater of the first organic phase, and wherein the heated low-oxygen-pyoil diluent recycle stream comprises a second hydroprocessed organic phase that has a second residual oxygen content of from about 5 to about 25 wt. % of the second hydroprocessed organic phase; and introducing the heated diluted pyoil feed stream to a first hydroprocessing reactor that contains a first deoxygenating catalyst in the presence of hydrogen at first hydroprocessing conditions effective to partially deoxygenate the heated diluted pyoil feed stream and form a low-oxygen biomass-derived pyrolysis oil effluent that comprises a third hydroprocessed organic phase that has a third residual oxygen content of from about 5 to about 25 wt. % of the third hydroprocessed organic phase. ### Claim 20 (depends on 19) The method of claim 19, further comprising the steps of: removing water from and separating the low-oxygen biomass-derived pyrolysis oil effluent to form a water-depleted low-oxygen-pyoil intermediate stream; and introducing the water-depleted low-oxygen-pyoil intermediate stream to a second hydroprocessing reactor that contains a second deoxygenating catalyst in the presence of hydrogen at second hydroprocessing conditions effective to deoxygenate the water-depleted low-oxygen-pyoil intermediate stream and form an ultralow-oxygen biomass-derived pyrolysis oil effluent that comprises a fourth hydroprocessed organic phase that has a fourth residual oxygen content of about 1 wt. % or less of the fourth hydroprocessed organic phase.