# US 2013/0158329 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 2013/0158329 A1 - Document ID: US20130158329A1 - Status: Published application - Kind: A1 - Application number: 13/326,059 - Filed: 2011-12-14 - Published: 2013-06-20 - Earliest claimed: 2011-12-14 - Assignees: Uop LLC - Inventors: Timothy A. Brandvold - Web page: https://patentgrep.com/patent/US20130158329A1 ## 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 2300/44: Solvents - C10G 2300/802: Diluents - 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 comprises the steps of diluting the biomass-derived pyrolysis oil with a phenolic-containing diluent to form a diluted pyoil-phenolic feed. The diluted pyoil-phenolic feed is contacted with a deoxygenating catalyst in the presence of hydrogen at 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: diluting the biomass-derived pyrolysis oil with a phenolic-containing diluent to form a diluted pyoil-phenolic feed; and contacting the diluted pyoil-phenolic feed with a deoxygenating catalyst in the presence of hydrogen at 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 diluting comprises diluting the biomass-derived pyrolysis oil with the phenolic-containing diluent that comprises phenolic compounds present in an amount of about 25 wt. % or greater of the phenolic-containing diluent. ### Claim 3 (depends on 1) The method of claim 1, wherein the step of diluting comprises diluting the biomass-derived pyrolysis oil with the phenolic-containing diluent that comprises phenolic compounds present in an amount of from about 50 to about 100 wt. % of the phenolic-containing diluent. ### Claim 4 (depends on 1) The method of claim 1, wherein the step of diluting comprises forming the diluted pyoil-phenolic feed comprising the biomass-derived pyrolysis oil that is present in an amount of from about 10 to about 90 wt. % of the diluted pyoil-phenolic feed. ### Claim 5 (depends on 1) The method of claim 1, wherein the step of diluting comprises diluting the biomass-derived pyrolysis oil with the phenolic-containing diluent that comprises a phenolic mixture derived from a biorenewable source including wood creosote. ### Claim 6 (depends on 1) The method of claim 1, wherein the step of diluting comprises diluting the biomass-derived pyrolysis oil with the phenolic-containing diluent that comprises phenol, methylphenol, tert-butylphenol, trimethylphenol, dimethylphenol, dimethoxyphenol, cyclopentylphenol, ethylphenol, ethyl-methylphenol, methoxyphenol, methoxy-propylphenol, methyl-isopropylphenol, propylphenol, methyl-propylphenol, ethyl-methoxyphenol, methoxy-propenylphenol, dimethoxy-propenylphenol, or combinations thereof. ### Claim 7 (depends on 1) The method of claim 1, wherein the step of diluting comprises diluting the biomass-derived pyrolysis oil with the phenolic-containing diluent that comprises phenol, methylphenol, trimethylphenol, dimethylphenol, ethylphenol, ethyl-methylphenol, or combinations thereof. ### Claim 8 (depends on 1) The method of claim 1, wherein the step of contacting comprises contacting the diluted pyoil-phenolic feed at the hydroprocessing conditions that include a reactor temperature of from about 150 to about 500° C. ### Claim 9 (depends on 1) The method of claim 1, wherein the step of contacting comprises contacting the diluted pyoil-phenolic feed at the hydroprocessing conditions that include a reactor pressure of from about 2.76 to about 20.7 MPa gauge. ### Claim 10 (depends on 1) The method of claim 1, further comprising the step of: separating and recycling a phenolic-containing portion from the low-oxygen biomass-derived pyrolysis oil effluent to form at least a portion of the phenolic-containing diluent. ### Claim 11 A method for deoxygenating a biomass-derived pyrolysis oil, the method comprising the steps of: combining a pyoil-containing stream that comprises the biomass-derived pyrolysis oil with a phenolic-containing diluent at a predetermined diluent ratio to form a diluted pyoil-phenolic feed stream, wherein the predetermined diluent ratio is defined by a diluent mass flow rate of the phenolic-containing diluent to a pyoil mass flow rate of the pyoil-containing stream; and introducing the diluted pyoil-phenolic feed stream and a hydrogen-containing gas stream to a reactor that contains a deoxygenating catalyst and that is operating at hydroprocessing conditions effective to form a low-oxygen biomass-derived pyrolysis oil effluent. ### Claim 12 (depends on 11) The method of claim 11, wherein the step of combining comprises combining the pyoil-containing stream with the phenolic-containing diluent at the predetermined diluent ratio of from about 1:10 to about 10:1. ### Claim 13 (depends on 11) The method of claim 11, wherein the step of combining comprises combining the pyoil-containing stream with the phenolic-containing diluent that comprises a phenolic-containing diluent fresh feed stream. ### Claim 14 (depends on 11) The method of claim 11, wherein the step of introducing comprises introducing the hydrogen-containing gas stream to the reactor such that the hydroprocessing conditions include a hydrogen-containing gas treat rate of from about 175 to about 2,700 SL H2/L feed. ### Claim 15 (depends on 11) The method of claim 11, wherein the step of introducing comprises introducing the diluted pyoil-phenolic feed stream to the reactor such that the hydroprocessing conditions include a liquid hourly space velocity on a basis of volume of the biomass-derived pyrolysis oil per volume of catalyst of from about 0.1 to about 1 hr−1. ### Claim 16 (depends on 11) The method of claim 11, wherein the step of combining comprises introducing the pyoil-containing stream that has a temperature of from about 15 to about 50° C. to the phenolic-containing diluent. ### Claim 17 (depends on 11) The method of claim 11, wherein the step of combining comprises introducing the pyoil-containing stream to the phenolic-containing diluent that has a temperature of from about 50 to about 150° C. ### Claim 18 (depends on 11) The method of claim 11, further comprising the steps of: introducing the low-oxygen biomass-derived pyrolysis oil effluent to a separation zone to separate a phenolic-containing portion from the low-oxygen biomass-derived pyrolysis oil effluent; and recycling the phenolic-containing portion to form at least a portion of the phenolic-containing diluent. ### Claim 19 (depends on 18) The method of claim 18, wherein the step of introducing the low-oxygen biomass-derived pyrolysis oil effluent comprises removing water. ### Claim 20 A method for deoxygenating a biomass-derived pyrolysis oil, the method comprising the steps of: separating a phenolic-containing diluent recycle stream from a low-oxygen biomass-derived pyrolysis oil effluent that was formed in a reactor that contains a deoxygenating catalyst and that is operating at hydroprocessing conditions effective for hydroprocessing the biomass-derived pyrolysis oil in the presence of hydrogen; combining the phenolic-containing diluent recycle stream with a pyoil-containing stream that comprises the biomass-derived pyrolysis oil at a predetermined recycle ratio to form a diluted pyoil-phenolic feed stream, wherein the predetermined recycle ratio is defined by a recycle diluent mass flow rate of the phenolic-containing diluent recycle stream to a pyoil mass flow rate of the pyoil-containing stream, wherein the predetermined recycle ratio is from about 1:10 to about 10:1; and introducing a hydrogen-containing gas stream and the diluted pyoil-phenolic feed stream to the reactor.