# US 8,735,637 B2 · Conversion of crude tall oil to renewable feedstock for diesel range fuel compositions > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,735,637 B2 - Document ID: US8735637B2 - Status: Granted - Kind: B2 - Application number: 12/937,762 - Filed: 2009-03-31 - Published: 2011-03-03 - Granted: 2014-05-27 - Earliest claimed: 2008-04-21 - Assignees: Sunpine AB - Applicants: Lars Stigsson; Valeri Naydenov - Inventors: Lars Stigsson; Valeri Naydenov - Web page: https://patentgrep.com/patent/US8735637B2 ## CPC - C11C 3/12: by hydrogenation - C10L 1/026: {for compression ignition} - C11B 3/04: with acids - C11B 3/10: by adsorption - C11B 3/12: by distillation - C11B 13/005: {of residues of the fabrication of wood-cellulose (in particular tall-oil)} - C10G 2300/1014: of vegetal origin - C10G 2400/04: Diesel oil - Y02E 50/10: Biofuels, e.g. bio-diesel - Y02P 30/20: using bio-feedstock - Y02W 30/74: Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes - C11C: FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM - C10L: FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS - C11B: PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES (drying-oils C09F) - 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 - Y02W: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT ## Abstract A method for converting crude tall oil into high quality diesel fuels include the steps of (a) removal of non-oil contaminants present in the crude tall oil and recovery of valuable organic, (b) heating and removing the volatile fractions of the refined tall oil stream from step (a) and forming a volatiles free oil stream comprising organic components with boiling points of 170° C. and higher, (c) vacuum distilling the volatiles free oil stream of from step (b) to produce a first and second stream the first stream including components with boiling points between 170-400° C. and the second stream comprising components having boiling points greater than 400° C. and (d) passing the first stream into a catalytic reactor wherein hydrogenation and deoxygenation take place to produce a diesel range fuel depleted in oxygen. ## Claims ### Claim 1 Method for conversion of crude tall oil into a renewable diesel fuel composition by a sequence of reaction and separation steps wherein the method comprises the steps of: a) removal of non-oil contaminants present in the crude tall oil and recovering valuable organic compounds present in the crude tall oil, thereby forming a refined tall oil stream; b) removal of the volatile fraction of the refined tall oil stream from step a), thereby forming a volatiles free oil stream comprising organic components with boiling points, at atmospheric pressure, of 170° C. or higher; c) separation in a vacuum distillation system, said system comprising a vacuum distillation column and a thin-film evaporator, of the volatiles free oil stream of step b) into at least two process streams or phases wherein a first process stream or phase is substantially comprising components with boiling points, at atmospheric pressure, in the range of 170-400° C. and a second process stream or phase is substantially comprising components with boiling points, at atmospheric pressure, over 400° C.; d) directly or indirectly passing components from the first process stream or phase of step c) through a catalytic bed comprising a deoxygenation catalyst at elevated temperature, thereby forming a diesel range fuel depleted in oxygen. ### Claim 2 Method for conversion of crude tall oil into a renewable diesel fuel composition by a sequence of separation steps wherein the method comprises the steps of: b) removal of non-oil contaminants including the volatile fraction present in the crude tall oil, thereby forming a volatiles free oil stream comprising organic components with boiling points, at atmospheric pressure, of 170° C. or higher; c) separation in a vacuum distillation system, said system comprising a vacuum distillation column and a thin-film evaporator, of the volatiles free oil stream of step b) into at least two process streams or phases wherein a first process stream or phase is substantially comprising components with boiling points, at atmospheric pressure, in the range of 170-400° C. and a second process stream or phase is substantially comprising components with boiling points, at atmospheric pressure, over 400° C.; d) directly or indirectly passing components from the first process stream or phase of step c) through a catalytic bed comprising a deoxygenation catalyst at elevated temperature, thereby forming a diesel range fuel depleted in oxygen. ### Claim 3 (depends on 1, 2) Method according to claim 1 or 2, wherein in step c) the first process stream or phase substantially comprising components with boiling points, at atmospheric pressure, in the range of 170-400° C. is discharged from the vacuum distillation column and the second process stream or phase substantially comprising components with boiling points, at atmospheric pressure, over 400° C. is discharged from the thin-film evaporator. ### Claim 4 (depends on 1) Method according to claim 1, wherein the vacuum distillation column in step c) is connected to, or the vacuum distillation system in step c) comprises, a reboiler arrangement comprising one or more reboilers which reboilers supplies heat for distillation in the vacuum distillation column and heat for vaporization of tall oil components in the thin film evaporator. ### Claim 5 (depends on 1) Method according to claim 1, wherein step a) is achieved by washing crude tall oil with sulfuric acid, phosphoric acid or a mixture thereof. ### Claim 6 (depends on 1) Method according to claim 1, wherein step a) is achieved by treatment of crude tall oil in a fixed bed reactor containing heterogeneous system selected from acidic clays, minerals, zeolites, acid modified inorganic supports, ion exchange resins, chelating resins, poly-functional resins and mixtures thereof. ### Claim 7 (depends on 1) Method according to claim 1, wherein step a) is achieved by filtration of crude tall oil, ultra-filtration, centrifugation or a combination thereof. ### Claim 8 (depends on 1) Method according to claim 1, wherein volatiles including water is removed from the tall oil in step b) by a heating and flashing arrangement. ### Claim 9 (depends on 1) Method according to claim 1, wherein the tall oil volatiles present within the refined tall oil are removed in at least one expansion vessel that follows a heat-exchanging unit. ### Claim 10 (depends on 1) Method according to claim 1, wherein the tall oil volatiles present within the refined tall oil are removed in at least one stripping unit during step b). ### Claim 11 (depends on 1) Method according to claim 1, wherein tall oil volatiles in step b) are removed in a vessel operated at moderate vacuum, preferably in the range of 500-800 mbar. ### Claim 12 (depends on 1) Method according to claim 1, wherein a vacuum distillation column comprises a bed of at least one structured packing. ### Claim 13 (depends on 1) Method according to claim 1, wherein a distillation column for the separation in step c) is equipped with a reflux configuration near its column top end. ### Claim 14 (depends on 1) Method according to claim 1, wherein the high end sharpness of the stream comprised of components with boiling points 170-400° C. is improved by the selection of a suitable reflux ratio. ### Claim 15 (depends on 1) Method according to claim 1, wherein the homogeneity of the reflux stream entering back to a column within step c) is achieved by auxiliary structured packing. ### Claim 16 (depends on 1) Method according to claim 1, wherein a distillation column for separation in step c) is equipped with a reboiler arrangement near its column bottom end. ### Claim 17 (depends on 1) Method according to claim 1, wherein the temperature profile of the distillation column for separation in step c) is controlled by management of a forced circulation heat exchanging. ### Claim 18 (depends on 1) Method according to claim 1, wherein deoxygenation in step d) is effected at elevated temperatures of 150-350° C. ### Claim 19 (depends on 1) Method according to claim 1, wherein deoxygenation in step d) is performed in the presence of hydrogen gas in a petroleum refinery. ### Claim 20 (depends on 1) Method according to claim 1, wherein deoxygenation in step d) is effected at elevated temperatures of 150-350° C. in the presence of hydrogen gas. ### Claim 21 (depends on 1) Method according to claim 1, wherein at least one catalyst is used in step d) to promote deoxygenation and in that said at least one catalyst is chosen from the group consisting of activated alumina, zirconia, Fuller earths, alkali and alkali-earth carbonates, supported transition metals, zeolites, alkali and alkali-earth exchanged zeolite catalysts and mixtures thereof. ### Claim 22 (depends on 1) Method according to claim 1, wherein an oxygen depleted stream or phase obtained in step d) is further treated over a catalyst system comprising at least one hydrogenation and desulphurization catalyst to obtain low sulfur diesel range automotive fuel composition. ### Claim 23 Method for conversion of crude tall oil into a renewable diesel fuel composition by a sequence of reaction and separation steps comprising the steps of: a) removal of non-oil contaminants present in the crude tall oil and recovering valuable organic compounds present in the crude tall oil, thereby forming a refined tall oil stream; b) removal of the volatile fraction of the refined tall oil stream from step a), thereby forming a volatiles free oil stream comprising organic components with boiling points, at atmospheric pressure, of 170° C. or higher; c) separation in a vacuum distillation column of the volatiles free oil stream of step b) into two process streams or phases wherein a first process stream or phase is substantially comprising components with boiling points, at atmospheric pressure, in the range of 170-400° C. and a second process stream or phase is substantially comprising components with boiling points, at atmospheric pressure, over 400° C.; d) passing the first process stream or phase substantially comprising components with boiling points, at atmospheric pressure, in the range of 170-400° C. through a catalytic bed comprised of deoxygenation catalyst at elevated temperature, thereby forming a diesel range fuel depleted in oxygen.