Process for production of hydrocarbon fuels

Abstract

Provided is a continuous process for producing hydrocarbon products, such as jet fuel, diesel, and naphtha, from lignin-derived materials via hydrodeoxygenation in presence of catalysts under hydrogen pressure. The process comprises introducing a lignin-derived material into a feedstock stream; hydrodeoxygenating said feedstock stream in a first reactor to produce a partially hydrodeoxygenated intermediate; separating gaseous and aqueous by-products from said partially hydrodeoxygenated intermediate to obtain an organic intermediate; hydroprocessing said organic intermediate in a second reactor to produce a hydroprocessed product, said hydroprocessing comprising hydrodeoxygenation and hydrogenation; separating gaseous by-products and aqueous phase by-products from said hydroprocessed product to produce a hydrocarbon product; and fractionating said hydrocarbon product into fuels such as naphtha, jet fuel, or diesel.

Description

PROCESS FOR PRODUCTION OF HYDROCARBON FUELSCROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to US Provisional Patent Application No. 63 / 524,083, entitled “PRODUCTION OF HYDROCARBON FUELS FOR TRANSPORTATION APPLICATIONS FROM LIGNIN-DERIVED MATERIALS”, filed on June 29, 2023, the entire disclosure of which is hereby incorporated by reference.TECHNICAL FIELD

[0002] The present invention relates to the production of lignin-derived hydrocarbon products. More specifically, the present invention relates to a process for producing one or more hydrocarbon fuels, such as jet fuel, diesel, or naphtha, from lignin- derived materials.BACKGROUND

[0003] The transportation sector is a major contributor to CO2 emissions, which cause climate change. Major efforts are required to reach net zero carbon emissions by 2050. Although electrification of light-duty vehicles is feasible and is in progress, the aviation, long-haul trucking, rail, and marine sectors are hard to electrify.

[0004] One potential solution to reduce the carbon footprint of hard-to-electrify transportation sectors is in the use of sustainable biofuels. Preferably, the process for generating the sustainable biofuels should have a low carbon intensity. Generating sustainable biofuels using biogenic carbon-containing raw materials, especially if the sustainable biofuels can be directly substituted for currently used fossil fuels, would greatly assist in the decarbonisation of hard-to-electrify transportation sectors.

[0005] One such biogenic carbon-containing raw material is lignin. Lignin is a major constituent of lignocellulosic biomass, along with cellulose and hemicellulose. Lignin is a by-product at pulp and paper mills, at cellulosic ethanol production facilities and from biomass fractionation processes. Accordingly, lignin is an abundant and sustainable resource for producing biofuels and bioproducts.

[0006] There is therefore a need for systems and processes that generate sustainable hydrocarbon products, such as sustainable jet fuel, renewable diesel, and renewable naphtha. Preferably, these products are directly substitutable for fossil fuels (i.e., drop-in biofuels).SUMMARY

[0007] This document discloses a two-stage continuous flow process for producing hydrocarbon products, such as sustainable jet fuel, renewable diesel, and renewable naphtha, from lignin-derived materials. The lignin-derived materials may comprise pyrolytic lignin, lignin bio-oil, lignin biocrude, or a combination thereof. The process uses a two-stage reactor system, comprising a first and second reactor in series, for hydrodeoxygenation and hydroprocessing to convert the lignin-derived materials into hydrocarbon products. These hydrocarbon products can then be fractionated into fuels such as naphtha, jet fuel, or diesel. Preferably, these fuels meet transportation fuel specifications. Because lignin-derived materials are produced from lignocellulosic biomass, the hydrocarbon products, including sustainable jet fuel, renewable diesel, and naphtha produced by this process, can contain up to 100% biogenic carbon.

[0008] In a first aspect, this document discloses a two-stage process for producing hydrocarbon products comprising naphtha, jet fuel, and diesel fuel, said process comprising: (a) providing a lignin-derived material as a feedstock; (b) dispersing or mixing said lignin-derived material in a recycled stream from a first-stage reactor, or dispersing or mixing said lignin-derived material in a refinery stream, vegetable oils, or used cooking oils, or dissolving said lignin-derived material in a solvent, or pumping said lignin-derived material directly, thereby forming a first-stage feedstock stream; (c) hydrodeoxygenating said feedstock stream in a first reactor by contacting it with gaseous hydrogen in the presence of a first-stage hydrodeoxygenation catalystto produce a partially hydrodeoxygenated intermediate product that exits said first reactor; (d) separating gaseous and aqueous by-products from said partially hydrodeoxygenated intermediate to thereby obtain an organic intermediate; (e) hydroprocessing said organic intermediate in a second reactor by contacting it with gaseous hydrogen in the presence of a second-stage catalyst to produce a hydroprocessed product that exits said second reactor; said hydroprocessing comprising hydrodeoxygenation and hydrogenation; (f) separating gaseous byproducts and aqueous phase by-products from said hydroprocessed product to thereby produce said hydrocarbon products; and (g) fractionating said hydrocarbon product to thereby obtain naphtha, jet fuel, and diesel fuel.

[0009] In a second aspect, this document discloses a process for producing one or more hydrocarbon fuels, said process comprising: (a) providing a lignin-derived material as a feedstock; (b) introducing said feedstock into a feedstock stream; (c) hydrodeoxygenating said feedstock stream in a first reactor by contacting said feedstock stream with gaseous hydrogen in the presence of a first catalyst to thereby produce a partially hydrodeoxygenated intermediate that exits said first reactor; (d) separating gaseous and aqueous by-products from said partially hydrodeoxygenated intermediate to thereby obtain an organic intermediate; (e) hydroprocessing said organic intermediate in a second reactor by contacting said organic intermediate with gaseous hydrogen in the presence of a second catalyst to thereby produce a hydroprocessed product that exits said second reactor; said hydroprocessing comprising hydrodeoxygenation and hydrogenation; (f) separating gaseous byproducts and aqueous phase by-products from said hydroprocessed product to thereby produce a hydrocarbon product; and (g) fractionating said hydrocarbon product to obtain said one or more hydrocarbon fuels.

[0010] The present invention may be implemented such that the lignin-derived materials comprise: (a) pyrolytic lignin; (b) lignin bio-oil; (c) lignin biocrude; or (d) a combination thereof.

[0011] The present invention may be implemented such that said pyrolytic lignin has an oxygen content in the range of about 5 wt% to about 40 wt%, said lignin bio-oil has an oxygen content in the range of about 5 wt% to about 50 wt%, or said lignin biocrude has an oxygen content in the range of about 5 wt% to about 30 wt%.

[0012] In a third aspect, this document discloses a process for producing one or more hydrocarbon fuels, said process comprising: (a) providing a lignin-derived material as a feedstock; (b) introducing said feedstock into a feedstock stream; (c) hydrodeoxygenating said feedstock stream in a first reactor by contacting said feedstock stream with gaseous hydrogen in the presence of a first catalyst to thereby produce a partially hydrodeoxygenated intermediate that exits said first reactor; (d) separating gaseous and aqueous by-products from said partially hydrodeoxygenated intermediate to thereby obtain an organic intermediate; (e) hydroprocessing said organic intermediate in a second reactor by contacting said organic intermediate with gaseous hydrogen in the presence of a second catalyst to thereby produce a hydroprocessed product that exits said second reactor; said hydroprocessing comprising hydrodeoxygenation and hydrogenation; (f) separating gaseous byproducts and aqueous phase by-products from said hydroprocessed product to thereby produce a hydrocarbon product; and (g) fractionating said hydrocarbon product to obtain said one or more hydrocarbon fuels wherein said first reactor and said second reactor are continuous reactors.

[0013] The present invention may be implemented such that said lignin-derived material comprises at least one of: pyrolytic lignin; (b) lignin bio-oil; or (c) lignin biocrude.

[0014] The present invention may be implemented such that said pyrolytic lignin has an oxygen content in the range of about 5 wt% to about 40 wt%, wherein said lignin bio-oil has an oxygen content in the range of about 5 wt% to about 50 wt%, or wherein said lignin biocrude has an oxygen content in the range of about 5 wt% to about 30 wt%.

[0015] The present invention may be implemented such that step (b) comprises one of: dispersing said feedstock in at least one of: a recycled stream of said organic intermediate from said first continuous reactor or in an input stream, said input stream comprising at least one of a refinery stream, a vegetable oil stream, or a used- cooking-oil stream; dissolving said feedstock in a solvent; or when said lignin- derived material is a liquid: introducing said lignin-derived material directly into said feedstock stream; or mixing said lignin-derived material with said recycled stream or said input stream.

[0016] The present invention may be implemented such that said refinery stream comprises at least one of: naphtha, kerosene, gas oil, vacuum distillate, fuel oil #2, light cycle oil (LCO), vacuum gas oil (VGO), middle distillates, or a blend thereof.

[0017] The present invention may be implemented such that when said feedstock is dissolved in said solvent, said solvent comprises at least one of: 2-methoxyphenol, ethyl acetate, methanol, ethanol, propanol, butanol, or a blend thereof.

[0018] The present invention may be implemented such that said first catalyst is a metal catalyst, said metal catalyst comprising at least one metal, said at least one metal being selected from at least one of Group VIB elements or Group VIIIB elements.

[0019] The present invention may be implemented such that said Group VIB element is at least one of molybdenum or tungsten and wherein said Group VIIIB element is at least one of iron, cobalt, nickel, ruthenium, rhodium, palladium, or platinum.

[0020] The present invention may be implemented such that said first catalyst comprises at least one of metal sulphides, metal carbides, metal nitrides, or metal phosphides.

[0021] The present invention may be implemented such that first catalyst is supported on a catalyst support comprising at least one of: silicon dioxide, aluminum oxide, zirconium oxide, cerium oxide, titanium oxide, magnesium oxide, barium oxide, lanthanum oxide, activated carbon, magnesium aluminate spinel, or zeolites.

[0022] The present invention may be implemented such that said second catalyst is a metal catalyst, said metal catalyst comprising at least one metal, said at least one metal being selected from at least one of Group VIB elements or Group VIIIB elements.

[0023] The present invention may be implemented such that Group VIB element is at least one of molybdenum or tungsten and wherein said Group VIIIB element is at least one of: iron, cobalt, nickel, ruthenium, rhodium, palladium, or platinum.

[0024] The present invention may be implemented such that said second catalyst comprises at least one of: metal sulphides, metal carbides, metal nitrides, or metal phosphides.

[0025] The present invention may be implemented such that said second catalyst is supported on a catalyst support comprising at least one of: silicon dioxide, aluminumoxide, zirconium oxide, cerium oxide, titanium oxide, magnesium oxide, barium oxide, lanthanum oxide, activated carbon, magnesium aluminate spinel, or zeolites

[0026] The present invention may be implemented such that said first continuous reactor is one of: a fixed-bed reactor, a slurry reactor, or an ebullated-bed reactor.

[0027] The present invention may be implemented such that said second continuous reactor is one of: a fixed-bed reactor, a slurry reactor, or an ebullated-bed reactor.

[0028] The present invention may be implemented such that said first catalyst comprises one of: at least one Group VIB metal, the at least one Group VIB metal having a metal loading range of about 4 wt% to about 40 wt%; at least one non-noble Group VIIIB metal, the at least one non-noble Group VIIIB metal having a metal loading range of about 4 wt% to about 40 wt%; at least one Group VIB metal and at least one non-noble Group VIIIB metal, wherein the total metal loading range is about 4 wt% to about 40 wt%; at least one noble Group VIIIB metal, the at least one noble Group VIIIB metal having a metal loading range of about 0. 1 wt% to about 6 wt%; or at least one noble Group VIIIB metal and at least one non-noble Group VIIIB metal, wherein the metal loading range of the at least one noble Group VIIIB metal is about 0. 1 wt% to about 6 wt% and wherein the metal loading range of the at least one non- noble Group VIIIB metal is about 4 wt% to about 40 wt%, and wherein said first catalyst is suitable for hydrodeoxygenating said feedstock stream to thereby produce said partially hydrodeoxygenated intermediate.

[0029] The present invention may be implemented such that said second catalyst comprises one of: at least one Group VIB metal, the at least one Group VIB metal having a metal loading range of about 4 wt% to about 40 wt%; at least one non-noble Group VIIIB metal, the at least one non-noble Group VIIIB metal having a metal loading range of about 4 wt% to about 40 wt%; at least one Group VIB metal and at least one non-noble Group VIIIB metal, wherein the total metal loading range is about 4 wt% to about 40 wt%; at least one noble Group VIIIB metal, the at least one noble Group VIIIB metal having a metal loading range of about 0. 1 wt% to about 6 wt%; or at least one noble Group VIIIB metal and at least one non-noble Group VIIIB metal, wherein the metal loading range of the at least one noble Group VIIIB metal is about 0. 1 wt% to about 6 wt% and wherein the metal loading range of the at least one non-noble Group VIIIB metal is about 4 wt% to about 40 wt%, and wherein said second catalyst is suitable for hydrodeoxygenating said organic intermediate to thereby produce said hydrodeoxygenated product.

[0030] The present invention may be implemented such that each of said step (c) and said step (e) are conducted under operating conditions comprising: a temperature in the range of about 350 °C to about 450 °C; and a hydrogen gauge pressure in the range of about 6 MPa to about 18 MPa.

[0031] The present invention may be implemented such that said fractionating in said step (g) comprises fractionating by distillation of said hydrocarbon product to thereby produce at least one of jet fuel, diesel, or naphtha.BRIEF DESCRIPTION OF THE DRAWINGS

[0032] The present invention will now be described by reference to the following figures, in which identical reference numerals refer to identical elements and in which:Figure 1 is a diagram of an embodiment of the method of the present invention; andFigure 2 is a schematic diagram of the overall process that originates with lignin- derived material, passes through the organic intermediate, the hydrocarbon product, and produces hydrocarbon fuels comprising naphtha, jet fuel, and diesel products.DETAILED DESCRIPTION

[0033] In one aspect, the present invention relates to the production of one or more hydrocarbon fuels from lignin-derived materials. Such lignin-derived materials may comprise pyrolytic lignin, lignin bio-oil, and / or lignin biocrude. The lignin-derived material is used as a feedstock for a first continuous reactor having a first catalyst. Hydrodeoxygenating the feedstock in the first continuous reactor produces an organic intermediate that is then used in the second reactor. The organic intermediate is fed to a second continuous reactor system that completes further hydrodeoxygenation and hydrogenation. This produces a hydrocarbon product thatis then fractionated into the one or hydrocarbon fuels, such as naphtha, jet fuel, and diesel.

[0034] In one implementation, the lignin-derived material is from different lignin sources. For example, lignin can be taken from the waste product stream of a pulp and paper mill (i.e., black liquor) or the waste product stream of a cellulosic ethanol plant or from other biomass fractionation process. Such lignin can then be made into a lignin-derived material. Referring to Figure 1, the lignin-derived material 101 may comprise: (a) pyrolytic lignin, which is a water-insoluble fraction extracted from oils produced by the pyrolysis of lignocellulosic biomass; (b) lignin bio-oil, which is produced by the pyrolysis of lignin separated from lignocellulosic biomass; (c) lignin biocrude, which is produced by the hydrothermal liquefaction of lignin separated from lignocellulosic biomass; or (d) mixtures of the above materials.

[0035] Preferably, pyrolytic lignin has an oxygen content in the range of about 5 wt% and about 40 wt% oxygen. Preferably, lignin bio-oil has an oxygen content in the range of about 5 wt% to about 50 wt%. Preferably, lignin biocrude has an oxygen content in the range of about 5 wt% to about 30 wt%.

[0036] The lignin-derived material 101 is then placed into a feedstock stream 103. To form the feedstock stream 103, the lignin-derived material 101 can be dissolved in a solvent 102. Alternatively, the lignin-derived material 101 can be combined with a recycled stream 121 from the first reactor 104. In a further embodiment, the lignin- derived material can be combined with an input stream 122, such as a refinery stream, a stream comprising vegetable oils, or a stream comprising used cooking oils to form the feedstock stream 103. It should be clear that, when the lignin-derived material 101 is a liquid, the lignin-derived material 101 can be directly introduced as the feedstock stream 103 into the first reactor 104, or may be mixed with the recycled stream 121 or input stream 122.

[0037] In an embodiment where the lignin-derived material 101 is a solid and is used without the solvent 102, the lignin-derived material 101 can be dispersed into the recycled stream 121 or input stream 122 to thereby form the feedstock stream 103. In an embodiment where the lignin-derived material 101 is a liquid, the lignin- derived material 101 can form the feedstock stream 103 and thus can be pumpeddirectly into the first reactor 104. In a further embodiment where the lignin-derived material 101 is a liquid, the lignin-derived material may be mixed with the recycled stream 121 or input stream 122 to thereby form the feedstock stream 103.

[0038] In some embodiments, the refinery stream may comprise a typical refinery stream (e.g., naphtha, kerosene, middle distillate, gas oil, or vacuum distillate) or blends of such streams. Preferably, the refinery stream is at least one of: fuel oil #2, light cycle oil (LCO), vacuum gas oil (VGO), or middle distillates.

[0039] In embodiments in which a solvent 102 is used, the solvent 102 may comprise at least one of 2-methoxyphenol, ethyl acetate, methanol, ethanol, propanol, or butanol, or may be a combination of suitable solvents. To be clear, the solvent 102 is optional and the lignin-derived material 101 may form a slurry. It should be clear that a person of skill in the art would understand how to operate with such a slurry.

[0040] In a first stage, the feedstock stream 103 is fed to a first continuous reactor 104, where the feedstock stream 103 is contacted with gaseous hydrogen in the presence of a first catalyst 105 for hydrodeoxygenation. Hydrodeoxygenation is a reaction characterized by the removal of oxygen from oxygenated hydrocarbons by reacting such oxygenated hydrocarbons with hydrogen in the presence of a catalyst. In some embodiments, the first continuous reactor 104 is a fixed-bed reactor that is packed with the first catalyst 105. In yet further embodiments, the first continuous reactor 104 is a slurry reactor or an ebullated-bed reactor loaded with the first catalyst 105.

[0041] The hydrodeoxygenation reaction can be simplified as:CxHyOz + z H2 —> z H2O + CxHy

[0042] This hydrodeoxygenation reaction proceeds as the feedstock stream 103 is pumped through the first continuous reactor 104. As resulting liquid products exit the first continuous reactor 104, gaseous by-products 106 separate from liquid products 107. The liquid products 107 then undergo phase separation and aqueous byproducts 108 are removed, thereby leaving an organic intermediate 109. It should be understood that the organic intermediate 109 may comprise a mixture of organic compounds.

[0043] The organic intermediate 109 has many properties showing the transformation of the lignin-derived material 101 to a partially hydrodeoxygenated product. Notably, theorganic intermediate 109 is a liquid with significantly less water and oxygen than the original lignin-derived material 101.

[0044] Part of the organic intermediate 109 may be recycled back to disperse lignin-derived material 101 in the recycled stream 121.

[0045] The organic intermediate 109 is then fed to a second continuous reactor 111, where the organic intermediate 109 is contacted with gaseous hydrogen in the presence of a second catalyst 112 for hydrodeoxygenation.

[0046] As with the first continuous reactor 104, in some embodiments, the second continuous reactor 111 is either a fixed-bed reactor that is packed with the second catalyst 112 or a slurry reactor or an ebullated-bed reactor loaded with the second catalyst 112. The organic intermediate 109 undergoes further hydrodeoxygenation and hydrogenation in the second continuous reactor 111.

[0047] As the organic intermediate 109 passes through the second continuous reactor 111 and undergoes further hydrodeoxygenation and hydrogenation, a hydrodeoxygenated product 113 is generated. As the hydrodeoxygenated product 113 exits the second continuous reactor 111, second-stage gaseous by-products 110 separate from the hydrodeoxygenated product 113. In embodiments where a second-stage aqueous phase 114 is present in the hydrodeoxygenated product 113, the liquid products undergo phase separation and the second-stage aqueous phase 114 is removed. The removal of second-stage gaseous by-products 110 and, if present, second-stage aqueous phase 114, from the hydrodeoxygenated product 113 thus leaves a hydrocarbon product 115. It should be understood that the hydrocarbon product 115 may comprise multiple hydrocarbon compounds.

[0048] Various types of catalysts may be used as the first catalyst 105 and as the second catalyst 112. For example, supported or unsupported metal catalysts can be used. The metals in these metal catalysts may be Group VIB or Group VIIIB metals (i.e., are elements that are classified in Group VIB or Group VIIIB of the periodic table). Supported or unsupported metal sulphides, carbides, nitrides, or phosphides may also be used as catalysts. Supported catalysts may be supported on materials such as silicon dioxide, aluminum oxide, zirconium oxide, cerium oxide, titanium oxide, magnesium oxide, barium oxide, lanthanum oxide, activated carbon, magnesiumaluminate spinel, zeolites, or combinations of these materials. The catalysts may be promoted, or may be unpromoted.

[0049] In some embodiments, the first catalyst 105 and second catalyst 112 are metal catalysts that comprise Group VIB (e.g, molybdenum or tungsten) and / or non-noble (e.g, iron, cobalt, or nickel) Group VIIIB metals. Such catalysts have a total metal loading ranging from about 4 wt% to about 40 wt%.

[0050] In further embodiments, the first catalyst 105 and second catalyst 112 are metal catalysts that comprise at least one noble Group VIIIB metal (e.g, ruthenium, rhodium, palladium, or platinum). Such catalysts have a total metal loading ranging from about 0.1 wt% to about 6 wt%. It should be clear that a combination of (a) at least one non-noble Group VIIIB metal and (b) at least one noble Group VIIIB metal, can be used in one, or both, of the first catalyst 105 and the second catalyst 112. In an embodiment where both noble and non-noble Group VIIIB metals are present (e.g, platinum-iron), the noble Group VIIIB metals have a total metal loading range from 0.1 wt% to 6 wt% and the non-noble Group VIIIB metals have a total metal loading ranging from 4 wt% to 40 wt%.

[0051] Regarding the operating conditions for the reactions in the first reactor 104 and second reactor 111, a wide range of operating conditions may be used. Preferably, the first reactor 104 and the second reactor 111 are continuous reactors. The temperature in the first reactor 104 and the second reactor 111 should be at least about 350 °C, and preferably at least 370 °C. The normal optimum operating temperature is in the range of about 370 °C to about 450 °C. The hydrogen pressure can vary quite widely and is preferably in the range of about 6 MPa to about 18 MPa.

[0052] Once the hydrocarbon product 115 has been obtained, this hydrocarbon product is fractionated into different hydrocarbon fuels. In a preferred embodiment, the fractionation can be performed using vacuum distillation 116. The process that takes the lignin-derived material 101 to the various hydrocarbon fuels is schematically illustrated in Figure 2.

[0053] The fractionation process will produce fractions with boiling points corresponding to the one or more hydrocarbon fuels. For example, fractionation of the hydrocarbon product 115 produces naphtha 117, jet fuel 118, and heavy middle distillates 119.

[0054] Preferably, the naphtha 117, jet fuel 118, and diesel 120 (i.e., combined jet fuel 118 and heavy middle distillates 119) obtained from the above process meet established standards for the relevant fuel product. By meeting such standards, these products can preferably be used as “drop-in” biofuels that require no further treatment before they can be used as a fuel in existing systems. Such drop-in fuels can also be blended with conventional petroleum-derived fuels to reduce the carbon intensity of the fossil fuels.

[0055] It should be clear that there are a number of fuel standards that, preferably, the resulting fuels adhere to. Such fuel standards include: the ASTM™ D7566-22 specification for jet fuel, published August 2, 2022, and accessible at https: / / www.astm.org / d7566-22.html; the ASTM™ D975-21 specification for diesel, published October 20, 2021, and accessible at https: / / www.astm.org / d0975-21.html; the CAN / CGSB™-3.23-2020 specification for jet fuel, published October 2020, and accessible at https: / / publications.gc.ca / collections / collection 2021 / ongc-cgsb / P29- 003-023-2020-l-eng.pdf; the CAN / CGSB™-3.517-2020 specification for diesel, published February 2020 and accessible at https: / / publications.gc. ca / site / eng / 9,884942 / publication.html; the CAN / CGSB™-3.5-2021 specification for gasoline, published October 2021 and accessible at https: / / publications.gc.ca / collections / collection 2021 / ongc-cgsb / P29- 003-005-2021-eng.pdf; and the CAN / CGSB™-3.27-2018 specification for naphtha fuel, published 2018 and accessible at https: / / publications.gc.ca / collections / collection 2018 / ongc-cgsb / P29- 003-027-2018-eng.pdf.

[0056] The above references are hereby incorporated by reference in their entirety.

[0057] In a further aspect, this document discloses a two-stage continuous process for producing hydrocarbon products including naphtha 117, jet fuel 118, and diesel 120. The process first provides a lignin-derived material 101 as a feedstock. The lignin- derived material 101 may then be dispersed in a recycled stream 121 from a first continuous reactor 104, dispersed in an input stream 122, or dissolved in a solvent 102, all of which then form a feedstock stream 103. When the lignin-derivedmaterial 101 is a liquid, the lignin-derived material 101 can form the feedstock stream 103 and thus can be pumped directly into the first reactor 104. In a further embodiment where the lignin-derived material 101 is a liquid, the lignin-derived material may be mixed with the recycled stream 121 or input stream 122 to thereby form the feedstock stream 103.

[0058] The lignin-derived material 101 may comprise: (a) pyrolytic lignin, which is a waterinsoluble fraction extracted from oils produced by the pyrolysis of lignocellulosic biomass; (b) lignin bio-oil, which is produced by the pyrolysis of lignin separated from lignocellulosic biomass; (c) lignin biocrude, which is produced by the hydrothermal liquefaction of lignin separated from lignocellulosic biomass; or (d) mixtures of the above materials.

[0059] The feedstock stream 103 may then be hydrodeoxygenated in a first continuous reactor 104 by contacting the feedstock stream 103 with gaseous hydrogen in the presence of a first catalyst 105 to produce a partially hydrodeoxygenated intermediate that exits the first continuous reactor 104. Gaseous by-products 106 and aqueous by-products 108 may then be separated from the partially hydrodeoxygenated intermediate to thereby obtain an organic intermediate 109.

[0060] Further, the organic intermediate 109 may then be hydrodeoxygenated and / or hydrogenated in a second continuous reactor 111 by contacting the organic intermediate 109 with gaseous hydrogen in the presence of a second catalyst 112 to produce the hydrodeoxygenated product 113 that exits the second continuous reactor 111

[0061] Second-stage gaseous byproducts 110 and, if present, a second-stage aqueous phase 114 may then be separated from the hydrodeoxygenated product 113 to thereby produce the hydrocarbon product 115, which may then be fractionated to thereby obtain naphtha 117, jet fuel 118, and diesel fuel 120.

[0062] The present invention may be implemented such that the lignin-derived material 101 is dispersed in the recycled stream 121 of the organic intermediate 109 from the first continuous reactor 104. Alternatively or additionally, the lignin-derived material 101 may be dispersed in the input stream 122, which may comprise at least one typical refinery stream (e.g, naphtha, kerosene, middle distillate, gas oil, or vacuumdistillate), a recycled stream 121, a stream comprising vegetable oils, a stream comprising used cooking oils, or blends of such streams. Preferably, the refinery stream 122 comprises at least one of: fuel oil #2, light cycle oil (LCO), vacuum gas oil (VGO), middle distillates, or a blend thereof. As an alternative to dispersing the lignin-derived material in the recycled stream 121 and / or the input stream 122, the lignin-derived material 101 may be dissolved in the solvent 102, which may comprise at least one of: 2-methoxyphenol, ethyl acetate, methanol, ethanol, propanol, butanol, or a blend thereof. In a further embodiment, if the lignin-derived material 101 is a liquid, the lignin-derived material 101 can form the feedstock stream 103 and thus can be pumped directly into the first reactor 104. In a further embodiment where the lignin-derived material 101 is a liquid, the lignin-derived material may be mixed with the recycled stream 121 or input stream 122 to thereby form the feedstock stream 103.

[0063] The present invention may be implemented such that the first catalyst 105 is a supported or unsupported metal catalyst, the metal being selected from Group VIB or Group VIIIB elements on the periodic table, or combinations thereof. The Group VIB metal may be at least one of molybdenum or tungsten. The Group VIIIB metal may be at least one of iron, cobalt, nickel, ruthenium, rhodium, palladium, platinum, or combinations thereof. The first catalyst 105 may be a supported or unsupported catalyst comprising metal sulphides, metal carbides, metal nitrides, or metal phosphides. If the first catalyst 105 is a supported catalyst, it may be supported on a catalyst support, such as a catalyst support comprising silicon dioxide, aluminum oxide, zirconium oxide, cerium oxide, titanium oxide, magnesium oxide, barium oxide, lanthanum oxide, activated carbon, magnesium aluminate spinel, zeolites, or combinations of these materials. The first catalyst 105 may be promoted or unpromoted.

[0064] The present invention may be implemented such that the second catalyst 112 is a supported or unsupported metal catalyst, the metal being selected from Group VIB or Group VIIIB elements on the periodic table, or combinations thereof. The Group VIB metal may be at least one of molybdenum or tungsten. The Group VIIIB metal may be at least one of iron, cobalt, nickel, ruthenium, rhodium, palladium, platinum, or combinations thereof. The second catalyst 112 may be a supported orunsupported catalyst comprising metal sulphides, metal carbides, metal nitrides, or metal phosphides. If the second catalyst 112 is a supported catalyst, it may be supported on a catalyst support, such as a catalyst support comprising silicon dioxide, aluminum oxide, zirconium oxide, cerium oxide, titanium oxide, magnesium oxide, barium oxide, lanthanum oxide, activated carbon, magnesium aluminate spinel, zeolites, or combinations of these materials. The second catalyst 112 may be promoted or unpromoted.

[0065] For clarity, the second catalyst 112 may have the same or different properties from the first catalyst 105.

[0066] The present invention may be implemented such that the first continuous reactor 104 is one of: a fixed-bed reactor that is packed with the first catalyst 105, a slurry reactor that is loaded with the first catalyst 105, or an ebullated-bed reactor loaded with the first catalyst 105. It should be understood that a slurry reactor would be loaded with an unsupported first catalyst 105, while an ebullated-bed reactor would be loaded with a supported first catalyst 105.

[0067] The present invention may be implemented such that the second continuous reactor 111 is one of: a fixed-bed reactor that is packed with the second catalyst 112, a slurry reactor that is loaded with the second catalyst 112, or an ebullated-bed reactor loaded with the second catalyst 112. It should be understood that a slurry reactor would be loaded with an unsupported second catalyst 112, while an ebullated-bed reactor would be loaded with a supported second catalyst 112.

[0068] For clarity, the first continuous reactor 104 and the second continuous reactor 111 may be of the same type or may be of a different type from one another.

[0069] The present invention may be implemented such that the metal of the first catalyst 105 is at least one Group VIB metal, the first catalyst 105 having a total metal loading ranging from about 4 wt% to about 40 wt%.

[0070] The present invention may be implemented such that the metal of the first catalyst 105 is at least one non-noble Group VIIIB metal, the first catalyst 105 having a total metal loading ranging from about 4 wt% to about 40 wt%.

[0071] The present invention may be implemented such that the metal of the first catalyst 105 comprises at least one Group VIB metal and at least one non-noble Group VIIIB metal, the first catalyst 105 having a total metal loading ranging from about 4 wt% to about 40 wt%.

[0072] The present invention may be implemented such that the metal of the first catalyst 105 is at least one noble Group VIIIB metal, the first catalyst 105 having a total metal loading between about 0. 1 wt% and about 6 wt%.

[0073] The present invention may be implemented such that the first catalyst 105 has a first metal, the first metal being a non-noble Group VIIIB metal, and the first catalyst 105 having a metal loading ranging from about 4 wt% to about 40 wt% of the first metal. In this implementation, the first catalyst 105 may also have a second metal, the second metal being a noble Group VIIIB metal, and the first catalyst 105 having a metal loading ranging from about 0. 1 wt% to about 6 wt% of the second metal.

[0074] The present invention may be implemented such that the metal of the second catalyst 112 is at least one Group VIB metal, the second catalyst 112 having a total metal loading ranging from about 4 wt% to about 40 wt%.

[0075] The present invention may be implemented such that the metal of the second catalyst 112 is at least one non-noble Group VIIIB metal, the second catalyst 112 having a total metal loading ranging from about 4 wt% to about 40 wt%.

[0076] The present invention may be implemented such that the metal of the second catalyst 112 comprises at least one Group VIB metal and at least one non-noble Group VIIIB metal, the second catalyst 112 having a total metal loading ranging from about 4 wt% to about 40 wt%.

[0077] The present invention may be implemented such that the metal of the second catalyst 112 is at least one noble Group VIIIB metal, the second catalyst 112 having a total metal loading between about 0. 1 wt% and about 6 wt%.

[0078] The present invention may be implemented such that the second catalyst 112 has a first metal, the first metal being a non-noble Group VIIIB metal, and the second catalyst 112 having a metal loading ranging from about 4 wt% to about 40 wt% of the first metal. In this implementation, the second catalyst 112 may also have asecond metal, the second metal being a noble Group VIIIB metal, and the second catalyst 112 having a metal loading ranging from about 0. 1 wt% to about 6 wt% of the second metal.

[0079] For clarity, the metal composition of the first catalyst 105 and the second catalyst 112 may be the same or different. Further, the metal loading of the first catalyst 105 and the second catalyst 112 may be the same or different.

[0080] The present invention may be implemented such that the first continuous reactor 104 is operated at conditions comprising: a temperature in the range of about 350 °C to 450 °C; and a hydrogen gauge pressure in the range of about 6 MPa to about 18 MPa.

[0081] The present invention may be implemented such that the second continuous reactor 111 is operated at conditions comprising: a temperature in the range of about 350 °C to 450 °C; and a hydrogen gauge pressure in the range of about 6 MPa to about 18 MPa.

[0082] For clarity, the first continuous reactor 104 and the second continuous reactor 111 may be operated at the same or different temperatures. The first continuous reactor 104 and the second continuous reactor 111 may also be operated at the same or different hydrogen gauge pressures.

[0083] The present invention may be implemented such that the hydrocarbon product 115 is fractionated by distillation to thereby produce jet fuel 118, diesel 120 and naphtha 117 that may contain up to 100% biogenic carbon. The jet fuel 118 may be a renewable fuel that meets or exceeds key ASTM™ D7566 specifications and CAN / CGSB™-3.323-2020 specifications. The diesel 120 may be a renewable fuel that meets or exceeds key ASTM™ D975 specifications and CAN / CGSB™-3.517- 2020 specifications. The naphtha 117 may be a renewable fuel that meets or exceeds key CAN / CGSB™-3.5-2021 specifications.

[0084] The present invention will be further illustrated by means of a non-limiting example.Example 1

[0085] In a first example, lignin-derived material 101 was processed according to an embodiment of the invention.

[0086] Lignin-derived material 101 was first dissolved in a solvent 102 to form the feedstock stream 103. The lignin-derived material 101 comprised pyrolytic lignin, which is a water-insoluble fraction extracted from oils produced by the pyrolysis of lignocellulosic biomass. The pyrolytic lignin had the properties listed in Table 1 prior to processing according to an embodiment of the present invention.Table 1: Properties of pyrolytic lignin

[0087] The feedstock stream 103 was fed into a first continuous reactor 104 having a first packed-bed reactor with a first catalyst 105 comprising a supported platinum catalyst. The first continuous reactor 104 was operated under a hydrogen pressure ranging from about 6.0 MPa to about 18 MPa, at a temperature ranging from about 350 °C to about 450 °C. Organic intermediate 109 was produced after separating the gaseous by-products 106 and aqueous phase 108. The properties of organic intermediate 109 are shown in Table 2. The degree of deoxygenation in the first continuous reactor 104 was 96.3%.Table 2: Properties of organic intermediate 109

[0088] Notably, the sulphur, nitrogen, and oxygen contents of the organic intermediate 109 were significantly reduced relative to the feedstock stream 103. As shown in Table 3, the organic intermediate 109 contained 19.8 wt% naphtha, 37.2 wt% jet fuel and 35.7 wt% heavy middle distillates as classified by boiling point.Table 3: Boiling point distribution of organic intermediate 109

[0089] Based on the properties of organic intermediate 109 as shown in Tables 2 and 3, it should be clear that organic intermediate 109 can be further processed as described above in the second continuous reactor 111 to produce hydrocarbon product 115, which can then be fractionated in accordance with an embodiment of the invention as described above.

[0090] The expression ‘at least one of X and Y’, as used herein, means and should be construed as meaning ‘X, or Y, or both X and Y’.

[0091] The expression “about”, as used herein when referring to a numerical value, means and should be construed as meaning a range formed by that value, plus or minus 10%. For example, “about 100 °C” should be construed as “100 °C ± 10 °C”, that is, “90 °C to 110 °C”.

[0092] A person understanding this invention may now conceive of alternative structures and embodiments or variations of the above, all of which are intended to fall within the scope of the invention as defined in the claims that follow.

Claims

We claim:

1. A process for producing one or more hydrocarbon fuels, said process comprising:(a) providing a lignin-derived material as a feedstock;(b) introducing said feedstock into a feedstock stream;(c) hydrodeoxygenating said feedstock stream in a first reactor by contacting said feedstock stream with gaseous hydrogen in the presence of a first catalyst to thereby produce a partially hydrodeoxygenated intermediate that exits said first reactor;(d) separating gaseous and aqueous by-products from said partially hydrodeoxygenated intermediate to thereby obtain an organic intermediate;(e) hydroprocessing said organic intermediate in a second reactor by contacting said organic intermediate with gaseous hydrogen in the presence of a second catalyst to thereby produce a hydroprocessed product that exits said second reactor; said hydroprocessing comprising hydrodeoxygenation and hydrogenation;(f) separating gaseous by-products and aqueous phase by-products from said hydroprocessed product to thereby produce a hydrocarbon product; and(g) fractionating said hydrocarbon product to obtain said one or more hydrocarbon fuels wherein said first reactor and said second reactor are continuous reactors.

2. The process according to claim 1, wherein said lignin-derived material comprises at least one of: pyrolytic lignin; (b) lignin bio-oil; or (c) lignin biocrude.

3. The process according to claim 2, wherein said pyrolytic lignin has an oxygen content in the range of about 5 wt% to about 40 wt%, wherein said lignin bio-oil has an oxygen content in the range of about 5 wt% to about 50 wt%, or wherein said lignin biocrude has an oxygen content in the range of about 5 wt% to about 30 wt%.

4. The process according to claim 1, wherein step (b) comprises one of: dispersing said feedstock in at least one of: a recycled stream of said organic intermediate from said first continuous reactor or in an input stream, said input stream comprising at least one of a refinery stream, a vegetable oil stream, or a used-cooking-oil stream; dissolving said feedstock in a solvent; or when said lignin-derived material is a liquid: introducing said lignin-derived material directly into said feedstock stream; or mixing said lignin-derived material with said recycled stream or said input stream.

5. The process according to claim 4, wherein said refinery stream comprises at least one of: naphtha, kerosene, gas oil, vacuum distillate, fuel oil #2, light cycle oil (LCO), vacuum gas oil (VGO), middle distillates, or a blend thereof.

6. The process according to claim 4, wherein when said feedstock is dissolved in said solvent, said solvent comprises at least one of: 2-methoxyphenol, ethyl acetate, methanol, ethanol, propanol, butanol, or a blend thereof.

7. The process according to claim 1, wherein said first catalyst is a metal catalyst, said metal catalyst comprising at least one metal, said at least one metal being selected from at least one of Group VIB elements or Group VIIIB elements.

8. The process according to claim 7, wherein said Group VIB element is at least one of molybdenum or tungsten and wherein said Group VIIIB element is at least one of iron, cobalt, nickel, ruthenium, rhodium, palladium, or platinum.

9. The process according to claim 1, said first catalyst comprising at least one of metal sulphides, metal carbides, metal nitrides, or metal phosphides.

10. The process according to claim 1, wherein said first catalyst is supported on a catalyst support comprising at least one of: silicon dioxide, aluminum oxide, zirconium oxide, cerium oxide, titanium oxide, magnesium oxide, barium oxide, lanthanum oxide, activated carbon, magnesium aluminate spinel, or zeolites.

11. The process according to claim 1, wherein said second catalyst is a metal catalyst, said metal catalyst comprising at least one metal, said at least one metal being selected from at least one of Group VIB elements or Group VIIIB elements.

12. The process according to claim 11, wherein said Group VIB element is at least one of molybdenum or tungsten and wherein said Group VIIIB element is at least one of: iron, cobalt, nickel, ruthenium, rhodium, palladium, or platinum.

13. The process according to claim 1, said second catalyst comprising at least one of: metal sulphides, metal carbides, metal nitrides, or metal phosphides.

14. The process according to claim 1, wherein said second catalyst is supported on a catalyst support comprising at least one of: silicon dioxide, aluminum oxide, zirconium oxide, cerium oxide, titanium oxide, magnesium oxide, barium oxide, lanthanum oxide, activated carbon, magnesium aluminate spinel, or zeolites15. The process according to claim 1, wherein said first continuous reactor is one of: a fixed-bed reactor, a slurry reactor, or an ebullated-bed reactor.

16. The process according to claim 1, wherein said second continuous reactor is one of: a fixed- bed reactor, a slurry reactor, or an ebullated-bed reactor.

17. The process according to claim 1, wherein said first catalyst comprises one of: at least one Group VIB metal, the at least one Group VIB metal having a metal loading range of about 4 wt% to about 40 wt%; at least one non-noble Group VIIIB metal, the at least one non-noble Group VIIIB metal having a metal loading range of about 4 wt% to about 40 wt%; at least one Group VIB metal and at least one non-noble Group VIIIB metal, wherein the total metal loading range is about 4 wt% to about 40 wt%; at least one noble Group VIIIB metal, the at least one noble Group VIIIB metal having a metal loading range of about 0.1 wt% to about 6 wt%; or at least one noble Group VIIIB metal and at least one non-noble Group VIIIB metal, wherein the metal loading range of the at least one noble Group VIIIB metal is about 0.1 wt% toabout 6 wt% and wherein the metal loading range of the at least one non-noble Group VIIIB metal is about 4 wt% to about 40 wt%, and wherein said first catalyst is suitable for hydrodeoxygenating said feedstock stream to thereby produce said partially hydrodeoxygenated intermediate.

18. The process according to claim 1, wherein said second catalyst comprises one of: at least one Group VIB metal, the at least one Group VIB metal having a metal loading range of about 4 wt% to about 40 wt%; at least one non-noble Group VIIIB metal, the at least one non-noble Group VIIIB metal having a metal loading range of about 4 wt% to about 40 wt%; at least one Group VIB metal and at least one non-noble Group VIIIB metal, wherein the total metal loading range is about 4 wt% to about 40 wt%; at least one noble Group VIIIB metal, the at least one noble Group VIIIB metal having a metal loading range of about 0. 1 wt% to about 6 wt%; or at least one noble Group VIIIB metal and at least one non-noble Group VIIIB metal, wherein the metal loading range of the at least one noble Group VIIIB metal is about 0.1 wt% to about 6 wt% and wherein the metal loading range of the at least one non-noble Group VIIIB metal is about 4 wt% to about 40 wt%, and wherein said second catalyst is suitable for hydrodeoxygenating said organic intermediate to thereby produce said hydrodeoxygenated product.

19. The process according to claim 1, wherein each of said step (c) and said step (e) are conducted under operating conditions comprising: a temperature in the range of about 350 °C to about 450 °C; and a hydrogen gauge pressure in the range of about 6 MPa to about 18 MPa.

20. The process according to claim 1, wherein said fractionating in said step (g) comprises fractionating by distillation of said hydrocarbon product to thereby produce at least one of jet fuel, diesel, or naphtha.

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