Process and system for converting non-pretreated lipid feedstock into renewable products

Abstract

A process and system for making a renewable product from a non-pretreated lipid feedstock is provided herein. The process comprises hydroprocessing the non-pretreated lipid feedstock with at least one macroporous hydroprocessing catalyst under hydroprocessing conditions to produce the renewable product, where the macroporous hydroprocessing catalyst removes at least one contaminant from the non-pretreated lipid feedstock.

Description

T-12086-W001PROCESS AND SYSTEM FOR CONVERTING NON-PRETREATED LIPID FEEDSTOCK INTO RENEWABLE PRODUCTS CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 760,615, filed February 19, 2025, the disclosure of which is incorporated herein by reference in its entirety.FIELD OF THE DISCLOSURE

[0002] A process and system for converting non-pretreated lipid feedstock into renewable products.BACKGROUND OF THE DISCLOSURE

[0003] The use of renewable resources has garnered significant attention and effort in the drive to develop fossil fuel alternatives. The variety, availability and versatility of various biofeedstocks has been of great interest, particularly certain lipid sources and other carbohydrates, leading to the development and commercial use of a number of bio-based fuel technologies. Ongoing economic interests, and the desire to reduce fossil fuel use, have provided incentives for improvements in existing technologies, and the development of new processes for utilizing renewable feedstocks (e.g., biofeedstocks) to produce renewable fuels and other renewable products.

[0004] Renewable fuels (e.g., biofuels) are seen as being important to reduce carbon and greenhouse emissions. Biofuels derived from food are fuels typically made from food sources produced on arable land, while biofuels derived from non-food sources are typically produced from lignocellulosic biomass like forestry residuals or agricultural residues / waste. Typical biofeedstocks in the food source category include a wide variety of lipids (e.g., vegetable oil, including used cooking oil, seed oils, animal fats, waste oils, and the like).

[0005] There is a need for improved systems and processes for converting biofeedstock into renewable products.

[0006] The background herein is included solely to explain the context of the disclosure. This is not to be taken as an admission that any of the material referred to was published, known, or part of the common general knowledge as of the priority date.SUMMARY OF THE DISCLOSURE

[0007] In one aspect, there is provided a process for making a renewable product from a nonpretreated lipid feedstock, the process comprising: hydroprocessing the non-pretreated lipid feedstock with at least one macroporous hydroprocessing catalyst under hydroprocessingT-12086-W001conditions to produce the renewable product, wherein the macroporous hydroprocessing catalyst removes at least one contaminant from the non-pretreated lipid feedstock.

[0008] In an embodiment, the macroporous hydroprocessing catalyst has a suitable density to provide effective catalyst suspension.

[0009] In an embodiment, the macroporous hydroprocessing catalyst has an average macropore pore size of about 1200 A or greater than about 1200 A.

[0010] In an embodiment, the macroporous hydroprocessing catalyst has a macropore volume at about 0.05 cc / g or greater and a macropore peak greater than about 1000 A.

[0011] In an embodiment, the macroporous hydroprocessing catalyst has a particle density of about 0.95 g / cc or less than about 0.95 g / cc.

[0012] In an embodiment, the non-pretreated lipid feedstock with the macroporous hydroprocessing catalyst forms a first product comprising at least one of less than about 2% oxygen, less than about 30 ppm N, and less than about 20 ppm combined phosphorus and at least one metal contaminant.

[0013] In an embodiment, the macroporous hydroprocessing catalyst removes at least one of greater than about 90% oxygen, greater than about 80% nitrogen, greater than about 99% phosphorus, greater than about 99% of at least one metal.

[0014] In an embodiment, the macroporous hydroprocessing catalyst comprises one or more transition metals selected from Group VIA (Group 6) and Group VIII (Groups 8-10) metals.

[0015] In an embodiment, the macroporous hydroprocessing catalyst comprises one or more transition metals selected from Mo, Fe, W, Co, Ni, Zn, Pt and Pd.

[0016] In an embodiment, the macroporous hydroprocessing catalyst is a self-supported catalyst that comprises at least one catalyst of Mo, MoS2, NiMo, NiS, CoO, MoO3, NiO, and / or a mixture thereof.

[0017] In an embodiment, the macroporous hydroprocessing catalyst comprises a selfsupported MoS2 and NiS catalyst.

[0018] In an embodiment, the macroporous hydroprocessing catalyst further comprises one or more support materials such as zeolite, alumina, silica, alumina-silica, zirconia, alumina-silica-zeolite or activated carbon.

[0019] In an embodiment, the macroporous hydroprocessing catalyst comprises NiMo supported catalysts on alumina.

[0020] In an embodiment, the macroporous hydroprocessing catalyst is a precursor, such as an organo-metal precursor, which can be activated in-situ to form colloidal or nanometer or micron size catalysts.T-12086-W001

[0021] In an embodiment, the macroporous hydroprocessing catalyst is a pre-activated micron-size slurry catalyst.

[0022] In an embodiment, the macroporous hydroprocessing catalyst is selected from a macroporous ebullated (EB) reactor catalyst, a macroporous slurry catalyst, a macroporous upflow reactor catalyst, a macroporous hydrocracking catalyst, or a combination thereof.

[0023] In an embodiment, the macroporous hydroprocessing catalyst has a particle density of less than about 0.95 g / cc, less than about 0.9 g / cc, less than about 0.85 g / cc, less than about 0.8 g / cc, less than about 0.75 g / cc, less than about 0.7 g / cc, less than about 0.65 g / cc, less than about 0.6 g / cc, less than about 0.5 g / cc, less than about 0.4 g / cc, or less than about 0.3 g / cc, about 0.3 to about 0.9 g / cc, about 0.4 to about 0.9 g / cc, about 0.5 to about 0.9 g / cc, about 0.6 to about 0.9 g / cc, or about 0.65 to about 0.9 g / cc

[0024] In an embodiment, the macroporous hydroprocessing catalyst has a macropore peak position that is at about 1200 A or greater than 1200 A, at about 1300 A or greater than 1300 A, at about 1400 A or greater than 1400 A, at about 1500 A or greater than 1500 A, at about 1600 A or greater than 1600 A, at about 1700 A or greater than 1700 A, at about 1800 A or greater than 1800 A, at about 1900 A or greater than 1900 A, at about 2000 A or greater than 2000 A, at about 2100 A or greater than 2100 A, at about 2200 A or greater than 2200 A, at about 2300 A or greater than 2300 A, at about 2400 A or greater than 2400 A, at about 2500 A or greater than 2500 A, at about 2600 A or greater than 2600 A, at about 2700 A or greater than 2700 A, at about 2800 A or greater than 2800 A, at about 2900 A or greater than 2900 A, at about 3000 A or greater than 3000 A, at about 1200 A to about 5000 A, at about 1500 A to about 5000 A, at about 1700 A to about 5000 A, at about 2000 A to about 5000 A, at about 2000 A to about 4000 A, and / or at about 2000 A to about 3000 A.

[0025] In an embodiment, the macroporous hydroprocessing catalyst has a macropore volume of at least 0.01 cc / g, at least about 0.05 cc / g, at least about 0.10 cc / g, at least about 0.20 cc / g, at least about 0.30 cc / g, at least about 0.40 cc / g, at least about 0.50 cc / g, at least about 0.60 cc / g, at least about 0.70 cc / g, at least about 0.80 cc / g, at least about 0.90 cc / g, at least about 1.0 cc / g, at least about 1.1 cc / g, at least about 1.2 cc / g, at least about 1.3 cc / g, at least about 1.4 cc / g, at least about 1.5 cc / g, at least about 1.6 cc / g, at least about 1.7 cc / g, at least about 1.8 cc / g, at least about 1.9 cc / g, about 0.10 to about 2.0 cc / g, about 0.10 to about 1.9 cc / g, about 0.10 to about 1.8 cc / g, about 0.10 to about 1.7 cc / g, about 0.10 to about 1.6 cc / g, about 0.10 to about 1.5 cc / g, about 0.20 to about 1.6 cc / g, about 0.20 to about 1.5 cc / g, or about 0.50 to about 1.5 cc / g.

[0026] In an embodiment, the macroporous hydroprocessing catalyst has a total pore volume of at least about 0.50 cc / g, at least about 0.60 cc / g, at least about 0.70 cc / g, at least about 0.80 g / cc, at least about 0.9 g / cc, at least about 1.0 cc / g, at least about 1.5 cc / g, at least about 2.0 cc / g,T-12086-W001at least about 2.50 cc / g, at least about 3.0 cc / g, about 0.50 to about 3.0 cc / g, about 1.0 to about 3.0 cc / g, about 1.0 to about 2.9 cc / g, about 1.0 to about 2.8 cc / g, about 1.0 to about 2.7 cc / g, about 1.0 to about 2.6 cc / g, about 1.0 to about 2.5 cc / g, or about 1.0 to about 2.5 cc / g.

[0027] In an embodiment, the at least one contaminant in the non-pretreated feedstock is present in an amount of less than about 2000 ppm; less than about 1500 ppm;, less than about 1000 ppm; less than about 900 ppm; less than about 800 ppm; less than about 700 ppm; less than about 600 ppm; less than about 500 ppm; less than about 400 ppm; less than about 300 ppm; less than about 200 ppm; or less than about 100 ppm.

[0028] In an embodiment, the at least one contaminant comprises at least one liquid and / or at least one solid.

[0029] In an embodiment, the at least one contaminant is selected from at least one of nitrogen, phosphorus, and at least one metal.

[0030] In an embodiment, the at least one contaminant is selected from at least one of a Group I, II, and transition metals, optionally, at least one of K, Ca, Mg, Ba, Si, Na, Fe, Si.

[0031] In an embodiment, the hydroprocessing of the non-pretreated lipid feedstock occurs in a first stage comprising at least one reactor.

[0032] In an embodiment, the at least one reactor is selected from an ebullating-bed (EB) reactor, a slurry-bed reactor, and an up-flow reactor (UFR).

[0033] In an embodiment, the at least one contaminant is removed in the first stage via deposition on / impregnation in the catalyst and removing at least a portion of the catalyst from the first stage.

[0034] In an embodiment, the removing of said at least a portion of the catalyst comprises removing the catalyst intermittently.

[0035] In an embodiment, the removing of said at least a portion of the catalyst comprises removing the catalyst via a liquid product.

[0036] In an embodiment, the hydroprocessing comprises at least one of i) heating from about 500 °F to about 800°F; ii) pressure is about 300 psig to about 3000 psig; iii) liquid hourly space velocity (LHSV) at about 0.1 h-1 to about 3.0 h-1; iv) hydrogen-containing gas flow rate of about 2000 SCF / bbl to about 10000 SCF / bbl.

[0037] In an embodiment, the hydroprocessing comprises, in a first stage, at least one of i) heating from about 580 °F to about 780°F; ii) pressure is about 300 psig to about 3000 psig; iii) liquid hourly space velocity (LHSV) at about 0.1 h-1 to about 3.0 h-1; iv) hydrogen-containing gas flow rate of about 2500 SCF / bbl to about 10000 SCF / bbl.

[0038] In an embodiment, the hydroprocessing comprises, in a second stage, at least one of i) heating from about 500 °F to about 800°F; ii) pressure is about 300 psig to about 3000 psig; iii)T-12086-W001liquid hourly space velocity (LHSV) at about 0.1 h-1 to about 3.0 h-1; iv) hydrogen-containing gas flow rate of about 2000 SCF / bbl to about 10000 SCF / bbl.

[0039] In an embodiment, the hydroprocessing further comprises adding a sulfiding agent to maintain a ratio of H2S to the non-pretreated feedstock at about 100 ppm or greater.

[0040] In an embodiment, the hydroprocessing further comprises at least one hydrotreating catalyst.

[0041] In an embodiment, partial conversion of oxygen occurs in the first stage.

[0042] In an embodiment, the process further comprises separating i) gaseous product(s) from ii) liquid(s) and solid(s).

[0043] In an embodiment, the process further comprises substantially separating the liquid(s) from the solid(s) in ii).

[0044] In an embodiment, the process further comprises hydrotreating the liquid(s) from ii).

[0045] In an embodiment, the liquid-solid separation comprises at least one of filtration, centrifuge, electrostatic precipitation, settling, and evaporation.

[0046] In an embodiment, the liquid-solid separation comprises at least one of dead-end filter, cross-flow filter, and filter press.

[0047] In an embodiment, the non-pretreated lipid feedstock comprises plant oil(s).

[0048] In an embodiment, the plant oil(s) comprises greater than about 50 ppm N and greater than about 100 ppm combined phosphorus and at least one metal contaminant.

[0049] In an embodiment, the plant oil(s) are derived from a plant and / or plant seeds that have been pressed and / or extracted.

[0050] In an embodiment, the non-pretreated lipid feedstock comprises triglycerides.

[0051] In an embodiment, the non-pretreated lipid feedstock comprises greater than about 90% triglycerides and has greater than about 5% oxygen.

[0052] In an embodiment, the non-pretreated lipid feedstock further comprises other sources of lipids.

[0053] In an embodiment, the other sources of lipids comprise at least one of animal fats, used cooking oil, waste grease, and a combination thereof.

[0054] In an embodiment, the non-pretreated lipid feedstock comprises plastic pyrolysis-oil.

[0055] In an embodiment, hydroprocessing comprises hydrogenation of the olefins of triglycerides (Tg) to obtain hydrogenated triglycerides (HTg) and the hydrogenated triglycerides are transformed by hydrogenolysis into fatty acids (FA), and waxes.

[0056] In an embodiment, hydroprocessing further comprises hydrodeoxygenation (HDO), decarbonylation (DCO), decarboxylation (DCO2), hydrocracking, isomerization, dehydrogenation, and / or dearomatization.T-12086-W001

[0057] In an embodiment, the hydroprocessing comprises a first and a second stage, the second stage including a fixed-bed reactor.

[0058] In an embodiment, the second stage further comprises at least one catalyst selected from at least one of a hydrotreating catalyst for removing at least one contaminant and an isodewaxing catalyst to improve pour point and cloud point.

[0059] In an embodiment, the second stage has at least three types of catalysts comprising hydrotreating catalyst, a hydrogenation catalyst, and an isomerization catalyst.

[0060] In an embodiment, the second stage has a first layer having the hydrotreating catalyst; a second layer having the hydrogenation catalyst; and a third layer having an isomerization catalyst.

[0061] In an embodiment, the second stage has a first layer having about 5% to about 20% of the hydrotreating catalyst; a second layer having about 3% to about 10% of the hydrogenation catalyst; and a third layer having an isomerization catalyst.

[0062] In an embodiment, the first layer substantially eliminates contaminants, the second layer converts CO to methane and the third layer substantially converts n-paraffins into isoparaffins.

[0063] In an embodiment, product(s) from the first stage comprise liquid product(s) that are fed into the second stage and solid product(s).

[0064] In an embodiment, a portion of the liquid product(s) from the first stage are fed back to the first stage.

[0065] In an embodiment, at least a portion of the solid product(s) is recovered.

[0066] In an embodiment, if the solid product(s) contain macroporous hydroprocessing catalyst, the solid product(s) is washed to remove salt(s) and fed back to the first stage.

[0067] In an embodiment, the washed solid product(s) is added to the non-pretreated lipid feedstock and fed back to the first stage.

[0068] In an embodiment, the process further comprises separating and fractionating to separate gaseous products from renewable products.

[0069] In an embodiment, the hydroprocessing conditions in the first stage comprise first deoxygenation reaction conditions.

[0070] In an embodiment, the hydroprocessing of the non-pretreated lipid feedstock in the first stage comprises at least one of hydrodeoxygenation (HDO), hydrotreating and hydrocracking.

[0071] In an embodiment, the hydroprocessing of the at least partially pretreated lipid feedstock in the first stage comprises an at least partial hydrodeoxygenation of the non-pretreated lipid feedstock.T-12086-W001

[0072] In an embodiment, the at least partial hydrodeoxygenation of the non-pretreated lipid feedstock in the first stage removes at least about 60% of the oxygen from the non-pretreated lipid feedstock.

[0073] In an embodiment, the at least partial hydrodeoxygenation of the non-pretreated lipid feedstock in the first stage produces a partially-deoxygenated intermediate product.

[0074] In an additional embodiment, complete oxygen conversion and removal of contaminants from the at least one intermediate product occurs in the second stage.

[0075] In an embodiment, the at least one macroporous hydroprocessing catalyst comprises at least one macroporous hydrodeoxygenation catalyst.

[0076] In an embodiment, the non-pretreated lipid feedstock is at least partially treated via a physical treatment process.

[0077] In an embodiment, the physical treatment processes comprise at least one of cold pressing, solvent extraction, decanting, and / or filtration.

[0078] According to another aspect, there is provided a system for making a renewable product from a non-pretreated lipid feedstock, the system comprising: a first stage having at least one reactor for hydroprocessing the non-pretreated lipid feedstock with at least one macroporous hydroprocessing catalyst under hydroprocessing conditions to produce the renewable product, wherein the macroporous hydroprocessing catalyst removes at least one contaminant from the non-pretreated lipid feedstock.

[0079] In an embodiment, the at least one reactor is configured for at least partially converting oxygen within the non-pretreated lipid feedstock via the at least one macroporous hydroprocessing catalyst.

[0080] In an embodiment, the system further comprises a second stage having at least one secondary reactor for hydrotreating at least one intermediate product produced in the first stage to complete oxygen conversion and remove contaminants.

[0081] In an embodiment, the at least one reactor of the first stage comprises an ebullating-bed or a slurry-bed reactor.

[0082] In an embodiment, the at least one secondary reactor of the second stage comprises a fixed-bed reactor.

[0083] In an embodiment, the macroporous hydroprocessing catalyst has a suitable density to provide effective catalyst suspension.

[0084] In an embodiment, the macroporous hydroprocessing catalyst has an average macropore pore size of about 1200 A or greater than about 1200 A.

[0085] In an embodiment, the macroporous hydroprocessing catalyst has a macropore volume at about 0.05 cc / g or greater and a macropore peak greater than about 1000 A.T-12086-W001

[0086] In an embodiment, the macroporous hydroprocessing catalyst has a particle density of about 0.95 g / cc or less than about 0.95 g / cc.

[0087] In an embodiment, the non-pretreated lipid feedstock with the macroporous hydroprocessing catalyst forms a first product comprising at least one of less than about 2% oxygen, less than about 30 ppm N, and less than about 20 ppm combined phosphorus and at least one metal contaminant.

[0088] In an embodiment, the macroporous hydroprocessing catalyst removes at least one of greater than about 90% oxygen, greater than about 80% nitrogen, greater than about 99% phosphorus, greater than about 99% of at least one metal.

[0089] In an embodiment, the macroporous hydroprocessing catalyst comprises one or more transition metals selected from Group VIA (Group 6) and Group VIII (Groups 8-10) metals.

[0090] In an embodiment, the macroporous hydroprocessing catalyst comprises one or more transition metals selected from Mo, Fe, W, Co, Ni, Zn, Pt and Pd.

[0091] In an embodiment, the macroporous hydroprocessing catalyst is a self-supported catalyst that comprises at least one catalyst of Mo, MoS2, NiMo, NiS, CoO, MoO3, NiO, and / or a mixture thereof.

[0092] In an embodiment, the macroporous hydroprocessing catalyst comprises a selfsupported MoS2 and NiS catalyst.

[0093] In an embodiment, the macroporous hydroprocessing catalyst further comprises one or more support materials such as zeolite, alumina, silica, alumina-silica, zirconia, alumina-silica-zeolite or activated carbon.

[0094] In an embodiment, the macroporous hydroprocessing catalyst comprises NiMo supported catalysts on alumina.

[0095] In an embodiment, the macroporous hydroprocessing catalyst is a precursor, such as an organo-metal precursor, which can be activated in-situ to form colloidal or nanometer or micron size catalysts.

[0096] In an embodiment, the macroporous hydroprocessing catalyst is a pre-activated micron-size slurry catalyst.

[0097] In an embodiment, the macroporous hydroprocessing catalyst is selected from a macroporous ebullated (EB) reactor catalyst, a macroporous slurry catalyst, a macroporous upflow reactor catalyst, a macroporous hydrocracking catalyst, or a combination thereof.

[0098] In an embodiment, the macroporous hydroprocessing catalyst has a particle density of less than about 0.95 g / cc, less than about 0.9 g / cc, less than about 0.85 g / cc, less than about 0.8 g / cc, less than about 0.75 g / cc, less than about 0.7 g / cc, less than about 0.65 g / cc, less than about 0.6 g / cc, less than about 0.5 g / cc, less than about 0.4 g / cc, or less than about 0.3 g / cc, about 0.3T-12086-W001to about 0.9 g / cc, about 0.4 to about 0.9 g / cc, about 0.5 to about 0.9 g / cc, about 0.6 to about 0.9 g / cc, or about 0.65 to about 0.9 g / cc

[0099] In an embodiment, the macroporous hydroprocessing catalyst has a macropore peak position that is at about 1200 A or greater than 1200 A, at about 1300 A or greater than 1300 A, at about 1400 A or greater than 1400 A, at about 1500 A or greater than 1500 A, at about 1600 A or greater than 1600 A, at about 1700 A or greater than 1700 A, at about 1800 A or greater than 1800 A, at about 1900 A or greater than 1900 A, at about 2000 A or greater than 2000 A, at about 2100 A or greater than 2100 A, at about 2200 A or greater than 2200 A, at about 2300 A or greater than 2300 A, at about 2400 A or greater than 2400 A, at about 2500 A or greater than 2500 A, at about 2600 A or greater than 2600 A, at about 2700 A or greater than 2700 A, at about 2800 A or greater than 2800 A, at about 2900 A or greater than 2900 A, at about 3000 A or greater than 3000 A, at about 1200 A to about 5000 A, at about 1500 A to about 5000 A, at about 1700 A to about 5000 A, at about 2000 A to about 5000 A, at about 2000 A to about 4000 A, and / or at about 2000 A to about 3000 A.

[0100] In an embodiment, the macroporous hydroprocessing catalyst has a macropore volume of at least about 0.05 cc / g, at least about 0.10 cc / g, at least about 0.20 cc / g, at least about 0.30 cc / g, at least about 0.40 cc / g, at least about 0.50 cc / g, at least about 0.60 cc / g, at least about 0.70 cc / g, at least about 0.80 cc / g, at least about 0.90 cc / g, at least about 1.0 cc / g, at least about 1.1 cc / g, at least about 1.2 cc / g, at least about 1.3 cc / g, at least about 1.4 cc / g, at least about 1.5 cc / g, at least about 1.6 cc / g, at least about 1.7 cc / g, at least about 1.8 cc / g, at least about 1.9 cc / g, about 0.10 to about 2.0 cc / g, about 0.10 to about 1.9 cc / g, about 0.10 to about 1.8 cc / g, about 0.10 to about 1.7 cc / g, about 0.10 to about 1.6 cc / g, about 0.10 to about 1.5 cc / g, about 0.20 to about 1.6 cc / g, about 0.20 to about 1.5 cc / g, or about 0.50 to about 1.5 cc / g.

[0101] In an embodiment, the macroporous hydroprocessing catalyst has a total pore volume of at least about 0.50 cc / g, at least about 0.60 cc / g, at least about 0.70 cc / g, at least about 0.80 g / cc, at least about 0.9 g / cc, at least about 1.0 cc / g, at least about 1.5 cc / g, at least about 2.0 cc / g, at least about 2.50 cc / g, at least about 3.0 cc / g, about 0.50 to about 3.0 cc / g, about 1.0 to about 3.0 cc / g, about 1.0 to about 2.9 cc / g, about 1.0 to about 2.8 cc / g, about 1.0 to about 2.7 cc / g, about 1.0 to about 2.6 cc / g, about 1.0 to about 2.5 cc / g, or about 1.0 to about 2.5 cc / g.

[0102] In an embodiment, the at least one contaminant in the non-pretreated feedstock is present in an amount of less than about 2000 ppm; less than about 1500 ppm, less than about 1000 ppm; less than about 900 ppm; less than about 800 ppm; less than about 700 ppm; less than about 600 ppm; less than about 500 ppm; less than about 400 ppm; less than about 300 ppm; less than about 200 ppm; or less than about 100 ppmT-12086-W001

[0103] In an embodiment, the at least one contaminant comprises at least one liquid and / or at least one solid.

[0104] In an embodiment, the at least one contaminant is selected from at least one of nitrogen, phosphorus, and at least one metal.

[0105] In an embodiment, the at least one contaminant is selected from at least one of a Group I, II, and transition metals, optionally, at least one of K, Ca, Mg, Ba, Si, Na, Fe, Si.

[0106] In an embodiment, the at least one reactor is selected from an ebullating-bed (EB) reactor, a slurry-bed reactor, and an up-flow reactor (UFR).

[0107] In an embodiment, the at least one contaminant is removed in the first stage via deposition on or impregnation in the catalyst and removing at least a portion of the catalyst from the first stage.

[0108] In an embodiment, a portion of the catalyst is removed periodically.

[0109] In an embodiment, a portion of the catalyst is removed in a liquid product.

[0110] In an embodiment, the hydroprocessing comprises at least one of i) heating from about 500 °F to about 800°F; ii) pressure is about 300 psig to about 3000 psig; iii) liquid hourly space velocity (LHSV) at about 0.1 h-1 to about 3.0 h-1; iv) hydrogen-containing gas flow rate of about 2000 SCF / bbl to about 10000 SCF / bbl.

[0111] In an embodiment, the hydroprocessing in the first stage comprises at least one of i) heating from about 580 °F to about 780°F; ii) pressure is about 300 psig to about 3000 psig; iii) liquid hourly space velocity (LHSV) at about 0.1 h-1 to about 3.0 h-1; iv) hydrogen-containing gas flow rate of about 2500 SCF / bbl to about 10000 SCF / bbl.

[0112] In an embodiment, the hydroprocessing in the second stage comprises at least one of i) heating from about 500 °F to about 800°F; ii) pressure is about 300 psig to about 3000 psig; iii) liquid hourly space velocity (LHSV) at about 0.1 h-1 to about 3.0 h-1; iv) hydrogen-containing gas flow rate of about 2000 SCF / bbl to about 10000 SCF / bbl.

[0113] In an embodiment, the hydroprocessing further comprises adding a sulfiding agent to maintain a ratio of H2S to the non-pretreated feedstock at about 100 ppm or greater.

[0114] In an embodiment, the hydroprocessing further comprises at least one hydrotreating catalyst.

[0115] In an embodiment, a partial conversion of oxygen occurs in the first stage.

[0116] In an embodiment, the system further comprises a separation stage for separating i) gaseous product(s) from ii) liquid(s) and solid(s).

[0117] In an embodiment, the separation stage substantially separates the liquid(s) from the solid(s) in ii).T-12086-W001

[0118] In an embodiment, the second stage is configured for hydrotreating the liquid(s) from ii).

[0119] In an embodiment, the separation stage comprises at least one of a filtration system, a centrifuge system, an electrostatic precipitation system, a settling system, and an evaporation system.

[0120] In an embodiment, wherein the separation stage comprises at least one of a dead-end filter, a cross-flow filter, and a filter press.

[0121] In an embodiment, the non-pretreated lipid feedstock comprises plant oil(s).

[0122] In an embodiment, the plant oil(s) comprises greater than about 50 ppm N and greater than about 100 ppm combined phosphorus and at least one metal contaminant.

[0123] In an embodiment, the plant oil(s) being used after pressing and / or solvent extraction from a plant and / or plant seeds.

[0124] In an embodiment, the non-pretreated lipid feedstock comprises triglycerides.

[0125] In an embodiment, the non-pretreated lipid feedstock comprises greater than about 90% triglycerides and has greater than about 5% oxygen.

[0126] In an embodiment, the non-pretreated lipid feedstock further comprises other sources of lipids.

[0127] In an embodiment, the other sources of lipids comprise at least one of animal fats, used cooking oil, waste grease, and a combination thereof.

[0128] In an embodiment, the non-pretreated feedstock comprises plastic pyrolysis-oil.

[0129] In an embodiment, the hydroprocessing comprises hydrogenation of the olefins of triglycerides (Tg) to obtain hydrogenated triglycerides (HTg) and the hydrogenated triglycerides are transformed by hydrogenolysis into fatty acids (FA), and waxes.

[0130] In an embodiment, the hydroprocessing further comprises hydrodeoxygenation (HDO), decarbonylation (DCO), decarboxylation (DCO2), hydrocracking, isomerization, dehydrogenation, and / or aromatization.

[0131] In an embodiment, the second stage further comprises at least one catalyst selected from at least one of a hydrotreating catalyst for removing at least one contaminant and an isodewaxing catalyst to improve pour point and cloud point.

[0132] In an embodiment, the second stage has at least three types of catalysts comprising hydrotreating catalyst, a hydrogenation catalyst, and an isomerization catalyst.

[0133] In an embodiment, the second stage has a first layer having the hydrotreating catalyst; a second layer having the hydrogenation catalyst; and a third layer having an isomerization catalyst.T-12086-W001

[0134] In an embodiment, the second stage has a first layer having about 5% to about 20% of the hydrotreating catalyst; a second layer having about 3% to about 10% of the hydrogenation catalyst; and a third layer having an isomerization catalyst.

[0135] In an embodiment, the first layer substantially eliminates contaminants; the second layer converts CO to methane; and the third layer substantially converts n-paraffins into isoparaffins.

[0136] In an embodiment, product(s) from the first stage comprise liquid product(s) that are fed into the second stage and solid product(s).

[0137] In an embodiment, a portion of the liquid product(s) from the first stage is fed back to the first stage.

[0138] In an embodiment, at least a portion of the solid product(s) is recovered.

[0139] In an embodiment, if the solid(s) contains the macroporous hydroprocessing catalyst, the solids are washed to remove salt(s) and recycled.

[0140] In an embodiment, the washed solid(s) are added to the non-pretreated lipid feedstock and fed to the first stage.

[0141] In an embodiment, the system further comprises separating and fractionating to separate gaseous products from renewable product(s).

[0142] In an embodiment, the hydroprocessing conditions in the first stage comprise first deoxygenation reaction conditions.

[0143] In an embodiment, the hydroprocessing of the non-pretreated lipid feedstock in the first stage comprises at least one of hydrodeoxygenation (HDO), hydrotreating and hydrocracking.

[0144] In an embodiment, the hydroprocessing of the at least partially pretreated lipid feedstock in the first stage comprises an at least partial hydrodeoxygenation of the non-pretreated lipid feedstock.

[0145] In an embodiment, the at least partial hydrodeoxygenation of the non-pretreated lipid feedstock in the first stage removes at least about 60% of the oxygen from the non-pretreated lipid feedstock.

[0146] In an embodiment, the at least partial hydrodeoxygenation of the non-pretreated lipid feedstock in the first stage produces a partially-deoxygenated intermediate product.

[0147] In an additional embodiment, complete oxygen conversion and removal of contaminants from the at least one intermediate product occurs in the second stage.

[0148] In an embodiment, the at least one macroporous hydroprocessing catalyst comprises at least one macroporous hydrodeoxygenation catalyst.T-12086-W001

[0149] The novel features of the present disclosure will become apparent to those of skill in the art upon examination of the following detailed description. It should be understood, however, that the detailed description and the specific examples presented, while indicating certain aspects, are provided for illustration purposes only because various changes and modifications within the spirit and scope will become apparent to those of skill in the art from the detailed description and claims that follow.BRIEF DESCRIPTION OF DRAWINGS

[0150] Reference will now be made, by way of example, to the accompanying drawings, in which like numbers denote like parts, and by which the present application can be further understood from the following description with reference to the Figure(s):

[0151] FIG. 1 shows a schematic diagram that illustrates an embodiment of a hydroprocessing system for converting non-pretreated lipid feedstock into renewable fuel; and

[0152] FIG. 2 shows a schematic diagram that illustrates an alternate embodiment of the hydroprocessing system for converting non-pretreated lipid feedstock into renewable fuel.DETAILED DESCRIPTION

[0153] In general, the disclosure relates to a process and system for converting lipid feedstock into renewable fuel.

[0154] Unless otherwise explained, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice for testing of the present disclosure, the typical materials and methods are described herein.

[0155] In addition, in describing and claiming the present disclosure, the common terminology generally used is described herein below. If a term is used in this disclosure but is not specifically described herein, the definition from the IUPAC Compendium of Chemical Terminology can be applied, as long as that definition does not conflict with any other disclosure or description applied herein or render indefinite or non-enabled any claim to which that definition is applied. All references herein to elements or metals belonging to a certain Group refer to the Periodic Table of the Elements and Hawley's Condensed Chemical Dictionary, 13th Edition. Also, any references to the Group or Groups shall be to the Group or Groups as reflected in the Periodic Table of Elements using the CAS system for numbering groups. To the extent that any definition, description, or usage provided by any document incorporated herein by reference conflicts with the description or usage provided herein, the description or usageT-12086-W001provided herein controls. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting.

[0156] Many patent applications, patents, and publications are referred to herein to assist in understanding the aspects described. Each of these references are incorporated herein by reference in their entirety.

[0157] When introducing elements disclosed herein, the articles “a”, “an”, “the”, and “said” are intended to mean that there may be one or more of the elements.

[0158] The term "comprising" and its derivatives, as used herein, are intended to be open ended terms that specify the presence of the stated features, elements, components, groups, integers, and / or steps, but do not exclude the presence of other unstated features, elements, components, groups, integers, and / or steps. The foregoing also applies to words having similar meanings such as the terms, "including", "having" and their derivatives. It will be understood that any embodiments described as “comprising” certain components may also “consist of’ or “consist essentially of,” these components, wherein “consisting of’ has a closed-ended or restrictive meaning and “consisting essentially of’ means including the components specified but excluding other components except for materials present as impurities, unavoidable materials present as a result of processes used to provide the components, and components added for a purpose other than achieving the technical effects described herein. For example, a composition defined using the phrase “consisting essentially of’ encompasses any known acceptable additive, excipient, diluent, carrier, and the like, suitable for the composition described herein. Typically, a composition consisting essentially of a set of components will comprise less than 5% by weight, typically less than 3% by weight, more typically less than 1% by weight of non-specified components.

[0159] It will be understood that any component defined herein as being included may be explicitly excluded from the claimed invention by way of proviso or negative limitation, such as any specific compounds or method steps, whether implicitly or explicitly defined herein.

[0160] In addition, all ranges given herein include the end of the ranges and also any intermediate range points, whether explicitly stated or not.

[0161] Unless otherwise specified, the recitation of a genus of elements, materials, or other components from which an individual component or mixture of components can be selected is intended to include all possible sub-generic combinations of the listed components and mixtures thereof.

[0162] Finally, terms of degree such as "substantially", "about" and "approximately" as used herein mean a reasonable amount of deviation of the modified term such that the end result is not significantly changed. These terms of degree should be construed as including a deviation of atT-12086-W001least ±5% of the modified term if this deviation would not negate the meaning of the word it modifies.

[0163] The abbreviation, “e.g.” is derived from the Latin exempli gratia and is used herein to indicate a non-limiting example. Thus, the abbreviation “e.g.” is synonymous with the term “for example.” The word “or” is intended to include “and” unless the context clearly indicates otherwise.

[0164] The phrase “at least one of’ is understood to be one or more. The phrase “at least one of...and...” is understood to mean at least one of the elements listed or a combination thereof, if not explicitly listed. For example, “at least one of A, B, and C” is understood to mean A alone or B alone or C alone or a combination of A and B or a combination of A and C or a combination of B and C or a combination of A, B, and C.

[0165] The terms "hydroconversion" or "hydroprocessing" are used interchangeably and are meant to define any process that is carried out in the presence of hydrogen, including, but not limited to, methanation, water gas shift reactions, hydrogenation, hydrotreating, hydrodesulphurization, hydrodenitrogenation, hydrodemetallation, hydrodearomatization, hydroisomerization, hydrodewaxing and hydrocracking including selective hydrocracking. Depending on the type of hydroprocessing and the reaction conditions, the productsof hydroprocessing can show improved viscosities, viscosity indices, saturates content, low temperature properties, volatilities, and depolarization, etc. The terms generally encompass all processes in which a feedstock is reacted with hydrogen in the presence of a catalyst and under hydroprocessing conditions, typically, at elevated temperature and elevated pressure.Hydroprocessing includes, for example, processes such as hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrodechlorination, hydrodecarboxylation, hydrodecarbonylation, hydrodearomatization, hydroisomerization, hydrodewaxing, hydrocracking and / or mild hydrocracking. The terms may refer to processes or steps performed in the presence of hydrogen for the hydrocracking, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallation, hydrodechlorination, hydrodecarboxylation, hydrodecarbonylation and / or hydrodearomatization of components (e.g., impurities) of a feedstock, and / or for the hydrogenation of unsaturated compounds in the feedstock. Depending on the type of hydroconversion / hydroprocessing and the reaction conditions, and products may have improved specific gravity, acidity, aromatic content, viscosities, viscosity indices, saturates content, low temperature properties, volatilities, and depolarization, for example.

[0166] The term "hydrotreating" refers to processes or steps performed in the presence of hydrogen for the hydrodesulfurization, hydrodenitrogenation, hydrodeoxygenation,T-12086-W001hydrodemetallation, and / or hydrodearomatization of components (e.g., impurities) of a feedstock, and / or for the hydrogenation of unsaturated compounds in the feedstock.

[0167] The term “renewable feedstock” as used herein refers to a material originating from a renewable resource (e.g., plants) and non-geologically derived. The term “renewable” is also synonymous with the term “sustainable,” “sustainably derived,” or “from sustainable sources.” The term “geologically derived” means originating from, for example, crude oil, natural gas, or coal. “Geologically derived” materials cannot be easily replenished or regrown (e.g., in contrast to plant- or algae-produced oils).

[0168] The term "biofeedstock" as used herein refers to biocomponent feeds that are from or are derived from a biological source. Exemplary biofeedstocks include lipids (e.g. lipid feedstock), pyrolysis oils, biomass derived feeds, and the like. Triglycerides are a component of some biofeedstocks, such as lipid feedstock. The biofeedstock typically has a boiling range suitable for producing a diesel, aviation or other fuel, or distillate therefrom. In the case of some biofeedstocks comprising triglycerides, such are referred to as lipid feedstocks and have an "apparent" boiling temperature range (based on the GC elution time of the triglyceride peaks according to ASTM D7398 or SIMDIST method ASTM D-6352 or D7169) suitable for producing a diesel, aviation or other fuel, or distillate therefrom. The lipid feedstock boiling range (or apparent boiling range) may also be suitable for producing a base oil or a component thereof. In some embodiments, the lipid feedstock has a boiling point greater than about 250°F (121°C), for example, greater than about 300°F (149°C), greater than about 500°F (260°C), or greater than about 650°F (343°C).

[0169] The term “lipid feedstock” as used herein may refer to feeds that contain or are at least partially derived from at least one lipid component. In embodiments, the lipid feedstock may be partially decomposed and / or hydrolyzed. Suitable lipid feedstocks for use herein can comprise, for example, from 0 to about 90 wt. % of free fatty acids, about 5 to 100 wt. % fatty acid glycerol esters (e.g., mono-, di-, triglycerides) and 0 to about 20 wt. % of one or more compounds selected from the group consisting of fatty acid esters of the non-glycerol type, fatty amides, and fatty alcohols. In an illustrative embodiment, as may be combined with the preceding embodiment, the lipid feedstock comprises more than about 50 wt. % of free fatty acids and fatty acid glycerol esters such as about 70 wt. % or more, for example, about 80 wt. % or more and up to 100 wt. %.

[0170] A lipid feedstock may include lipids (e.g., fats or oils) that originate, for example, from any type of plant, animal, microorganisms such as algae (e.g., algae oil, algae biomass, algae cultivation), fish and microbiological process. In an embodiment, the lipid feedstocks used include triglycerides. Many different lipid feedstocks derived from plants can be used. InT-12086-W001embodiments, plant-based lipid feedstocks can include, for example, rapeseed oil,soybean oil (including degummed soybean oil), canola oil, cottonseed oil, grape seed oil, mustard seed oil, corn oil, linseed oil, safflower oil, sunflower oil, poppy-seed oil, pecan oil, walnut oil, oat oil, peanut oil, rice bran oil, camellia oil, castor oil, and olive oil, palm oil, coconut oil, rice oil, algae oil, seaweed oil, Chinese Tallow tree oil. Other plant-based lipid feedstocks can be obtained from, for example, argan, avocado, babassu palm, balanites, borneo tallow nut, brazil nut, calendula, camelina, caryocar, cashew nut, Chinese vegetable tallow, cocoa, coffee, cohune palm, coriander, cucurbitaceae, euphorbia, hemp, illipe, Jatropha, jojoba, kenaf, kusum, macadamia nuts, mango seed, nogg abyssinia, nutmeg, opium poppy, perilla, pili nut, pumpkin seed, rice bran, sacha inche, seje, sesame, shea nut, teased, allanblackia, almond, chaulmoogra, cuphea, jatropa curgas, karanja seed, neem, papaya, tonka bean, tong, and ucuuba, cajuput, clausena anisata, davana, galbanum natural oleoresin, gennan chamomile, hexastylis, high-geraniol monarda, juniapa-hinojo sabalero, Melissa officinalis, milfoil, ninde, patchouli, tarragon, and wormwood. In some embodiments, the lipid feedstock is selected from canola oil, corn oil, soy oils, castor oil, camelina oil, palm oil and / or combinations thereof.

[0171] Many different lipid feedstocks derived from animals (i.e., animal-based lipid feedstocks) can also be used. In embodiments, animal-based lipid feedstocks can include, for example, choice white grease, lard (pork fat), tallow (beef fat), fish oil, and poultry fat.

[0172] Many different lipid feedstocks derived from microorganisms (Eukaryotes, Eubacteria and Archaea) can also be used. In embodiments, microbe-based lipid feed stocks can include, for example, the L-glycerol lipids of Archaea and algae and diatom oils. In some embodiments, lipid feed stocks derived from microorganisms can include bacteria, protozoa, algae, and fungi.

[0173] In some embodiments, lipid feedstocks derived from both plant and animal sources can be used such as, for example, yellow grease, white grease, and brown grease. In non-limiting illustrative embodiments, yellow, white, or brown grease can include frying oils from deep fryers and can thus include fats of both plant and animal origin. Lipid feedstocks can specifically include used cooking oil. Brown grease (also known as trap grease) can include fats extracted from sewage systems and can thus include fats of both plant and animal origin. In some embodiments, lipid feedstocks used in embodiments can include non-biological lipid feedstocks. Lipid feedstocks of the present disclosure can also include black oil.

[0174] In embodiments, the lipid feedstocks include feedstocks originating from low value renewable waste materials, side streams, by-products, refining waste and residues, sewage sludge, and any combinations thereof.T-12086-W001

[0175] In embodiments, the lipid feedstocks may be selected from the group consisting of acidulated soap-stocks, fatty acid distillates from physical refining of plant oils or animal fats, distillers com oil (DCO) from ethanol production, waste cooking oils, lard, brown grease, yellow grease, trap grease, waste fats, low-grade oils, supercritical water liquefaction oils (SCWL oils), plant oils, animal fats and any combination thereof.

[0176] In some embodiments, the lipid feedstock has a boiling point greater than about 250°F (121°C), for example, greater than about 300°F (149°C), greater than about 500°F (260°C), or greater than about 650°F (343°C) at atmospheric pressure. In some embodiments, the lipid feedstock has a 90 % distillation temperature of greater than about 1000°F (538°C), or 900°F (482°C), or 800°F (427°C) or 700°F (371°C), or less than about 650°F (343°C). In some embodiments, the lipid feedstock has a 90% distillation temperature in the range of about 550°F (288°C) to about 1400°F (760°C), for example about 500°F (260°C) to about 1200°F (649°C), about 700°F (371°C) to about 1400°F (680°C). The 90% distillation temperature may be determined in accordance with ASTM D-2887, or ASTM D7169. In some embodiments, the lipid feedstock has a 5% distillation temperature in the range of about 250°F (121°C) to about 600°F (316°C), for example about 300°F (149°C) to about 600°F (316°C), or about 400°F (about 204°C) to about 600°F (316°C). The 5 % distillation temperature may be determined in accordance with ASTM D 2887.

[0177] In some embodiments, the lipid feedstock is selected from vegetable oils and / or animal fats comprising, or consisting essentially of, triglycerides and free fatty acids (FFA). In some embodiments, the lipid feedstock comprises vegetable oils and / or animal fats which comprise triglycerides and free fatty acids, for example wherein the lipid feedstock is selected from canola oil, com oil, soy oils, castor oil, camelina oil, palm oil, and / or a combination thereof.

[0178] In some embodiments, the triglycerides and FFAs contain aliphatic hydrocarbon chains in their structure having 6-24 carbon atoms (for example, 8 to 24, 8 to 20, or 10-16 carbon atoms). In some embodiments, the lipid feedstock comprises triglycerides having the general formula (1):T-12086-W001

[0179] where R, R1and R2are independently aliphatic hydrocarbon chains having from 6-24 carbon atoms (for example, 8 to 24, 8 to 20, 10-20, 10-18, or 10-16 carbon atoms). In some embodiments, R, R1and R2are independently branched or un-branched, substituted, or unsubstituted, completely saturated or contain one or more (for example 1-4, 1-3 or 1 or 2) unsaturated carbon-carbon bonds. In some embodiments, R, R1 and R2 are unsubstituted. In some embodiments, R, R1 and R2 are independently completely saturated or contain one or more (for example 1-4, 1-3 or 1 or 2) unsaturated carbon-carbon bonds. In some embodiments, R, R1 and R2 are un-branched.

[0180] In some embodiments, the lipid feedstock comprises free fatty acids (FFAs) having aliphatic hydrocarbon tails of 6 to 24 carbon atoms, for example 8 to 24 carbon atoms, 8 to 20 carbon atoms, 10 to 20 carbon atoms, 10 to 18 carbon atoms, or 10-16 carbon atoms. In some embodiments, the FFAs comprise unsaturated or saturated aliphatic hydrocarbon tails. In some embodiments, the FFAs comprise unbranched or branched aliphatic hydrocarbon tails.

[0181] Lipid feedstock may be obtained via extraction, for example, via plant or plant seed pressing and extraction.

[0182] In an embodiment, as may be combined with one or more of the preceding paragraphs, the lipid feedstocks comprise one or more of alkali metals, alkaline earth metals, and / or other metals, such as iron and manganese. Even in low amounts, the one or more metals within the lipid feedstock may cause the lipid feedstock to be regarded as not suitable for catalytic treatment in refinery operations, as each of the metals is an effective catalyst poison or can cause plugging to occur within the catalyst bed (e.g. fixed-bed reactors). The alkali metals, alkaline earth metals and other metals may typically comprise Na, K, Mg, Ca, Mn, Fe, or a combination thereof. In embodiments, the lipid feedstock may comprise at least about 1 ppm (e.g., about 1 to about 250 ppm, about 1 to about 100 ppm, about 1 to about 50 ppm, about 1 to about 25 ppm, about 2 to about 250 ppm, about 2 to about 100 ppm, or about 2 to about 25 ppm) of alkali metals, alkaline earth metals, metals of Groups VIIB and VIIIB, or combinations thereof, calculated as elemental metals, in total. Total metal content can be determined using AOCS Recommended Practice Ca 17-01 or by Inductively Coupled Plasma (ICP) metal analysis.

[0183] In other embodiments, the lipid feedstocks can include low value lipid feedstocks, such as various types of animal fats and waste oils, which generally have a relatively high concentration of free fatty acids. One method of assessing the concentration of free fatty acids is to determine the total acid number (TAN) of the feedstock. The total acid number is the mass of potassium hydroxide (KOH) in milligrams that is required to neutralize one gram of the chemical substance being assessed.T-12086-W001

[0184] In embodiments, as may be combined with one or more of the preceding paragraphs, the lipid feedstocks may have a total acid number of at least about 2 mg KOH / g (e.g., about 2 to about 150 mg KOH / g, about 10 to about 150 mg KOH / g, from about 10 to about 100 mg KOH / g, from about 5 to about 50 mg KOH / g, from about 10 to about 25 mg KOH / g, or from about 10 to about 20 mg KOH / g). The total acid number can be determined using ASTM D664.

[0185] Lipid feedstocks typically contain varying amounts of impurities such as, for example, phosphorus, silicon, chloride, alkali metals, earth alkaline metals, other metals, etc. In an embodiment, as may be combined with one or more of the preceding paragraphs, the lipid feedstocks can contain varying amounts of chloride such as at least about 2 ppm, or at least about 4 ppm or at least about 10 ppm (e.g., about 2 to about 100 ppm, about 2 to about 75 ppm, about 2 to about 50 ppm, about 10 to about 100 ppm, or about 10 to about 50 ppm), where any of the lower limits can be combined with any of the upper limits. In another embodiment, as may be combined with one or more of the preceding paragraphs / embodiments, the lipid feedstocks can contain varying amounts of phosphorus, such as, for example, at least about 2 ppm, or at least about 10 ppm or at least about 50 ppm (e.g., about 2 to about 1000 ppm, about 5 to about 750 ppm, about 5 to about 500 ppm, about 10 to about 100 ppm, or about 10 to about 1500 ppm), where any of the lower limits can be combined with any of the upper limits.

[0186] Non-renewable feedstock components may be added to the lipid feedstock. For example, plastic pyrolysis-oil can also be included in the lipid feedstock.

[0187] The term “lipid” is known in the art and refers to FFAs and their derivatives.Accordingly, examples of lipids include FFAs (both saturated and unsaturated); glycerides or glycerolipids, also referred to as acylglycerols (such as monoglycerides (monoacylgycerols), diglycerides (diacylglycerols), triglycerides (triacylglycerols, TAGs, or neutral fats); phosphoglycerides (glycerophospholipids); nonglycerides (sphingolipids, sterol lipids, including cholesterol and steroid hormones, prenol lipids including terpenoids, fatty alcohols, waxes, and polyketides); and complex lipid derivatives (sugar-linked lipids or glycolipids, and protein-linked lipids).

[0188] The term “pretreated” as used herein refers to a feedstock or other compounds that have been partially or fully treated via a chemical treatment process for removing at least one contaminant prior to hydroprocessing. The chemical treatment process can involve, for example, a chemical reaction such as degumming to remove phospholipids, neutralization to remove free fatty acids, bleaching, deodorization, RBD (refining, bleaching, and drying), hydrothermal cleanup processes to remove contaminants, etc. The contaminant(s) removed during these chemical treatment processes can include, for example, phosphorus and / or combined metals (Ca, Mg, K, Na, Fe, etc.).T-12086-W001

[0189] The term “non-pretreated lipid feedstock” as used herein refers to a lipid feedstock that has not been chemically pretreated to remove at least one contaminant. In embodiments, the non-pretreated lipid feedstock may be partially or fully treated via a physical treatment process. The physical treatment processes may include cold pressing, solvent extraction, decanting, and / or filtration.

[0190] Unless otherwise specified, the "feed rate" of a feedstock being fed to a catalytic stage is expressed herein as the volume of feed per volume of catalyst per hour, which may be referred to as liquid hourly space velocity (LHSV) with units of reciprocal hours (h 1).

[0191] The term, “catalyst”, as used herein is not particularly limited and should be known or understood by a person of skill in the art. A catalyst refers to a substance that can increase the rate of a chemical reaction, or lowers the temperature or pressure needed to start one. The increase in reaction rate can occur as the catalyst allows for the reaction to occur by an alternative mechanism that can require a lower activation energy.

[0192] The term "catalyst support" is used in the conventional sense according to the normal usage in the art and includes typical catalyst support materials such as alumina, silica-alumina, metal oxides, zeolites, and non-zeolite materials, activated carbon, and the like.

[0193] The term "catalyst precursor" refers to a compound containing one or more catalytically active metals, from which compound the catalyst is eventually formed, and which compound may be catalytically active as a hydroprocessing catalyst. An example is a waterbased catalyst prior to a transformation step with a hydrocarbon diluent, another example is a sulfided metal precursor. Catalyst precursors and the preparation of catalysts are described in various patents, e.g., US 8,802,586, WO 2012 / 092006, and the like.

[0194] The term ’’macroporous hydroprocessing catalyst” is any catalyst that may be used in a “hydroconversion" or "hydroprocessing" process as defined above. The macroporous hydroprocessing catalyst of the present disclosure is a macroporous catalyst that provides the combined functionality of contaminant removal and hydroprocessing catalysis. The macroporous hydroprocessing catalyst may include a Group VI metal, a Group VIII metal (including noble and non-noble metals), or combinations thereof. The macroporous hydroprocessing catalyst can also include transition metals selected from Group VIA (Group 6) and Group VIII (Groups 8-10) metals. Group 6 elements may include chromium, molybdenum, and tungsten. Group 8-10 elements may include iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum. The macroporous hydroprocessing catalyst may be in the oxidic and / or the sulphidic form. In some embodiments, the macroporous hydroprocessing catalyst comprises one or more components of nickel and / or cobalt and one or more components of molybdenum and / or tungsten or one or more components of platinum and / or palladium. The macroporousT-12086-W001hydroprocessing catalyst may include a combination of nickel or cobalt with molybdenum or tungsten. Alternatively, the macroporous hydroprocessing catalyst may include a noble metal such as palladium or platinum. The macroporous hydroprocessing catalyst may also be an interstitial metal hydride. The term “macroporous hydroprocessing catalyst” as used herein may refer solely to the coated active component (as used as a catalyst) or a combination catalyst incorporating a selectively coated active component.

[0195] The term "pore volume", as used to describe the porosity of a catalyst, may be described in terms of the "wet pore volume" and the "pore volume" determined by mercury intrusion. The "incipient wet pore volume" or "wet pore volume" is measured by the incipient wetness impregnation method. In the method, an amount of dried catalyst is impregnated with a liquid, typically water, by capillary action until all the pores are saturated. The wet "pore volume" is calculated by dividing the total volume of water absorbed in the pores by the total weight of the catalyst. The mercury intrusion pore volume of the catalyst is measured according to ASTM D4284 and is typically provided by a commercial mercury intrusion porosimeter.

[0196] The terms “macroporous,” “mesoporous,” and “microporous” are known to those of ordinary skill in the art and are used herein in consistent fashion with their description in the International Union of Pure and Applied Chemistry (IUPAC) Compendium of Chemical Terminology, Version 2.3.2, Aug. 19, 2012 (informally known as the “Gold Book”). Generally, microporous materials include those having pores with cross-sectional diameters of less than 2 nm (0.002 pm). Mesoporous materials include those having pores with cross-sectional diameters of from 2 to 50 nm (0.002 to 0.05 pm). Macroporous materials include those having pores with cross-sectional diameters of greater than about 50 nm (0.05 pm). It will be appreciated that a given material or composition may have pores in two or more such size regimes, e.g., a particle may comprise macroporosity, mesoporosity and microporosity. Each of the definitions of micropore, mesopore and macropore are considered distinct such that there is no overlap, and pores are not counted twice when summing up percentages or values in a distribution of pore sizes for any given sample.

[0197] The term "hydroisomerization catalyst" as used herein refers to a catalyst that facilitates the skeletal isomerization of hydrocarbon molecules. In some embodiments, suitable hydroisomerization catalysts include catalysts comprising zeolite SSZ-91. Other hydroisomerization catalysts may also be suitable, including various types of zeolites e.g., catalysts based on zeolite SSZ-32, zeolite SSZ-32x, zeolite SSZ-13, and / or zeolite SSZ-16. Combinations of suitable hydroisomerization catalysts based on the same or different zeolite supports may also be used. In some embodiments, the hydroisomerization catalyst comprises zeolite SSZ-91, or from about 5 to about 95 wt.% zeolite SSZ-91 by total weight of theT-12086-W001hydroisomerization catalyst, or from about 10 to about 95 wt.% zeolite SSZ-91, from about 20 to about 90 wt.% zeolite SSZ-91, or from about 25 to about 85 wt.% zeolite SSZ-91, or from about 30 to about 80 wt.% zeolite SSZ-91, or from about 35 to about 75 wt.% zeolite SSZ-91, or from about 35 to about 65 wt.% zeolite SSZ-91, or from about 35 to about 55 wt.% zeolite SSZ-91, or from about 45 to about 75 wt.% zeolite SSZ-91, or from about 55 to about 75 wt.% zeolite SSZ-91 by total weight of the hydroisomerization catalyst. The hydroisomerization catalyst further comprises a metal modifier, for example a metal modifier selected from Group 2, 8, 9 and 10 metals or combinations thereof. In some embodiments, the metal modifier is selected from Group 8, 9 or 10 metals and combinations thereof, for example the metal modifier may be selected from Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt and combinations thereof. In some embodiments, the metal modifier is selected from Group 10 metals and combinations thereof. In some embodiments, the hydroisomerization catalyst comprises platinum, palladium, or a combination thereof. Base metals may be included in the catalyst.

[0198] The term, “ebullated bed catalyst” or the like, as used herein refers to catalyst included in the ebullated bed reactors of the systems and processes disclosed herein, and can comprise hydroconversion catalysts, i.e., catalysts that may be used for the hydrotreating or hydrocracking of a hydrocarbon feedstock. The ebullated bed catalyst (EB catalyst) can be present as pellets or as an extrudate catalyst and can be >0.5 mm in diameter and 1-8 mm in length. In another embodiment, for example and without limitation, the EB catalyst has a spherical shape having a diameter of from 1 to 4 mm. In certain embodiments, the hydrotreating catalyst is a catalyst composition that may be used to catalyze the hydrogenation of hydrocarbon feedstocks to increase its hydrogen content and / or remove heteroatom contaminants. A hydrocracking catalyst, for example and without limitation, may include any catalyst composition that may be used to catalyze the addition of hydrogen to large or complex hydrocarbon molecules as well as the cracking of the molecules to obtain smaller, lower molecular weight molecules. In a further embodiment, for example and without limitation, the ebullated bed (EB) hydrocracking catalyst is a NiMo supported catalysts on alumina, having a total pore volume of >0.5 cc / g and a surface area of >100 m2 / g.

[0199] As used herein, the term, “slurry catalyst”, slurry or dispersed catalyst refers to a solid (such as, for example and without limitation, a powder) or a liquid medium, e.g., oil, water, or mixtures thereof, in which catalyst and / or catalyst precursor particles (particulates or crystallites) having very small average dimensions are dispersed within. The slurry catalyst as used herein are in the particle size range of less than about 100 micrometers (pm). Further to the above, the slurry catalyst can be present as a precursor, such as organo-Mo, like Mo-octoate, which can beT-12086-W001activated in-situ to form colloidal or nanometer or micron size catalysts. The slurry catalyst can also be pre-sulfided and pre-activated and injected to a slurry reactor with a liquid carrier.

[0200] The term, “hydrogen-containing gas” or the like, as used herein is not particularly limited and should be known or understood by a person of skill in the art. As used herein, hydrogen-containing gas refers to a gas that comprises hydrogen. For example, and without being limited to, the hydrogen-containing gas is hydrogen. In another example and without being limited to, the hydrogen-containing gas comprises hydrogen and another gas.

[0201] The term, “sulfiding agent” or the like, as used herein is not particularly limited and should be known or understood by a person of skill in the art. As used herein, “sulfiding agent” refers to a gas or liquid that may comprise sulfur, H2S, and / or can form H2S in a reactor unit for converting active components, e.g., Mo, Ni, W, Co, or the like, into their sulfide form. In an example, the sulfiding agent is a gas or liquid that comprises H2S. In another example, the sulfiding agent comprises H2S and another gas. In yet another example, the sulfiding agent contains dimethyl disulfide (DMDS) and / or tertiary-butyl polysulfide (TBPS). In yet another example, the sulfiding agent contains elemental sulfur. In yet another additional example, the sulfiding agent is a sulfur-containing hydrocarbon.

[0202] In at least some embodiments of the present disclosure, the “sulfiding agent” is gas or liquid that is provided into the reactor and forms H2S with partial pressure such that a quantity of H2S is at least about 10 ppm. For example, then sulfiding agent can form H2S such that the quantity of H2S is at least about 50 ppm, at least about 100 ppm, at least about 150 ppm, from about 50 ppm to about 150 ppm, from about 50 ppm to about 200 ppm, from about 50 ppm to about 250 ppm, from about 50 ppm to about 300 ppm, from about 100 ppm to about 500 ppm, or from about 20 ppm to about 500 ppm.

[0203] The term, “ebullated bed reactor,” as used herein is not particularly limited and should be known or understood by a person of skill in the art. Ebullated bed reactors are a type of fluidized bed reactor that utilizes ebullition, or bubbling, to achieve appropriate distribution of reactants and catalysts. Ebullated bed technology utilizes a three-phase reactor (liquid, vapor, and solid), and is most applicable for exothermic reactions and for feedstocks which are difficult to process in fixed-bed or plug flow reactors, including for feeds having higher levels of contaminants. Ebullated bed reactors generally provide high-quality, continuous mixing of liquid and catalyst particles and have the characteristics of stirred reactor type operation with a fluidized catalyst. The advantages of ebullated bed reactors include, e.g., good back-mixed bed performance, excellent temperature control, and low and constant pressure drops due to reduced bed plugging and channeling. Ebullated bed reactors are used in the hydroconversion of renewable feedstock. In one embodiment, the ebullated bed reactors can have internalT-12086-W001recirculation (LC-FINING type) or external recirculation (H-Oil type). Embodiments of ebullated bed reactors are disclosed in US 2015 / 0329790 Al and WO 2023 / 137350 (both incorporated herein by reference).

[0204] The term, “slurry reactor” or the like, as disclosed herein is not particularly limited, and should be known or understood by a person of skill in the art. The slurry reactor are three-phase reactors, in that they can be used to react solids, liquids, and gases simultaneously. A slurry reactor, as disclosed herein, may contain a slurry catalyst (solid) suspended in a liquid, and in which a gas is bubbled. They can operate in either semi-batch or continuous mode.

[0205] If a standard test is mentioned herein, unless otherwise stated, the version of the test to be referred to is the most recent at the time of filing this patent application.

[0206] As mentioned above, there is an increasing interest in alternative feedstocks for replacing at least partly crude oil, in the production of hydrocarbons suitable as fuels or fuel components, for example, as transportation fuels, or compatible with fuels. Biofuels are typically manufactured from feedstock originating from renewable sources. These feedstocks, particularly the various waste streams and side streams, contain varying amounts of contaminants, such as gums, organic chlorine compounds, phospholipids and other phosphorus compounds, metals and metal compounds, and residual soaps, which are, for example, deleterious to converting catalysts.

[0207] In a general embodiment, there is provided a process for making a renewable product from a non-pretreated lipid feedstock. The process comprises hydroprocessing the non-pretreated lipid feedstock with at least one macroporous hydroprocessing catalyst under hydroprocessing conditions to produce the renewable product, where the macroporous hydroprocessing catalyst functions to remove at least one contaminant from the lipid feedstock and as a hydroprocessing catalyst.

[0208] In another general embodiment, there is provided a system for making a renewable product from a non-pretreated lipid feedstock. The process comprises a first stage having at least one reactor for hydroprocessing the non-pretreated lipid feedstock with at least one macroporous hydroprocessing catalyst under hydroprocessing conditions to produce the renewable product, where the macroporous hydroprocessing catalyst functions to remove at least one contaminant from the lipid feedstock within the system.

[0209] In embodiments disclosed herein, two-stage hydroprocessing is used to convert nonpretreated lipid feedstock into renewable product(s) (e.g. renewable fuels). The first stage of the process and / or system comprises partial conversion of oxygen of the non-pretreated lipid feedstock using at least one macroporous hydroprocessing catalyst. In the second stage of the process and / or system, the intermediate product(s) from the first stage are hydrotreated toT-12086-W001complete oxygen conversion and remove additional contaminants to provide renewable product(s).

[0210] In other embodiments disclosed herein, the first stage is featured by partial conversion of oxygen in an ebullating-bed or a slurry -bed reactor using at least one macroporous hydroprocessing catalyst. In the second stage, a fixed-bed reactor is used for hydrotreating the intermediate product(s) to complete the oxygen conversion, remove other contaminants such as nitrogen, and perform dewaxing to provide renewable product(s). The process and system may also, in some embodiments, further comprise separating and fractionating the renewable product(s) to separate gaseous products from renewable fuels (e.g., gasoline, sustainable aviation fuel (SAF) and renewable diesel).

[0211] FIG. 1 illustrates an embodiment of the process and / or system in which nonpretreated lipid feedstock 10 is fed to an ebullating-bed or a slurry-bed reactor platform 20 using at least one macroporous hydroprocessing catalyst as part of the first stage of a two-stage reactor system. Intermediate products undergo gas / liquid / solid separation and gas stream (40), and solid byproduct (42) are withdrawn before the second stage. The liquid intermediate products are fed 30 to fixed-bed reactor 50 for hydroprocessing (e.g. hydrotreating / methanation / hydro-isomerization), to produce renewable product(s) 60 as part of the second stage.

[0212] In the second stage, hydroprocessing may be carried out within a single reactor in some embodiments and in other embodiments, the process and / or system may be carried out in two or more reactors connected in series, with a first reactor, or catalyst section, comprising a hydrotreating section and a reactor, or catalyst section, downstream from the first reactor or catalyst section comprising a hydroisomerization section.

[0213] In some embodiments, all of the products from the hydrotreating section are directly passed to the hydroisomerization section, i.e., no intermediate products are removed between the sections. The skilled person will appreciate that various reactor configurations and catalyst loading arrangements are possible herein.

[0214] The embodiments of the lipid feedstocks described herein may be used alone or in any combination described herein. The lipid feedstocks are provided without pretreatment to remove contaminant(s). Pretreatment may comprise degumming (water washing, acid washing, etc.), neutralization, bleaching, deodorizing, hydrothermal cleanup, or any combination thereof.

[0215] In embodiments, non-pretreated lipid feedstock is feedstock that has not undergone such cleanup processes. Exemplary embodiments of non-pretreated lipid feedstock according to the present disclosure can include plant seed oil that is used immediately after pressing, untreated animal fats, and used cooking oil with no contaminant removal. It can be challenging to process such non-pretreated lipid feedstock without a suitable reaction platform and catalyst system.T-12086-W001

[0216] As mentioned above, non-renewable feedstock components may be added to the lipid feedstock. For example, plastic pyrolysis-oil can also be part of the feedstock.

[0217] In embodiments, the first stage reactor platform may include an ebullating-bed reactor, a slurry -bed reactor, or a Upflow Reactor (UFR), with the macroporous hydroprocessing catalyst (e.g., a hydroprocessing catalyst having high macropore volume) to remove solids and / or contaminants.

[0218] In embodiments, the lipid feedstocks do not undergo pretreatment before being fed to the first-stage reactor. Therefore, the feedstock contains high levels of contaminants which can be removed in the first stage with the at least one macroporous hydroprocessing catalyst. The macroporous hydroprocessing catalyst comprises a macroporous hydroprocessing catalyst (e.g. a macroporous ebullating-bed catalyst, a macroporous slurry -bed catalyst, or a macroporous upflow reactor catalyst) whereby, the contaminants may be either deposited on and / or impregnated in the catalyst and removed by catalyst withdrawal / removal and / or deposited on and / or impregnated in the catalyst and removed via the removal of the catalyst with at least one intermediate product. Several mechanisms may be involved in the removal of the contaminant(s).

[0219] In embodiments, the second stage reactor platform may include a fixed-bed reactor having a hydrotreating catalyst to clean-up any other contaminants (oxygen, nitrogen, etc.) and an isodewaxing catalyst to convert normal paraffins to iso-paraffins to improve pour point and cloud point.

[0220] In one embodiment, the processing conditions comprise liquid hourly space velocity at about 0.08 to about 2 hr-1, pressure at about 1000 to about 3000 psig, temperature at about 580 to about 850°F, and H2 to feed ratio at about 1000 to about 8000 SCF / bbl.

[0221] The hydroprocessing conditions are known to those skilled in the art. Conditions typically comprise a temperature in the range of about 300°F to about 800°F (149°C to 427°C); a pressure in the range of about 200 to about 3000 psig (1.4 to 20.7 MPa gauge); a feed rate of lipid feedstock in the range from about 0.1 to about 20 h 1 LHSV; a hydrogen feed rate at about 2500 to about 10,000 standard cubic feet H2 per barrel lipid feedstock (SCF / bbl), and hydrogen and lipid feedstock feed rates in a ratio of about 1000 to about 8,000 standard cubic feet H2 per barrel lipid feedstock (SCF / bbl). In embodiments, in the first stage, the temperature is about 580 to about 800°F, the pressure is about 300 to about 3000 psig, the feed rate of lipid feedstock is about 0.1 to about 3.0 hr-1 LHSV, and the hydrogen feed rate is at about 2500 to about 10000 SCF / bbl. In embodiments, in the second stage, the temperature is about 500 to about 800°F, the pressure is about 300 to about 3000 psig, the feed rate of lipid feedstock is about 0.1 to about 3.0 hr-1 LHSV, and the hydrogen feed rate is at about 2000 to about 10000 SCF / bbl.T-12086-W001

[0222] After the first stage of the process and / or system, and in embodiments, there may be a separation section, fractionation section, solid separation to remove solids and other contaminants high level solids in a heavy product. The heavy product and any solids may be separated via filtration using dead-end filter, cross-flow filter or filter press, or using centrifuge, electrostatic precipitation, etc. In embodiments, the intermediate product(s) from the first stage can enter a separation step to be separated into two streams: gaseous products (CO, CO2, H2O and light hydrocarbons), liquid products, and solids (e.g., macroporous hydroprocessing catalyst or solids generated from contaminants in non-pretreated feedstock). In additional embodiments, a liquid-solid separation step to separate liquid from solids may be applied (e.g., via filtration using dead-end filter, cross-flow filter or filter press, or using centrifuge, electrostatic precipitation, etc.). The liquid can be fed to a downstream second stage reactor (e.g., fixed-bed reactor). Optionally, a portion, about 10 to about 20% may be recycled back to the first stage reactor. Optionally, any solids may proceed to metal and salt recovery. If the solids contain any catalyst, it may be water-washed to remove soluble inorganic salt, re-slurried with non-pretreated lipid feedstock and fed to the reactor in the first stage for further processing.

[0223] In embodiments, the second stage reactor has three types of catalysts: a first layer (contacting liquid first) has a hydrotreating catalyst (e.g. about 5 to about 20% hydrotreating catalyst) to completely or substantially remove contaminant(s) (e.g. oxygen and nitrogen); a middle layer having a hydrogenation catalyst (e.g. about 3 to about 10% hydrogenation catalyst) for conversion of CO to methane (i.e. methanation) as CO may poison the subsequent catalyst and accelerate catalyst deactivation; and a third layer having an isomerization catalyst for conversion of n-paraffins into iso-paraffins.

[0224] Optionally, a further separation and fractionation step can be performed to separate gaseous products from renewable product(s) (e.g., fuels such as renewable gasoline, SAF and renewable diesel).

[0225] FIG. 2 illustrates a specific embodiment of the process and / or system in which lipid feedstock is fed into the first stage reactor, and where the hydroprocessing system also comprises intermediate product removal stages and additional solid handling and removal stages. In this embodiment, a relatively high contaminant, non-pretreated lipid feedstock 10 is fed into an ebullating-bed or slurry -bed reactor platform 20 as part of the first stage of the two-stage reactor system. The ebullating-bed or slurry-bed reactor platform 20 uses the at least one macroporous hydroprocessing catalyst. Intermediate products are produced from the reaction of the nonpretreated lipid feedstock 10 within the reactor platform 20 and the intermediate products are then fed 22 into a gas-liquid separation stage 32 and a subsequent liquid-solid separation stage 34 for withdrawing 40 gases and withdrawing 42 solids from the intermediate products. TheT-12086-W001gases withdrawn from the intermediate products can include, for example, light hydrocarbons, CO, CO2 and / or H2O. The products from the gas-liquid separation stage 32 can be fed into the liquid-solid separation stage 34 to produce a substantially solid-free liquid intermediate product. The solids withdrawn 42 from the liquid-solid separation stage 34 can be fed back and reintroduced to the ebullating-bed or slurry-bed reactor platform 20 together with the nonpretreated lipid feedstock 10. Alternatively, or in addition, the solids extracted 42 in the liquidsolid separation stage 34 can be disposed of, recycled, or fed into additional systems as part of a regeneration or recovery stage 36. The substantially solid-free liquid intermediate product is fed 30 into a fixed bed reactor platform 50 as part of the second stage reactor platform. The fixed bed reactor platform 50 comprises a first layer of catalyst 52 that is a hydrotreating catalyst for cleaning-up any other remaining contaminants. The fixed bed reactor platform 50 also comprises a middle layer 54 having a methanization catalyst and the third layer 56 having the isomerization catalyst for conversion of n-paraffins into iso-paraffins. The fixed bed reactor platform 50 outputs a final reaction product 60, and the final reaction product 60 is passed through a separation and fractionation stage 70 to separate gaseous products 72 from the renewable product(s) 80 e.g., fuels such as gasoline, SAF and renewable diesel) of the final reaction product. Again, the gases separated from the intermediate products can include, for example, light hydrocarbons, CO, CO2 and / or H2O.

[0226] In embodiments, the process and system disclosed herein can have one or more reactors, where the reactors are in series or in parallel. The process and system disclosed herein can utilize multiple reactors in series or in parallel (e.g., ebullated bed, slurry, UFR, fixed-bed, etc.). Similar to the ebullated bed reactor in series, the process and system disclosed herein can have multiple slurry column reactors in series.

[0227] All feeds in reactors undergo various reactions in the presence of hydrogen and catalyst, that include, for example and without limitation, pyrolysis, hydrogenation, hydrotreating, hydroisomerization, hydrocracking, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenization, hydrodemetallization, decarboxylation, and decarbonylation.Non-pretreated Lipid Feedstock

[0228] The non-pretreated lipid feedstock may comprise at least one contaminant in an amount of less than about 2000 ppm; less than about 1500 ppm; less than about 1000 ppm; less than about 900 ppm; less than about 800 ppm; less than about 700 ppm; less than about 600 ppm; less than about 500 ppm; less than about 400 ppm; less than about 300 ppm; less than about 200 ppm; or less than about 100 ppm.T-12086-W001

[0229] In embodiments, the at least one contaminant can be in liquid or solid form. The at least one contaminant may be at least one of nitrogen, phosphorus, halogen (e.g., F, Cl, Br), and at least one metal. In embodiments, the at least one contaminant is at least one of a Group I, II, and transition metals, optionally, at least one of K, Ca, Mg, Ba, Si, Na, Fe, Si.

[0230] The non-pretreated lipid feedstock may comprise nitrogen as a contaminant. For example, the non-pretreated lipid feedstock may comprise greater than about 50 ppm nitrogen, greater than about 60 ppm nitrogen, greater than about 70 ppm nitrogen, greater than about 80 ppm nitrogen, greater than about 90 ppm nitrogen, greater than about 100 ppm nitrogen, about 50 ppm to about 200 ppm nitrogen, about 60 ppm to about 200 ppm nitrogen, about 70 ppm to about 200 ppm nitrogen, about 80 ppm to about 200 ppm nitrogen, or about 90 ppm to about 200 ppm nitrogen.

[0231] The non-pretreated lipid feedstock may comprise phosphorus as a contaminant. For example, the non-pretreated lipid feedstock may comprise greater than about 50 ppm phosphorus, greater than about 80 ppm phosphorus, greater than about 100 ppm phosphorus, greater than about 200 ppm phosphorus, greater than about 300 ppm phosphorus, greater than about 500 ppm phosphorus, about 50 ppm to about 700 ppm phosphorus, about 60 ppm to about 600 ppm phosphorus, about 70 ppm to about 500 ppm phosphorus, about 80 ppm to about 300 ppm phosphorus, or about 90 ppm to about 200 ppm phosphorus.

[0232] The non-pretreated lipid feedstock may comprise metal(s) as a contaminant. For example, the non-pretreated lipid feedstock may comprise greater than about 50 ppm metal(s), greater than about 80 ppm metal(s), greater than about 100 ppm metal(s), greater than about 150 ppm metal(s), greater than about 200 ppm metal(s), greater than about 300 ppm metal(s), about 50 ppm to about 600 ppm metal(s), about 60 ppm to about 500 ppm metal(s), about 70 ppm to about 300 ppm metal(s), about 80 ppm to about 200 ppm metal(s), or about 90 ppm to about 400 ppm metal(s). The metal(s) may be metal(s) selected from any of Group I, II, IV, and VIII metals (K, Ca, Mg, Ba, Si, Na, Fe, Si, etc.).

[0233] The non-pretreated lipid feedstock may comprise metal(s), nitrogen and / or phosphorus as contaminant(s), including but not limited to, any of the amounts described above. For example, the non-pretreated lipid feedstock may comprise greater than about 100 ppm metal(s) and phosphorus, greater than about 200 ppm metal(s) and phosphorus, greater than about 300 ppm metal(s) and phosphorus, greater than about 400 ppm metal(s) and phosphorus, greater than about 500 ppm metal(s) and phosphorus, greater than about 600 ppm metal(s) and phosphorus, about 100 ppm to about 1000 ppm metal(s) and phosphorus, about 150 ppm to about 600 ppm metal(s) and phosphorus, about 200 ppm to about 400 ppm metal(s) and phosphorus,T-12086-W001about 250 ppm to about 600 ppm metal(s) and phosphorus, or about 300 ppm to about 500 ppm metal(s) and phosphorus.

[0234] In embodiments, the non-pretreated lipid feedstock comprises a non-pretreated plant oil (e.g., may be used as-is after pressing or solvent extraction from plant(s) or plant seeds). The non-pretreated plant oil may have high levels of contaminants, including for example, nitrogen, phosphorus, and metals (K, Ca, Mg, Ba, Si, Na, Fe, Si, etc.). The number of contaminants may be those listed herein. In other embodiments, the plant oil comprises triglycerides and oxygen. In particular embodiments, there is greater than about 90% by wt. triglycerides and greater than about 5% by wt. oxygen.

[0235] In embodiments, the non-pretreated lipid feedstock comprises a non-pretreated plant oil (e.g., may be used as-is after pressing or solvent extraction from plant(s) or plant seeds) and at least one other source of lipids, such as animal fats, used cooking oil, waste grease, etc. The feedstock may have high levels of contaminants, including for example, nitrogen, phosphorus, and metals (K, Ca, Mg, Ba, Si, Na, Fe, Si, etc.). The amount of contaminants may be those listed herein (e.g., greater than about 50 ppm nitrogen and greater than about 100 ppm of combined phosphorus and metal contaminants).

[0236] Macroporous Hydroprocessing Catalyst

[0237] With respect to the macroporous hydroprocessing catalyst as used herein, the macroporous hydroprocessing catalyst comprises one or more macroporous hydroprocessing catalysts having a dual function. The macroporous hydroprocessing catalyst can remove at least one contaminant from a lipid feedstock and can function as a hydroprocessing catalyst. The macroporous hydroprocessing catalyst comprises one or more transition metals selected from Group VIA (Group 6) and Group VIII (Groups 8-10) metals. Group 6 elements may include chromium, molybdenum, and tungsten. Group 8-10 elements may include iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum. The catalyst may be in the oxidic and / or the sulphidic form. In some embodiments, the catalyst comprises one or more components of nickel and / or cobalt and one or more components of molybdenum and / or tungsten or one or more components of platinum and / or palladium. Catalysts containing nickel and molybdenum, nickel and tungsten, platinum and / or palladium are useful. Some examples are Mo, Fe, W, Co, Ni, Zn, Pt and Pd. The catalyst(s) may also contain one or more support materials, for example zeolite, alumina, silica, alumina-silica, zirconia, alumina-silica-zeolite and activated carbon. In embodiments, the catalyst may be Mo, MoS2, NiMo, NiS, CoO, MoO3, NiO, and / or a mixture thereof (e.g. self-supported). The catalyst may have one or more support materials selected from zeolite, alumina, silica, zeolite-alumina, alumina-silica, alumina-silica-T-12086-W001zeolite and activated carbon. In embodiments, the macroporous hydroprocessing catalyst comprises one or more self-supported Mo, MoS2, NiS, and alumina supported NiMo catalysts.

[0238] In embodiments, the macroporous hydroprocessing catalysts may be in sulfide form, comprising at least one Group VIB metal such as Mo or W, or at least one Group VIII metal such as Co, Ni or Fe, or at least one Group IIB metal such as Zn, or a combination thereof, e.g., molybdenum sulfide, nickel sulfide, molybdenum nickel sulfide, molybdenum cobalt sulfide, tungsten nickel sulfide, iron sulfide, zinc sulfide, or iron zinc sulfide. It can also be the precursor of those catalysts which can be activated in the reactors. Organo-metal compounds, such as organo-Mo, organo-Ni, or organo-Fe, can also be used.

[0239] The macroporous hydroprocessing catalyst may be a precursor, such as an organometallic precursor (e.g. organo-Mo like Mo-octanoate), which can be activated in-situ to form colloidal or nanometer or micron sized catalysts. The macroporous hydroprocessing catalyst may be a pre-activated nano-size or micron-sized slurry catalyst.

[0240] In embodiments, the macroporous hydroprocessing catalyst is capable of removing at least one contaminant from the non-pretreated lipid feedstock. For example, the macroporous hydroprocessing catalyst can remove at least one of: greater than about 90% oxygen, greater than about 80% nitrogen, greater than about 99% phosphorus, and greater than about 99% of at least one metal.

[0241] In embodiments, the macroporous hydroprocessing catalysts have large macropore volume and peak position, low density, etc. Without being bound by theory, the macroporous hydroprocessing catalyst may allow access of at least one contaminant to catalyst pores (e.g., large pore size), provide enough macropore volume to catch contaminants (e.g., greater macropore volume), and achieve effective catalyst suspension (e.g., low catalyst density).

[0242] In embodiments, the macroporous hydroprocessing catalyst has at least one macropore peak, per the pore size distribution profile measured by a suitable pore size measurement process (e.g. via a mercury intrusion porosimeter according to ASTM D4284), wherein the macropore peak position (i.e., average macropore diameter) is at about 1200 A or greater than 1200 A. In other examples, the macropore peak position is at about 1300 A or greater than 1300 A, at about 1400 A or greater than 1400 A, at about 1500 A or greater than 1500 A, at about 1600 A or greater than 1600 A, at about 1700 A or greater than 1700 A, at about 1800 A or greater than 1800 A, at about 1900 A or greater than 1900 A, at about 2000 A or greater than 2000 A, at about 2100 A or greater than 2100 A, at about 2200 A or greater than 2200 A, at about 2300 A or greater than 2300 A, at about 2400 A or greater than 2400 A, at about 2500 A or greater than 2500 A, at about 2600 A or greater than 2600 A, at about 2700 A or greater than 2700 A, at about 2800 A or greater than 2800 A, at about 2900 A or greater thanT-12086-W0012900 A, at about 3000 A or greater than 3000 A, at about 1200 A to about 5000 A, at about 1500 A to about 5000 A, at about 1700 A to about 5000 A, at about 2000 A to about 5000 A, at about 2000 A to about 4000 A, and / or at about 2000 A to about 3000 A.

[0243] In embodiments, the macroporous hydroprocessing catalyst has a suitable density to, for example, provide effective catalyst suspension (e.g., ebullition). The particle density may be less than about 0.95 g / cc, less than about 0.9 g / cc, less than about 0.85 g / cc, less than about 0.8 g / cc, less than about 0.75 g / cc, less than about 0.7 g / cc, less than about 0.65 g / cc, less than about 0.6 g / cc, less than about 0.5 g / cc, less than about 0.4 g / cc, or less than about 0.3 g / cc, about 0.3 to about 0.9 g / cc, about 0.4 to about 0.9 g / cc, about 0.5 to about 0.9 g / cc, about 0.6 to about 0.9 g / cc, or about 0.65 to about 0.9 g / cc.

[0244] In embodiments, the macropores of the macroporous hydroprocessing catalyst are pores having a pore size of at least about 1000 A, and the the macroporous hydroprocessing catalyst has a macropore volume of at least about 0.05 cc / g, at least about 0.10 cc / g, at least about 0.20 cc / g, at least about 0.30 cc / g, at least about 0.40 cc / g, at least about 0.50 cc / g, at least about 0.60 cc / g, at least about 0.70 cc / g, at least about 0.80 cc / g, at least about 0.90 cc / g, at least about 1.0 cc / g, at least about 1.1 cc / g, at least about 1.2 cc / g, at least about 1.3 cc / g, at least about 1.4 cc / g, at least about 1.5 cc / g, at least about 1.6 cc / g, at least about 1.7 cc / g, at least about 1.8 cc / g, at least about 1.9 cc / g, about 0.10 to about 2.0 cc / g, about 0.10 to about 1.9 cc / g, about 0.10 to about 1.8 cc / g, about 0.10 to about 1.7 cc / g, about 0.10 to about 1.6 cc / g, about 0.10 to about 1.5 cc / g, about 0.20 to about 1.6 cc / g, about 0.20 to about 1.5 cc / g, or about 0.50 to about 1.5 cc / g.

[0245] In embodiments, the macroporous hydroprocessing catalyst has a total pore volume of at least about 0.50 cc / g, at least about 0.60 cc / g, at least about 0.70 cc / g, at least about 0.80 g / cc, at least about 0.9 g / cc, at least about 1.0 cc / g, at least about 1.2 g / cc, at least about 1.5 cc / g, at least about 2.0 cc / g, at least about 2.50 cc / g, at least about 3.0 cc / g, about 0.50 to about 3.0 cc / g, about 1.0 to about 3.0 cc / g, about 1.0 to about 2.9 cc / g, about 1.0 to about 2.8 cc / g, about 1.0 to about 2.7 cc / g, about 1.0 to about 2.6 cc / g, about 1.0 to about 2.5 cc / g, or about 1.0 to about 2.5 cc / g.

[0246] In embodiments, the macroporous hydroprocessing catalyst has a fractionof macropore volume relative to the total pore volume of at least about 10%, at least about 15%, at least about 20%, about 10 to about 50%, about 15 to about 50%, about 15 to about 45%, about 15 to about 40%, about 20 to about 50%, about 20 to about 45%, about 20 to about 40%, about 25 to about 50%, about 25 to about 45%, or about 25 to about 40%.

[0247] In embodiments, the macroporous hydroprocessing catalyst may be a slurry catalyst, an extrudate catalyst, a pellet catalyst, or a sphere catalyst. The particle size / particle diameterT-12086-W001may be determined using suitable techniques such as sieve analysis, laser diffraction, dynamic light scattering and direct imaging techniques. One example is to determine particle size distribution using laser diffraction, with standard test method ASTM D4464-15.

[0248] In one embodiment, the macroporous hydroprocessing catalyst is a slurry catalyst. The mean particle size of the catalyst solids in the slurry catalyst is greater than about 1 micron, greater than about 3 microns, greater than about 5 microns, greater than about 10 microns, about 5 microns to about 300 microns, about 10 microns to about 100 microns, about 10 microns to about 30 microns, or about 10 microns to about 20 microns.

[0249] In one embodiment, the macroporous hydroprocessing catalyst has a nominal particle size of at least about 0.65 mm (1 / 40"). In some embodiments, the particles of the macroporous hydroprocessing catalyst have a spherical shape with a particle diameter of at least about 0.5 mm, at least about 1 mm, at least about 2 mm, about 1 mm to about 6 mm, or about 2 mm to about 5 mm. In another embodiment, the macroporous hydroprocessing catalyst comprises pellets or grains that are about 1 mm to about 1.5 mm in size. In one embodiment, the macroporous hydroprocessing catalyst is an extrudate having a cylindrical shape with a cross-sectional diameter of at least about 0.5 mm (1 / 50”), at least about 0.65 mm (1 / 40”), at least about 0.79 mm (1 / 32”), at least about 1.06 mm (1 / 24”), at least about 1.27 mm (1 / 20”), or about 0.5 mm to about 1.5 mm. The length of the extrudate catalyst ranges from about 0.5 mm to about 10 mm, about 2 mm to about 8 mm, about 2 mm to about 6 mm, or longer than about 1 mm, In another embodiment, the extrudate catalyst is in quadruple shape, with the cross section diameter (long side) in the range from about 1.0 mm (0.04 inch) to about 10 mm (0.4 inch), and a length normal to the cross sectional diameter such that the length to diameter ratio is in the range from about 1 to about 8. In one embodiment, the macroporous hydroprocessing catalyst has an irregular shape.

[0250] While it is desirable to employ macroporous hydroprocessing catalyst with uniform dimensions, a small fraction of macroporous hydroprocessing catalyst may have dimensions that fall outside of these ranges. The macroporous hydroprocessing catalyst may have one or more of the features recited herein.

[0251] The macroporous hydroprocessing catalyst may be any suitable macroporous hydroprocessing catalyst. It may be a macroporous ebullated (EB) reactor catalyst, a macroporous slurry catalyst, a macroporous UFR catalyst, a macroporous hydrocracking catalyst, or a combination thereof.

[0252] The macroporous hydroprocessing catalyst may, in some embodiments, be an ebullated bed catalyst having one or more of the properties listed above. The ebullated bed catalyst may be a supported ebullated bed catalyst and may be a commercial grade catalyst suchT-12086-W001as those which can be purchased at Advanced Refining Technologies, LLC. The macroporous hydroprocessing catalyst may be a catalyst such as those described in U.S. Patent No. 7,642,212, the entire disclosure of which is hereby incorporated by reference herein.

[0253] The macroporous hydroprocessing catalyst may, in at least some other embodiments, be a slurry catalyst having one or more of the properties listed above. The slurry catalyst may be a preactivated slurry catalyst. The macroporous hydroprocessing catalyst may be a catalyst such as those described in U.S. Patent No. 8,703,637 and US Patent No. 8,802,587, the entire disclosures of which are hereby incorporated by reference herein.

[0254] Non-pretreated Lipid Feedstock and Macroporous hydroprocessing catalyst

[0255] In embodiments, once the non-pretreated lipid feedstock is reacted with the macroporous hydroprocessing catalyst, a first product (e.g., intermediate product(s)) is formed. The first product may comprise at least one of less than about 2% oxygen, less than about 30 ppm nitrogen, and less than about 20 ppm combined phosphorus and at least one metal contaminant.

[0256] In embodiments, the first product (e.g., intermediate product(s)) comprises less than about 2% oxygen, less than about 1.5% oxygen, less than about 1.0% oxygen, less than about 0.5% oxygen, or less than about 0.25% oxygen.

[0257] In embodiments, the first product (e.g., intermediate product(s)) comprises less than about 30 ppm nitrogen, less than about 25 ppm nitrogen, less than about 20 ppm nitrogen, less than about 15 ppm nitrogen, less than about 10 ppm nitrogen, or less than about 5 ppm nitrogen.

[0258] In embodiments, the first product (e.g., intermediate product(s)) comprises less than about 20 ppm combined phosphorus and at least one metal contaminant, less than about 15 ppm combined phosphorus and at least one metal contaminant, less than about 10 ppm combined phosphorus and at least one metal contaminant, or less than about 5 ppm combined phosphorus and at least one metal contaminant.

[0259] Various features disclosed herein are, for brevity, described in the context of a single embodiment, but may also be provided separately or in any suitable sub-combination. All combinations of the embodiments are specifically embraced by the embodiments disclosed herein just as if each and every combination was individually and explicitly disclosed. In addition, all sub-combinations listed in the embodiments describing such variables are also specifically embraced by the present compositions and are disclosed herein just as if each and every such sub-combination was individually and explicitly disclosed herein.

[0260] While the above description contains many specifics, these specifics should not be construed as limitations of the present disclosure, but merely as exemplifications of preferredT-12086-W001embodiments thereof. Those skilled in the art will envision many other embodiments within the scope and spirit of the present disclosure as defined by the claims appended hereto.

[0261] A more complete understanding can be obtained by reference to the following specific Examples. These Examples are described solely for purposes of illustration and are not intended to limit the scope of the invention. Changes in form and substitution of equivalents are contemplated as circumstances may suggest or render expedient. Without further description, it is believed that one of ordinary skill in the art can, using the preceding description and the following illustrative examples, make and utilize the constructs of the present disclosure and practice the claimed processes and / or systems. The following working examples, therefore, specifically point out the typical aspects of the present disclosure and are not to be construed as limiting in any way in the remainder of the disclosure. Although specific terms have been employed herein, such terms are intended in a descriptive sense and not for purposes of limitation.EXAMPLES

[0262] All feeds in reactors undergo various reactions in the presence of hydrogen and catalyst, such as hydrogenation, hydrocracking, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenization, hydrodemetallization, etc.Example 1

[0263] Table 1 lists the properties of a non-pretreated soybean oil feedstock (Example 1). This non-pretreated soybean oil feedstock contained 50 ppm sulfur, 220 ppm nitrogen and 11.5 wt% oxygen. It also contained about 1 ppm chlorine, 20.9 ppm calcium, 230 ppm potassium, 37 ppm magnesium and 606 ppm phosphorous. The Comparative Example 1 in Table l is a pretreated soybean oil that had been RBD (Refined, Bleached and Deodorized) processed, and that contained less than 5 ppm sulfur, 1 ppm nitrogen, and less than 0.5 ppm of Ca, Fe, K, Mg, Na and P.Table 1: Feedstock PropertiesComparative Example 1 Example 1Properties Test method RBD (Refined, Bleached Non-pretreatedand Deodorized) Soybean Soybean oilOilAPI, degree ASTM D4052 21.1 21.7Density at 15°C,ASTM D4052 0.93 0.92g / mlT-12086-W001S, wt-ppm ASTMD2622 50 <5N, wt-ppm ASTMD5762 220 1C, wt% ASTMD5291 77.2 78.0H, wt% ASTMD5291 11.3 11.3O, wt% By elemental „5 10 7balanceA™ ’m8' ASTM D664 1.19 <0.05KOH / gBr# ASTMD1159 59 59H2O, wt-ppm ASTMD6304-16 188 63Cl, wt-ppm ,Byion, 11 11chromatographCa, wt-ppm By ICP-AES 20.9 <0.11Fe, wt-ppm By ICP-AES <0.41 <0.21K, wt-ppm By ICP-AES 230 <0.41Mg, wt-ppm By ICP-AES 37 <0.11Na, wt-ppm By ICP-AES <4.8 <0.21P, wt-ppm By ICP-AES 606 <0.21Examples 2 and 3:Catalyst A (Example 2):

[0264] Catalyst A (Example 2) is a self-supported M0S2 and NiS catalyst that is structured as a slurry catalyst. The properties of Catalyst A are defined in Table 2. Catalyst A is a catalyst such as those described in U.S. Patent No. 8,703,637 and US Patent No. 8,802,587, the entire disclosures of which are incorporated by reference herein. In this specific example, the slurry form of Catalyst A was prepared with salt precursors of Mo and Ni. The salt precursors of Mo and Ni were put through sulfidation and reduction processes and were then dispersed in situ in a liquid oil carrier (such as VGO) to form a slurry. The solids in the slurry were then separated with liquid via filtration. Catalyst A had a total pore volume at 2.36 ml / g, a macropore volume (1000-50000 A) at 1.51 ml / g, and macropore peaks at 2000 and 22000 A.Catalyst B (Example 3):T-12086-W001

[0265] Catalyst B (Example 3) is an alumina supported NiMo catalyst that is an ebullated bed catalyst. Catalyst B was prepared via an incipient wetness impregnation method, by impregnating an aqueous solution containing molybdenum and nickel salts onto alumina support. The starting materials of the aqueous solution were molybdenum trioxide, nickel carbonate and phosphoric acid. After impregnation, the catalyst was extruded, dried, and calcined to form the final catalyst. The properties are defined in Table 2. Catalyst B can be a catalyst such as those described in U.S. Patent No. 7,642,212, the entire disclosure of which is incorporated by reference herein. Catalyst B had a total pore volume at 1.02 ml / g, a macropore volume at 0.26 ml / g, and a macropore peak at 2900 A.Table 2: Properties of Catalysts A and BExample 2 Example 3Catalyst A1Catalyst B1Total pore volume, ml / g 2.36 1.02Macropore volume (1000-500001.51 0.26A)Macropore peak position, A 2000 and 22000 2900'Mercury intrusion porosimetry of catalysts as measured by ASTM D4284 Examples 4 to 6:First Stage Reaction:

[0266] About 500 g of non-pretreated soybean oil (Example 1) was added into a 1-L autoclave slurry reactor with about 24 g of a slurry catalyst (i.e., about 10% solids and 90% carrier oil as vacuum gas oil). The slurry catalyst contained about 2.4 g of Catalyst A (Example 2). The feedstock was processed in the autoclave slurry reactor at about 371°C, at about 1400 psig, and in EE gas flowing at about 3.6 scf / hr, for about 5 min (Example 4), about 60 min (Example 5), or about 120 min (Example 6).

[0267] After reaction, the reactor was cooled down to ambient temperature to recover products. The reactor drainage contained liquid products and solids. The solids from the slurry phase were separated by filtration and analyzed. The conversion was calculated as follows:Conversion = [( Content in Feed x Amount of Feed) - ( Content in Liquid Product x Amount of Liquid Product) ] / (Content in Feed x Amount of Feed)where, the content refers to 538°C+, 360°C+, oxygen, nitrogen, phosphorous, or metal contaminants. The 538°C+ and 360°C+ components were determined based on ASTM D 7398,T-12086-W001ASTM D7169 or ASTM D6352. After about 2 hours (Example 6), 100% of 538°C+ components were converted to a product with a boiling point less than about 538°C. The conversion of components with boiling points at about 360°C or greater than about 360°C+ was about 93%, while the conversion of N and O was about 91% and about 99.8%, respectively. The products were mainly normal paraffins. The acid number was less than about 0.05 mg-KOH / g. Its oxygen content was about 0.03 wt% and nitrogen content were about 24 ppm. The level of P and metals, such as K, Ca, Mg, Na, Fe and Si, was under detection limit, and the combined total level of P with metals was less than about 10 ppm.

[0268] The above liquid products were further processed in a second stage fixed-bed reactor loaded with about 15% hydrotreating catalyst, about 10% methanation catalyst and about 75% isomerization catalyst. The reaction was carried out at about 600°C, with a liquid hourly space velocity (LHSV) at 1.0 hr’1. About 100% conversion of oxygen and nitrogen was achieved, and the n-paraffin was transformed into iso-paraffins and meeting the specifications for gasoline, SAF and diesel.Table 3: Performance of the Feedstock in Example 1 with Macroporous hydroprocessing catalyst AExample 4 Example 5 Example 6FeedFeed from Example 1 Feed from Example 1 Feed from Example 1 Pressure, psig 1400 1400 1400 Temperature, °C 371 371 371 Residence Time, min 5 60 120Conversion538°C+ 91% 96% 100%360°C+ 59% 84% 93%N 53% 69% 91%O * 62% 93% 99.8%Product QualityAPI, Degree 38.7 44.1 46.9Acid #, mg-KOH / g 57.0 8.9 0.05O *, wt% 4.40 1.00 0.03N, ppm 94 81 24P, ppm Under detection limit Under detection limit Under detection limitT-12086-W001K, Ca, Mg, Na, Si,Under detection limit Under detection limit Under detection limit PPm* Oxygen content in product was determined by fast-neutron activation analysis (FNAA) per ASTME385-16.

[0269] All publications, patents and patent applications cited above are herein incorporated by reference in their entirety to the same extent as if each individual publication, patent, or patent application were specifically and individually indicated to be incorporated by reference in its entirety.

[0270] Although certain embodiments have been described herein in detail, it will be understood by those skilled in the art that variations may be made thereto without departing from the spirit of the invention or the scope of the appended claims.

[0271] For the avoidance of doubt, the present application is directed to the subject-matter described in the following numbered paragraphs:1. A process for making a renewable product from a non-pretreated lipid feedstock, the process comprising:hydroprocessing the non-pretreated lipid feedstock with at least one macroporous hydroprocessing catalyst under hydroprocessing conditions to produce the renewable product, wherein the macroporous hydroprocessing catalyst removes at least one contaminant from the non-pretreated lipid feedstock.2. The process of paragraph 1, wherein the macroporous hydroprocessing catalyst has a suitable density to provide effective catalyst suspension.3. The process of paragraph 1 or 2, wherein the macroporous hydroprocessing catalyst has an average macropore pore size of about 1200 A or greater than about 1200 A.4. The process of any one of paragraphs 1 to 3, wherein the macroporous hydroprocessing catalyst has a macropore volume at about 0.05 cc / g or greater and a macropore peak greater than about 1000 A.5. The process of any one of paragraphs 1 to 4, wherein the macroporous hydroprocessing catalyst has a particle density of about 0.95 g / cc or less than about 0.95 g / cc.6. The process of any one of paragraphs 1 to 5, wherein the non-pretreated lipid feedstock with the macroporous hydroprocessing catalyst forms a first product comprising at least one of less than about 2% oxygen, less than about 30 ppm N, and less than about 20 ppm combined phosphorus and at least one metal contaminant.T-12086-W0017. The process of any one of paragraphs 1 to 6, wherein the macroporous hydroprocessing catalyst removes at least one of greater than about 90% oxygen, greater than about 80% nitrogen, greater than about 99% phosphorus, greater than about 99% of at least one metal.8. The process of any one of paragraphs 1 to 7, wherein the macroporous hydroprocessing catalyst comprises one or more transition metals selected from Group VIA (Group 6) and Group VIII (Groups 8-10) metals.9. The process of any one of paragraphs 1 to 8, wherein the macroporous hydroprocessing catalyst comprises one or more transition metals selected from Mo, Fe, W, Co, Ni, Zn, Pt and Pd.10. The process of any one of paragraphs 1 to 9, wherein the macroporous hydroprocessing catalyst is a self-supported catalyst that comprises at least one catalyst of Mo, M0S2, NiMo, NiS, CoO, MoOs, NiO, and / or a mixture thereof.11. The process of any one of paragraphs 1 to 10, wherein the macroporous hydroprocessing catalyst comprises a self-supported M0S2 and NiS catalyst.12. The process of any one of paragraphs 1 to 11, wherein the macroporous hydroprocessing catalyst further comprises one or more support materials such as zeolite, alumina, silica, alumina-silica, zirconia, alumina-silica-zeolite or activated carbon.13. The process of any one of paragraphs 1 to 12, wherein the macroporous hydroprocessing catalyst comprises NiMo supported catalysts on alumina.14. The process of any one of paragraphs 1 to 13, wherein the macroporous hydroprocessing catalyst is a precursor, such as an organo-metal precursor, which can be activated in-situ to form colloidal or nanometer or micron size catalysts.15. The process of any one of paragraphs 1 to 14, wherein the macroporous hydroprocessing catalyst is a pre-activated micron-size slurry catalyst.16. The process of any one of paragraphs 1 to 15, wherein the macroporous hydroprocessing catalyst is selected from a macroporous ebullated (EB) reactor catalyst, a macroporous slurry catalyst, a macroporous upflow reactor catalyst, a macroporous hydrocracking catalyst, or a combination thereof.17. The process of any one of paragraphs 1 to 16, wherein the macroporous hydroprocessing catalyst has a particle density of less than about 0.95 g / cc, less than about 0.9 g / cc, less than about 0.85 g / cc, less than about 0.8 g / cc, less than about 0.75 g / cc, less than about 0.7 g / cc, less than about 0.65 g / cc, less than about 0.6 g / cc, less than about 0.5 g / cc, less than about 0.4 g / cc,T-12086-W001or less than about 0.3 g / cc, about 0.3 to about 0.9 g / cc, about 0.4 to about 0.9 g / cc, about 0.5 to about 0.9 g / cc, about 0.6 to about 0.9 g / cc, or about 0.65 to about 0.9 g / cc18. The process of any one of paragraphs 1 to 17, wherein the macroporous hydroprocessing catalyst has a macropore peak position that is at about 1200 A or greater than 1200 A, at about 1300 A or greater than 1300 A, at about 1400 A or greater than 1400 A, at about 1500 A or greater than 1500 A, at about 1600 A or greater than 1600 A, at about 1700 A or greater than 1700 A, at about 1800 A or greater than 1800 A, at about 1900 A or greater than 1900 A, at about 2000 A or greater than 2000 A, at about 2100 A or greater than 2100 A, at about 2200 A or greater than 2200 A, at about 2300 A or greater than 2300 A, at about 2400 A or greater than 2400 A, at about 2500 A or greater than 2500 A, at about 2600 A or greater than 2600 A, at about 2700 A or greater than 2700 A, at about 2800 A or greater than 2800 A, at about 2900 A or greater than 2900 A, at about 3000 A or greater than 3000 A, at about 1200 A to about 5000 A, at about 1500 A to about 5000 A, at about 1700 A to about 5000 A, at about 2000 A to about 5000 A, at about 2000 A to about 4000 A, and / or at about 2000 A to about 3000 A.19. The process of any one of paragraphs 1 to 18, wherein the macroporous hydroprocessing catalyst has a macropore volume of at least 0.01 cc / g, at least about 0.05 cc / g, at least about 0.10 cc / g, at least about 0.20 cc / g, at least about 0.30 cc / g, at least about 0.40 cc / g, at least about 0.50 cc / g, at least about 0.60 cc / g, at least about 0.70 cc / g, at least about 0.80 cc / g, at least about 0.90 cc / g, at least about 1.0 cc / g, at least about 1.1 cc / g, at least about 1.2 cc / g, at least about 1.3 cc / g, at least about 1.4 cc / g, at least about 1.5 cc / g, at least about 1.6 cc / g, at least about 1.7 cc / g, at least about 1.8 cc / g, at least about 1.9 cc / g, about 0.10 to about 2.0 cc / g, about 0.10 to about 1.9 cc / g, about 0.10 to about 1.8 cc / g, about 0.10 to about 1.7 cc / g, about 0.10 to about 1.6 cc / g, about 0.10 to about 1.5 cc / g, about 0.20 to about 1.6 cc / g, about 0.20 to about 1.5 cc / g, or about 0.50 to about 1.5 cc / g.20. The process of any one of paragraphs 1 to 19, wherein the macroporous hydroprocessing catalyst has a total pore volume of at least about 0.50 cc / g, at least about 0.60 cc / g, at least about 0.70 cc / g, at least about 0.80 g / cc, at least about 0.9 g / cc, at least about 1.0 cc / g, at least about 1.5 cc / g, at least about 2.0 cc / g, at least about 2.50 cc / g, at least about 3.0 cc / g, about 0.50 to about 3.0 cc / g, about 1.0 to about 3.0 cc / g, about 1.0 to about 2.9 cc / g, about 1.0 to about 2.8 cc / g, about 1.0 to about 2.7 cc / g, about 1.0 to about 2.6 cc / g, about 1.0 to about 2.5 cc / g, or about 1.0 to about 2.5 cc / g.21. The process of any one of paragraphs 1 to 20, wherein the at least one contaminant in the non-pretreated feedstock is present in an amount of less than about 2000 ppm; less than about 1500 ppm; less than about 1000 ppm; less than about 900 ppm; less than about 800 ppm; lessT-12086-W001than about 700 ppm; less than about 600 ppm; less than about 500 ppm; less than about 400 ppm; less than about 300 ppm; less than about 200 ppm; or less than about 100 ppm.22. The process of any one of paragraphs 1 to 21, wherein the at least one contaminant comprises at least one liquid and / or at least one solid.23. The process of any one of paragraphs 1 to 22, wherein the at least one contaminant is selected from at least one of nitrogen, phosphorus, and at least one metal.24. The process of any one of paragraphs 1 to 23, wherein the at least one contaminant is selected from at least one of a Group I, II, and transition metals, optionally, at least one of K, Ca, Mg, Ba, Si, Na, Fe, Si.25. The process of any one of paragraphs 1 to 24, wherein the hydroprocessing of the nonpretreated lipid feedstock occurs in a first stage comprising at least one reactor.26. The process of paragraph 25, wherein the at least one reactor is selected from an ebullating-bed (EB) reactor, a slurry-bed reactor, and an up-flow reactor (UFR).27. The process of any one of paragraphs 1 to 24, wherein the at least one contaminant is removed in the first stage via deposition on / impregnation in the catalyst and removing at least a portion of the catalyst from the first stage.28. The process of paragraph 27, wherein the removing of said at least a portion of the catalyst comprises removing the catalyst intermittently.29. The process of paragraph 27 or 28, wherein the removing of said at least a portion of the catalyst comprises removing the catalyst via a liquid product.30. The process of paragraph 25, wherein the hydroprocessing comprises at least one of i) heating from about 500 °F to about 800°F; ii) pressure is about 300 psig to about 3000 psig; iii) liquid hourly space velocity (LHSV) at about 0.1 h'1to about 3.0 h’1; iv) hydrogen-containing gas flow rate of about 2000 SCF / bbl to about 10000 SCF / bbl.31. The process of paragraph 25, wherein the hydroprocessing comprises, in a first stage, at least one of i) heating from about 580 °F to about 780°F; ii) pressure is about 300 psig to about 3000 psig; iii) liquid hourly space velocity (LHSV) at about 0.1 h'1to about 3.0 h’1; iv) hydrogen-containing gas flow rate of about 2500 SCF / bbl to about 10000 SCF / bbl.32. The process of any one of paragraphs 25, 30, and 31, wherein the hydroprocessing comprises, in a second stage, at least one of i) heating from about 500 °F to about 800°F; ii) pressure is about 300 psig to about 3000 psig; iii) liquid hourly space velocity (LHSV) at aboutT-12086-W0010.1 h'1to about 3.0 h’1; iv) hydrogen-containing gas flow rate of about 2000 SCF / bbl to about 10000 SCF / bbl.33. The process of any one of paragraphs 25 and 30 to 32, wherein the hydroprocessing further comprises adding a sulfiding agent to maintain a ratio of H2S to the non-pretreated feedstock at about 100 ppm or greater.34. The process of any one of paragraphs 25 and 30 to 33, wherein hydroprocessing further comprises at least one hydrotreating catalyst.35. The process of any one of paragraphs 25 and 30 to 34, wherein partial conversion of oxygen occurs in the first stage.36. The process of any one of paragraphs 1 to 35, further comprising separating i) gaseous product(s) from ii) liquid(s) and solid(s).37. The process of paragraph 36, further comprising substantially separating the liquid(s) from the solid(s) in ii).38. The process of paragraph 36 or 37, further comprising hydrotreating the liquid(s) from ii).39. The process of paragraph 36 or 37, wherein the liquid-solid separation comprises at least one of filtration, centrifuge, electrostatic precipitation, settling, and evaporation.40. The process of any one of paragraphs 36 to 39, wherein the liquid-solid separation comprises at least one of dead-end filter, cross-flow filter, and filter press.41. The process of any one of paragraphs 1 to 40, wherein non-pretreated lipid feedstock comprises plant oil(s).42. The process of paragraph 41, wherein the plant oil(s) comprises greater than about 50 ppm N and greater than about 100 ppm combined phosphorus and at least one metal contaminant. 43. The process of any one of paragraphs 41 to 42, wherein the plant oil(s) are derived from a plant and / or plant seeds that have been pressed and / or extracted.44. The process of any one of paragraphs 1 to 43, wherein the non-pretreated lipid feedstock comprises triglycerides.45. The process of paragraph 44, wherein the non-pretreated lipid feedstock comprises greater than about 90% triglycerides and has greater than about 5% oxygen.46. The process of any one of paragraphs 1 to 45, wherein the non-pretreated lipid feedstock further comprises other sources of lipids.T-12086-W00147. The process of paragraph 46, wherein the other sources of lipids comprise at least one of animal fats, used cooking oil, waste grease, and a combination thereof.48. The process of any one of paragraphs 1 to 47, wherein the non-pretreated lipid feedstock comprises plastic pyrolysis-oil.49. The process of any one of paragraphs 1 to 47, wherein hydroprocessing comprises hydrogenation of the olefins of triglycerides (7g) to obtain hydrogenated triglycerides (HTg) and the hydrogenated triglycerides are transformed by hydrogenolysis into fatty acids ( 4), and waxes.50. The process of any one of paragraphs 1 to 48, wherein hydroprocessing further comprises hydrodeoxygenation (HDO), decarbonylation (DCO), decarboxylation (DCO2), hydrocracking, isomerization, dehydrogenation, and / or dearomatization.51. The process of any one of paragraphs 1 to 50, wherein the hydroprocessing comprises a first and a second stage, the second stage including a fixed-bed reactor.52. The process of paragraph 51, wherein the second stage further comprises at least one catalyst selected from at least one of a hydrotreating catalyst for removing at least one contaminant and an isodewaxing catalyst to improve pour point and cloud point.53. The process of paragraph 51, wherein the second stage has at least three types of catalysts comprising hydrotreating catalyst, a hydrogenation catalyst, and an isomerization catalyst.54. The process of paragraph 51, wherein the second stage has a first layer having the hydrotreating catalyst; a second layer having the hydrogenation catalyst; and a third layer having an isomerization catalyst.55. The process of paragraph 51, wherein the second stage has a first layer having about 5% to about 20% of the hydrotreating catalyst; a second layer having about 3% to about 10% of the hydrogenation catalyst; and a third layer having an isomerization catalyst.56. The process of any one of paragraphs 54 to 55, wherein the first layer substantially eliminates contaminants, the second layer converts CO to methane and the third layer substantially converts n-paraffins into iso-paraffins.57. The process of any one of paragraphs 51 to 56, wherein product(s) from the first stage comprise liquid product(s) that are fed into the second stage and solid product(s).58. The process of any one of paragraph 57, wherein a portion of the liquid product(s) from the first stage are fed back to the first stage.T-12086-W00159. The process of any one of paragraphs 57 to 58, wherein at least a portion of the solid product(s) is recovered.60. The process of paragraph 59, wherein if the solid product(s) contain macroporous hydroprocessing catalyst, the solid product(s) is washed to remove salt(s) and fed back to the first stage.61. The process of paragraph 60, wherein the washed solid product(s) is added to the nonpretreated lipid feedstock and fed back to the first stage.62. The process of any one of paragraphs 51 to 61, further comprising separating and fractionating to separate gaseous products from renewable products.63. A system for making a renewable product from a non-pretreated lipid feedstock, the system comprising:a first stage having at least one reactor for hydroprocessing the non-pretreated lipid feedstock with at least one macroporous hydroprocessing catalyst under hydroprocessing conditions to produce the renewable product;wherein the macroporous hydroprocessing catalyst removes at least one contaminant from the non-pretreated lipid feedstock.64. The system of paragraph 63, wherein the at least one reactor is configured for at least partially converting oxygen within the non-pretreated lipid feedstock via the at least one macroporous hydroprocessing catalyst.65. The system of paragraph 63 or 64, further comprising:a second stage having at least one secondary reactor for hydrotreating at least one intermediate product produced in the first stage to complete oxygen conversion and remove contaminants.66. The system of any one of paragraphs 63 to 65, wherein the at least one reactor of the first stage comprises an ebullating-bed or a slurry-bed reactor.67. The system of any one of paragraphs 65 to 66, wherein the at least one secondary reactor of the second stage comprises a fixed-bed reactor.68. The system of any one of paragraphs 63 to 67, wherein the macroporous hydroprocessing catalyst has a suitable density to provide effective catalyst suspension.69. The system of any one of paragraphs 63 to 68, wherein the macroporous hydroprocessing catalyst has an average macropore pore size of about 1200 A or greater than about 1200 A.T-12086-W00170. The system of any one of paragraphs 63 to 69, wherein the macroporous hydroprocessing catalyst has a macropore volume at about 0.05 cc / g or greater and a macropore peak greater than about 1000 A.71. The system of any one of paragraphs 63 to 70, wherein the macroporous hydroprocessing catalyst has a particle density of about 0.95 g / cc or less than about 0.95 g / cc.72. The system of any one of paragraphs 63 to 71, wherein the non-pretreated lipid feedstock with the macroporous hydroprocessing catalyst forms a first product comprising at least one of less than about 2% oxygen, less than about 30 ppm N, and less than about 20 ppm combined phosphorus and at least one metal contaminant.73. The system of any one of paragraphs 63 to 72, wherein the macroporous hydroprocessing catalyst removes at least one of greater than about 90% oxygen, greater than about 80% nitrogen, greater than about 99% phosphorus, greater than about 99% of at least one metal.74. The system of any one of paragraphs 63 to 73, wherein the macroporous hydroprocessing catalyst comprises one or more transition metals selected from Group VIA (Group 6) and Group VIII (Groups 8-10) metals.75. The system of any one of paragraphs 63 to 74, wherein the macroporous hydroprocessing catalyst comprises one or more transition metals selected from Mo, Fe, W, Co, Ni, Zn, Pt and Pd.76. The system of any one of paragraphs 63 to 75, wherein the macroporous hydroprocessing catalyst is a self-supported catalyst that comprises at least one catalyst of Mo, M0S2, NiMo, NiS, CoO, MoOs, NiO, and / or a mixture thereof.77. The system of any one of paragraphs 63 to 76, wherein the macroporous hydroprocessing catalyst comprises a self-supported M0S2 and NiS catalyst.78. The system of any one of paragraphs 63 to 77, wherein the macroporous hydroprocessing catalyst further comprises one or more support materials such as zeolite, alumina, silica, alumina-silica, zirconia, alumina-silica-zeolite or activated carbon.79. The system of any one of paragraphs 63 to 78, wherein the macroporous hydroprocessing catalyst comprises NiMo supported catalysts on alumina.80. The system of any one of paragraphs 63 to 78, wherein the macroporous hydroprocessing catalyst is a precursor, such as an organo-metal precursor, which can be activated in-situ to form colloidal or nanometer or micron size catalysts.81. The system of any one of paragraphs 63 to 80, wherein the macroporous hydroprocessing catalyst is a pre-activated micron-size slurry catalyst.T-12086-W00182. The system of any one of paragraphs 63 to 80, wherein the macroporous hydroprocessing catalyst is selected from a macroporous ebullated (EB) reactor catalyst, a macroporous slurry catalyst, a macroporous upflow reactor catalyst, a macroporous hydrocracking catalyst, or a combination thereof.83. The system of any one of paragraphs 63 to 82, wherein the macroporous hydroprocessing catalyst has a particle density of less than about 0.95 g / cc, less than about 0.9 g / cc, less than about 0.85 g / cc, less than about 0.8 g / cc, less than about 0.75 g / cc, less than about 0.7 g / cc, less than about 0.65 g / cc, less than about 0.6 g / cc, less than about 0.5 g / cc, less than about 0.4 g / cc, or less than about 0.3 g / cc, about 0.3 to about 0.9 g / cc, about 0.4 to about 0.9 g / cc, about 0.5 to about 0.9 g / cc, about 0.6 to about 0.9 g / cc, or about 0.65 to about 0.9 g / cc84. The system of any one of paragraphs 63 to 83, wherein the macroporous hydroprocessing catalyst has a macropore peak position that is at about 1200 A or greater than 1200 A, at about 1300 A or greater than 1300 A, at about 1400 A or greater than 1400 A, at about 1500 A or greater than 1500 A, at about 1600 A or greater than 1600 A, at about 1700 A or greater than 1700 A, at about 1800 A or greater than 1800 A, at about 1900 A or greater than 1900 A, at about 2000 A or greater than 2000 A, at about 2100 A or greater than 2100 A, at about 2200 A or greater than 2200 A, at about 2300 A or greater than 2300 A, at about 2400 A or greater than 2400 A, at about 2500 A or greater than 2500 A, at about 2600 A or greater than 2600 A, at about 2700 A or greater than 2700 A, at about 2800 A or greater than 2800 A, at about 2900 A or greater than 2900 A, at about 3000 A or greater than 3000 A, at about 1200 A to about 5000 A, at about 1500 A to about 5000 A, at about 1700 A to about 5000 A, at about 2000 A to about 5000 A, at about 2000 A to about 4000 A, and / or at about 2000 A to about 3000 A.85. The system of any one of paragraphs 63 to 84, wherein the macroporous hydroprocessing catalyst has a macropore volume of at least about 0.05 cc / g, at least about 0.10 cc / g, at least about 0.20 cc / g, at least about 0.30 cc / g, at least about 0.40 cc / g, at least about 0.50 cc / g, at least about 0.60 cc / g, at least about 0.70 cc / g, at least about 0.80 cc / g, at least about 0.90 cc / g, at least about 1.0 cc / g, at least about 1.1 cc / g, at least about 1.2 cc / g, at least about 1.3 cc / g, at least about 1.4 cc / g, at least about 1.5 cc / g, at least about 1.6 cc / g, at least about 1.7 cc / g, at least about 1.8 cc / g, at least about 1.9 cc / g, about 0.10 to about 2.0 cc / g, about 0.10 to about 1.9 cc / g, about 0.10 to about 1.8 cc / g, about 0.10 to about 1.7 cc / g, about 0.10 to about 1.6 cc / g, about 0.10 to about 1.5 cc / g, about 0.20 to about 1.6 cc / g, about 0.20 to about 1.5 cc / g, or about 0.50 to about 1.5 cc / g.86. The system of any one of paragraphs 63 to 85, wherein the macroporous hydroprocessing catalyst has a total pore volume of at least about 0.50 cc / g, at least about 0.60 cc / g, at least aboutT-12086-W0010.70 cc / g, at least about 0.80 g / cc, at least about 0.9 g / cc, at least about 1.0 cc / g, at least about 1.5 cc / g, at least about 2.0 cc / g, at least about 2.50 cc / g, at least about 3.0 cc / g, about 0.50 to about 3.0 cc / g, about 1.0 to about 3.0 cc / g, about 1.0 to about 2.9 cc / g, about 1.0 to about 2.8 cc / g, about 1.0 to about 2.7 cc / g, about 1.0 to about 2.6 cc / g, about 1.0 to about 2.5 cc / g, or about 1.0 to about 2.5 cc / g.87. The system of any one of paragraphs 63 to 86, wherein the at least one contaminant in the non-pretreated feedstock is present in an amount of less than about 2000 ppm; less than about 1500 ppm, less than about 1000 ppm; less than about 900 ppm; less than about 800 ppm; less than about 700 ppm; less than about 600 ppm; less than about 500 ppm; less than about 400 ppm; less than about 300 ppm; less than about 200 ppm; or less than about 100 ppm88. The system of any one of paragraphs 63 to 87, wherein the at least one contaminant comprises at least one liquid and / or at least one solid.89. The system of any one of paragraphs 63 to 88, wherein the at least one contaminant is selected from at least one of nitrogen, phosphorus, and at least one metal.90. The system of any one of paragraphs 63 to 89, wherein the at least one contaminant is selected from at least one of a Group I, II, and transition metals, optionally, at least one of K, Ca, Mg, Ba, Si, Na, Fe, Si.91. The system of any one of paragraphs 63 to 90, wherein the at least one reactor is selected from an ebullating-bed (EB) reactor, a slurry-bed reactor, and an up-flow reactor (UFR).92. The system of any one of paragraphs 63 to 91, wherein the at least one contaminant is removed in the first stage via deposition on or impregnation in the catalyst and removing at least a portion of the catalyst from the first stage.93. The system of paragraph 92, wherein a portion of the catalyst is removed periodically. 94. The system of paragraph 92 or 93, wherein a portion of the catalyst is removed in a liquid product.95. The system of any one of paragraphs 63 to 94, wherein the hydroprocessing comprises at least one of i) heating from about 500 °F to about 800°F; ii) pressure is about 300 psig to about 3000 psig; iii) liquid hourly space velocity (LHSV) at about 0.1 h'1to about 3.0 h’1; iv) hydrogen-containing gas flow rate of about 2000 SCF / bbl to about 10000 SCF / bbl.96. The system of paragraph 65 or 67, wherein the hydroprocessing in the first stage comprises at least one of i) heating from about 580 °F to about 780°F; ii) pressure is about 300 psig to aboutT-12086-W0013000 psig; iii) liquid hourly space velocity (LHSV) at about 0.1 h'1to about 3.0 h’1; iv) hydrogen-containing gas flow rate of about 2500 SCF / bbl to about 10000 SCF / bbl.97. The system of any one of paragraphs 65, 67 and 96, wherein the hydroprocessing in the second stage comprises at least one of i) heating from about 500 °F to about 800°F; ii) pressure is about 300 psig to about 3000 psig; iii) liquid hourly space velocity (LHSV) at about 0.1 h'l t0about 3.0 h’1; iv) hydrogen-containing gas flow rate of about 2000 SCF / bbl to about 10000 SCF / bbl.98. The system of any one of paragraphs 65, 67 and 96 to 97, wherein the hydroprocessing further comprises adding a sulfiding agent to maintain a ratio of H2S to the non-pretreated feedstock at about 100 ppm or greater.99. The system of any one of paragraphs 63 to 98, wherein hydroprocessing further comprises at least one hydrotreating catalyst.100. The system of any one of paragraphs 63 to 99, wherein a partial conversion of oxygen occurs in the first stage.101. The system of any one of paragraphs 63 to 100, further comprising a separation stage for separating i) gaseous product(s) from ii) liquid(s) and solid(s).102. The system of paragraph 101, wherein the separation stage substantially separates the liquid(s) from the solid(s) in ii).103. The system of paragraph 101 or 102, wherein the second stage is configured for hydrotreating the liquid(s) from ii).104. The system of paragraph 101 or 102, wherein the separation stage comprises at least one of a filtration system, a centrifuge system, an electrostatic precipitation system, a settling system, and an evaporation system.105. The system of any one of paragraphs 101 to 104, wherein the separation stage comprises at least one of a dead-end filter, a cross-flow filter, and a filter press.106. The system of any one of paragraphs 63 to 104, wherein the non-pretreated lipid feedstock comprises plant oil(s).107. The system of paragraph 106, wherein the plant oil(s) comprises greater than about 50 ppm N and greater than about 100 ppm combined phosphorus and at least one metal contaminant. 108. The system of paragraph 106 or 107, wherein the plant oil(s) being used after pressing and / or solvent extraction from a plant and / or plant seeds.T-12086-W001109. The system of any one of paragraphs 63 to 108, wherein the non-pretreated lipid feedstock comprises triglycerides.110. The system of paragraph 109, wherein the non-pretreated lipid feedstock comprises greater than about 90% triglycerides and has greater than about 5% oxygen.111. The system of any one of paragraphs 63 to 110, wherein the non-pretreated lipid feedstock further comprises other sources of lipids.112. The system of paragraph 111, wherein the other sources of lipids comprise at least one of animal fats, used cooking oil, waste grease, and a combination thereof.113. The system of any one of paragraphs 63 to 112, wherein the non-pretreated feedstock comprises plastic pyrolysis-oil.114. The system of any one of paragraphs 63 to 112, wherein hydroprocessing comprises hydrogenation of the olefins of triglycerides (7g) to obtain hydrogenated triglycerides (HTg) and the hydrogenated triglycerides are transformed by hydrogenolysis into fatty acids ( 4), and waxes.115. The system of any one of paragraphs 63 to 113, wherein hydroprocessing further comprises hydrodeoxygenation (HDO), decarbonylation (DCO), decarboxylation (DCO2), hydrocracking, isomerization, dehydrogenation, and / or aromatization.116. The system of paragraph 65 or 67, wherein the second stage further comprises at least one catalyst selected from at least one of a hydrotreating catalyst for removing at least one contaminant and an isodewaxing catalyst to improve pour point and cloud point.117. The system of paragraph 116, wherein the second stage has at least three types of catalysts comprising hydrotreating catalyst, a hydrogenation catalyst, and an isomerization catalyst.118. The system of paragraph 116 or 117, wherein the second stage has a first layer having the hydrotreating catalyst; a second layer having the hydrogenation catalyst; and a third layer having an isomerization catalyst.119. The system of paragraph 118, wherein the second stage has a first layer having about 5% to about 20% of the hydrotreating catalyst; a second layer having about 3% to about 10% of the hydrogenation catalyst; and a third layer having an isomerization catalyst.120. The system of any one of paragraphs 118 to 119, wherein the first layer substantially eliminates contaminants; the second layer converts CO to methane; and the third layer substantially converts n-paraffins into iso-paraffins.T-12086-W001121. The system of any one of paragraphs 63 to 120, wherein product(s) from the first stage comprise liquid product(s) that are fed into the second stage and solid product(s).122. The system of any one of paragraph 121, wherein a portion of the liquid product(s) from the first stage is fed back to the first stage.123. The system of any one of paragraphs 121 to 122, wherein at least a portion of the solid product(s) is recovered.124. The system of paragraph 123, wherein if the solid(s) contains the macroporous hydroprocessing catalyst, the solids are washed to remove salt(s) and recycled.125. The system of paragraph 123 or 124, wherein the washed solid(s) are added to the nonpretreated lipid feedstock and fed to the first stage.126. The system of any one of paragraphs 63 to 125, further comprising separating and fractionating to separate gaseous products from renewable product(s).127. The process of any one of paragraphs 1 to 62, wherein the non-pretreated lipid feedstock is at least partially treated via a physical treatment process.128. The process of paragraph 127, wherein the physical treatment processes comprise at least one of cold pressing, solvent extraction, decanting, and / or filtration.129. The system of any one of paragraphs 63 to 126, wherein the non-pretreated lipid feedstock is at least partially treated via a physical treatment process.130. The system of paragraph 129, wherein the physical treatment processes comprise at least one of cold pressing, solvent extraction, decanting, and / or filtration.

[0272] It will be understood that the invention is not limited to the embodiments described above and various modifications and improvements can be made without departing from the concepts described herein. Except where mutually exclusive, any of the features may be employed separately or in combination with any other features and the disclosure extends to and includes all combinations and sub-combinations of one or more features described herein.

Claims

T-12086-W001WE CLAIM:

1. A process for making a renewable product from a non-pretreated lipid feedstock, the process comprising:hydroprocessing the non-pretreated lipid feedstock with at least one macroporous hydroprocessing catalyst under hydroprocessing conditions to produce the renewable product, wherein the macroporous hydroprocessing catalyst removes at least one contaminant from the non-pretreated lipid feedstock.

2. The process of claim 1, wherein the macroporous hydroprocessing catalyst has a suitable density to provide effective catalyst suspension.

3. The process of claim 1 or 2, wherein the macroporous hydroprocessing catalyst has an average macropore pore size of about 1200 A or greater than about 1200 A.

4. The process of any one of claims 1 to 3, wherein the macroporous hydroprocessing catalyst has a macropore volume at about 0.05 cc / g or greater and a macropore peak greater than about 1000 A.

5. The process of any one of claims 1 to 4, wherein the macroporous hydroprocessing catalyst has a particle density of about 0.95 g / cc or less than about 0.95 g / cc.

6. The process of any one of claims 1 to 5, wherein the non-pretreated lipid feedstock with the macroporous hydroprocessing catalyst forms a first product comprising at least one of less than about 2% oxygen, less than about 30 ppm N, and less than about 20 ppm combined phosphorus and at least one metal contaminant.

7. The process of any one of claims 1 to 6, wherein the macroporous hydroprocessing catalyst removes at least one of greater than about 90% oxygen, greater than about 80% nitrogen, greater than about 99% phosphorus, greater than about 99% of at least one metal.

8. The process of any one of claims 1 to 7, wherein the macroporous hydroprocessing catalyst comprises one or more transition metals selected from Group VIA (Group 6) and Group VIII (Groups 8-10) metals.

9. The process of any one of claims 1 to 8, wherein the macroporous hydroprocessing catalyst comprises one or more transition metals selected from Mo, Fe, W, Co, Ni, Zn, Pt and Pd.

10. The process of any one of claims 1 to 9, wherein the macroporous hydroprocessing catalyst is a self-supported catalyst that comprises at least one catalyst of Mo, M0S2, NiMo, NiS, CoO, MoOs, NiO, and / or a mixture thereof.T-12086-W00111. The process of any one of claims 1 to 10, wherein the macroporous hydroprocessing catalyst comprises a self-supported M0S2 and NiS catalyst.

12. The process of any one of claims 1 to 11, wherein the macroporous hydroprocessing catalyst further comprises one or more support materials such as zeolite, alumina, silica, alumina-silica, zirconia, alumina-silica-zeolite or activated carbon.

13. The process of any one of claims 1 to 12, wherein the macroporous hydroprocessing catalyst comprises NiMo supported catalysts on alumina.

14. The process of any one of claims 1 to 13, wherein the macroporous hydroprocessing catalyst is a precursor, such as an organo-metal precursor, which can be activated in-situ to form colloidal or nanometer or micron size catalysts.

15. The process of any one of claims 1 to 14, wherein the macroporous hydroprocessing catalyst is a pre-activated micron-size slurry catalyst.

16. The process of any one of claims 1 to 15, wherein the macroporous hydroprocessing catalyst is selected from a macroporous ebullated (EB) reactor catalyst, a macroporous slurry catalyst, a macroporous upflow reactor catalyst, a macroporous hydrocracking catalyst, or a combination thereof.

17. The process of any one of claims 1 to 16, wherein the macroporous hydroprocessing catalyst has a particle density of less than about 0.95 g / cc, less than about 0.9 g / cc, less than about 0.85 g / cc, less than about 0.8 g / cc, less than about 0.75 g / cc, less than about 0.7 g / cc, less than about 0.65 g / cc, less than about 0.6 g / cc, less than about 0.5 g / cc, less than about 0.4 g / cc, or less than about 0.3 g / cc, about 0.3 to about 0.9 g / cc, about 0.4 to about 0.9 g / cc, about 0.5 to about 0.9 g / cc, about 0.6 to about 0.9 g / cc, or about 0.65 to about 0.9 g / cc18. The process of any one of claims 1 to 17, wherein the macroporous hydroprocessing catalyst has a macropore peak position that is at about 1200 A or greater than 1200 A, at about 1300 A or greater than 1300 A, at about 1400 A or greater than 1400 A, at about 1500 A or greater than 1500 A, at about 1600 A or greater than 1600 A, at about 1700 A or greater than 1700 A, at about 1800 A or greater than 1800 A, at about 1900 A or greater than 1900 A, at about 2000 A or greater than 2000 A, at about 2100 A or greater than 2100 A, at about 2200 A or greater than 2200 A, at about 2300 A or greater than 2300 A, at about 2400 A or greater than 2400 A, at about 2500 A or greater than 2500 A, at about 2600 A or greater than 2600 A, at about 2700 A or greater than 2700 A, at about 2800 A or greater than 2800 A, at about 2900 A or greater than 2900 A, at about 3000 A or greater than 3000 A, at about 1200 A to about 5000 A,T-12086-W001at about 1500 A to about 5000 A, at about 1700 A to about 5000 A, at about 2000 A to about 5000 A, at about 2000 A to about 4000 A, and / or at about 2000 A to about 3000 A.

19. The process of any one of claims 1 to 18, wherein the macroporous hydroprocessing catalyst has a macropore volume of at least 0.01 cc / g, at least about 0.05 cc / g, at least about 0.10 cc / g, at least about 0.20 cc / g, at least about 0.30 cc / g, at least about 0.40 cc / g, at least about 0.50 cc / g, at least about 0.60 cc / g, at least about 0.70 cc / g, at least about 0.80 cc / g, at least about 0.90 cc / g, at least about 1.0 cc / g, at least about 1.1 cc / g, at least about 1.2 cc / g, at least about 1.3 cc / g, at least about 1.4 cc / g, at least about 1.5 cc / g, at least about 1.6 cc / g, at least about 1.7 cc / g, at least about 1.8 cc / g, at least about 1.9 cc / g, about 0.10 to about 2.0 cc / g, about 0.10 to about 1.9 cc / g, about 0.10 to about 1.8 cc / g, about 0.10 to about 1.7 cc / g, about 0.10 to about 1.6 cc / g, about 0.10 to about 1.5 cc / g, about 0.20 to about 1.6 cc / g, about 0.20 to about 1.5 cc / g, or about 0.50 to about 1.5 cc / g.

20. The process of any one of claims 1 to 19, wherein the macroporous hydroprocessing catalyst has a total pore volume of at least about 0.50 cc / g, at least about 0.60 cc / g, at least about 0.70 cc / g, at least about 0.80 g / cc, at least about 0.9 g / cc, at least about 1.0 cc / g, at least about 1.5 cc / g, at least about 2.0 cc / g, at least about 2.50 cc / g, at least about 3.0 cc / g, about 0.50 to about 3.0 cc / g, about 1.0 to about 3.0 cc / g, about 1.0 to about 2.9 cc / g, about 1.0 to about 2.8 cc / g, about 1.0 to about 2.7 cc / g, about 1.0 to about 2.6 cc / g, about 1.0 to about 2.5 cc / g, or about 1.0 to about 2.5 cc / g.

21. The process of any one of claims 1 to 20, wherein the at least one contaminant in the nonpretreated feedstock is present in an amount of less than about 2000 ppm; less than about 1500 ppm; less than about 1000 ppm; less than about 900 ppm; less than about 800 ppm; less than about 700 ppm; less than about 600 ppm; less than about 500 ppm; less than about 400 ppm; less than about 300 ppm; less than about 200 ppm; or less than about 100 ppm.

22. The process of any one of claims 1 to 21, wherein the at least one contaminant comprises at least one liquid and / or at least one solid.

23. The process of any one of claims 1 to 22, wherein the at least one contaminant is selected from at least one of nitrogen, phosphorus, and at least one metal.

24. The process of any one of claims 1 to 23, wherein the at least one contaminant is selected from at least one of a Group I, II, and transition metals, optionally, at least one of K, Ca, Mg, Ba, Si, Na, Fe, Si.

25. The process of any one of claims 1 to 24, wherein the hydroprocessing of the nonpretreated lipid feedstock occurs in a first stage comprising at least one reactor.T-12086-W00126. The process of claim 25, wherein the at least one reactor is selected from an ebullating-bed (EB) reactor, a slurry-bed reactor, and an up-flow reactor (UFR).

27. The process of any one of claims 1 to 24, wherein the at least one contaminant is removed in the first stage via deposition on / impregnation in the catalyst and removing at least a portion of the catalyst from the first stage.

28. The process of claim 27, wherein the removing of said at least a portion of the catalyst comprises removing the catalyst intermittently.

29. The process of claim 27 or 28, wherein the removing of said at least a portion of the catalyst comprises removing the catalyst via a liquid product.

30. The process of claim 25, wherein the hydroprocessing comprises at least one of i) heating from about 500 °F to about 800°F; ii) pressure is about 300 psig to about 3000 psig; iii) liquid hourly space velocity (LHSV) at about 0.1 h'1to about 3.0 h’1; iv) hydrogen-containing gas flow rate of about 2000 SCF / bbl to about 10000 SCF / bbl.

31. The process of claim 25, wherein the hydroprocessing comprises, in a first stage, at least one of i) heating from about 580 °F to about 780°F; ii) pressure is about 300 psig to about 3000 psig; iii) liquid hourly space velocity (LHSV) at about 0.1 h'1to about 3.0 h’1; iv) hydrogencontaining gas flow rate of about 2500 SCF / bbl to about 10000 SCF / bbl.

32. The process of any one of claims 25, 30, and 31, wherein the hydroprocessing comprises, in a second stage, at least one of i) heating from about 500 °F to about 800°F; ii) pressure is about 300 psig to about 3000 psig; iii) liquid hourly space velocity (LHSV) at about 0.1 h'1to about 3.0 h’1; iv) hydrogen-containing gas flow rate of about 2000 SCF / bbl to about 10000 SCF / bbl.

33. The process of any one of claims 25 and 30 to 32, wherein the hydroprocessing further comprises adding a sulfiding agent to maintain a ratio of H2S to the non-pretreated feedstock at about 100 ppm or greater.

34. The process of any one of claims 25 and 30 to 33, wherein hydroprocessing further comprises at least one hydrotreating catalyst.

35. The process of any one of claims 25 and 30 to 34, wherein partial conversion of oxygen occurs in the first stage.

36. The process of any one of claims 1 to 35, further comprising separating i) gaseous product(s) from ii) liquid(s) and solid(s).T-12086-W00137. The process of claim 36, further comprising substantially separating the liquid(s) from the solid(s) in ii).

38. The process of claim 36 or 37, further comprising hydrotreating the liquid(s) from ii).

39. The process of claim 36 or 37, wherein the liquid-solid separation comprises at least one of filtration, centrifuge, electrostatic precipitation, settling, and evaporation.

40. The process of any one of claims 36 to 39, wherein the liquid-solid separation comprises at least one of dead-end filter, cross-flow filter, and filter press.

41. The process of any one of claims 1 to 40, wherein non-pretreated lipid feedstock comprises plant oil(s).

42. The process of claim 41, wherein the plant oil(s) comprises greater than about 50 ppm N and greater than about 100 ppm combined phosphorus and at least one metal contaminant.

43. The process of any one of claims 41 to 42, wherein the plant oil(s) are derived from a plant and / or plant seeds that have been pressed and / or extracted.

44. The process of any one of claims 1 to 43, wherein the non-pretreated lipid feedstock comprises triglycerides.

45. The process of claim 44, wherein the non-pretreated lipid feedstock comprises greater than about 90% triglycerides and has greater than about 5% oxygen.

46. The process of any one of claims 1 to 45, wherein the non-pretreated lipid feedstock further comprises other sources of lipids.

47. The process of claim 46, wherein the other sources of lipids comprise at least one of animal fats, used cooking oil, waste grease, and a combination thereof.

48. The process of any one of claims 1 to 47, wherein the non-pretreated lipid feedstock comprises plastic pyrolysis-oil.

49. The process of any one of claims 1 to 47, wherein hydroprocessing comprises hydrogenation of the olefins of triglycerides (7g) to obtain hydrogenated triglycerides (HTg) and the hydrogenated triglycerides are transformed by hydrogenolysis into fatty acids ( 4), and waxes.

50. The process of any one of claims 1 to 48, wherein hydroprocessing further comprises hydrodeoxygenation (HDO), decarbonylation (DCO), decarboxylation (DCO2), hydrocracking, isomerization, dehydrogenation, and / or dearomatization.T-12086-W00151. The process of any one of claims 1 to 50, wherein the hydroprocessing comprises a first and a second stage, the second stage including a fixed-bed reactor.

52. The process of claim 51, wherein the second stage further comprises at least one catalyst selected from at least one of a hydrotreating catalyst for removing at least one contaminant and an isodewaxing catalyst to improve pour point and cloud point.

53. The process of claim 51, wherein the second stage has at least three types of catalysts comprising hydrotreating catalyst, a hydrogenation catalyst, and an isomerization catalyst.

54. The process of claim 51, wherein the second stage has a first layer having the hydrotreating catalyst; a second layer having the hydrogenation catalyst; and a third layer having an isomerization catalyst.

55. The process of claim 51, wherein the second stage has a first layer having about 5% to about 20% of the hydrotreating catalyst; a second layer having about 3% to about 10% of the hydrogenation catalyst; and a third layer having an isomerization catalyst.

56. The process of any one of claims 54 to 55, wherein the first layer substantially eliminates contaminants, the second layer converts CO to methane and the third layer substantially converts n-paraffins into iso-paraffins.

57. The process of any one of claims 51 to 56, wherein product(s) from the first stage comprise liquid product(s) that are fed into the second stage and solid product(s).

58. The process of any one of claim 57, wherein a portion of the liquid product(s) from the first stage are fed back to the first stage.

59. The process of any one of claims 57 to 58, wherein at least a portion of the solid product(s) is recovered.

60. The process of claim 59, wherein if the solid product(s) contain macroporous hydroprocessing catalyst, the solid product(s) is washed to remove salt(s) and fed back to the first stage.

61. The process of claim 60, wherein the washed solid product(s) is added to the nonpretreated lipid feedstock and fed back to the first stage.

62. The process of any one of claims 51 to 61, further comprising separating and fractionating to separate gaseous products from renewable products.

63. A system for making a renewable product from a non-pretreated lipid feedstock, the system comprising:T-12086-W001a first stage having at least one reactor for hydroprocessing the non-pretreated lipid feedstock with at least one macroporous hydroprocessing catalyst under hydroprocessing conditions to produce the renewable product;wherein the macroporous hydroprocessing catalyst removes at least one contaminant from the non-pretreated lipid feedstock.

64. The system of claim 63, wherein the at least one reactor is configured for at least partially converting oxygen within the non-pretreated lipid feedstock via the at least one macroporous hydroprocessing catalyst.

65. The system of claim 63 or 64, further comprising:a second stage having at least one secondary reactor for hydrotreating at least one intermediate product produced in the first stage to complete oxygen conversion and remove contaminants.

66. The system of any one of claims 63 to 65, wherein the at least one reactor of the first stage comprises an ebullating-bed or a slurry-bed reactor.

67. The system of any one of claims 65 to 66, wherein the at least one secondary reactor of the second stage comprises a fixed-bed reactor.

68. The system of any one of claims 63 to 67, wherein the macroporous hydroprocessing catalyst has a suitable density to provide effective catalyst suspension.

69. The system of any one of claims 63 to 68, wherein the macroporous hydroprocessing catalyst has an average macropore pore size of about 1200 A or greater than about 1200 A.

70. The system of any one of claims 63 to 69, wherein the macroporous hydroprocessing catalyst has a macropore volume at about 0.05 cc / g or greater and a macropore peak greater than about 1000 A.

71. The system of any one of claims 63 to 70, wherein the macroporous hydroprocessing catalyst has a particle density of about 0.95 g / cc or less than about 0.95 g / cc.

72. The system of any one of claims 63 to 71, wherein the non-pretreated lipid feedstock with the macroporous hydroprocessing catalyst forms a first product comprising at least one of less than about 2% oxygen, less than about 30 ppm N, and less than about 20 ppm combined phosphorus and at least one metal contaminant.

73. The system of any one of claims 63 to 72, wherein the macroporous hydroprocessing catalyst removes at least one of greater than about 90% oxygen, greater than about 80% nitrogen, greater than about 99% phosphorus, greater than about 99% of at least one metal.T-12086-W00174. The system of any one of claims 63 to 73, wherein the macroporous hydroprocessing catalyst comprises one or more transition metals selected from Group VIA (Group 6) and Group VIII (Groups 8-10) metals.

75. The system of any one of claims 63 to 74, wherein the macroporous hydroprocessing catalyst comprises one or more transition metals selected from Mo, Fe, W, Co, Ni, Zn, Pt and Pd.

76. The system of any one of claims 63 to 75, wherein the macroporous hydroprocessing catalyst is a self-supported catalyst that comprises at least one catalyst of Mo, M0S2, NiMo, NiS, CoO, MoOs, NiO, and / or a mixture thereof.

77. The system of any one of claims 63 to 76, wherein the macroporous hydroprocessing catalyst comprises a self-supported M0S2 and NiS catalyst.

78. The system of any one of claims 63 to 77, wherein the macroporous hydroprocessing catalyst further comprises one or more support materials such as zeolite, alumina, silica, alumina-silica, zirconia, alumina-silica-zeolite or activated carbon.

79. The system of any one of claims 63 to 78, wherein the macroporous hydroprocessing catalyst comprises NiMo supported catalysts on alumina.

80. The system of any one of claims 63 to 78, wherein the macroporous hydroprocessing catalyst is a precursor, such as an organo-metal precursor, which can be activated in-situ to form colloidal or nanometer or micron size catalysts.

81. The system of any one of claims 63 to 80, wherein the macroporous hydroprocessing catalyst is a pre-activated micron-size slurry catalyst.

82. The system of any one of claims 63 to 80, wherein the macroporous hydroprocessing catalyst is selected from a macroporous ebullated (EB) reactor catalyst, a macroporous slurry catalyst, a macroporous upflow reactor catalyst, a macroporous hydrocracking catalyst, or a combination thereof.

83. The system of any one of claims 63 to 82, wherein the macroporous hydroprocessing catalyst has a particle density of less than about 0.95 g / cc, less than about 0.9 g / cc, less than about 0.85 g / cc, less than about 0.8 g / cc, less than about 0.75 g / cc, less than about 0.7 g / cc, less than about 0.65 g / cc, less than about 0.6 g / cc, less than about 0.5 g / cc, less than about 0.4 g / cc, or less than about 0.3 g / cc, about 0.3 to about 0.9 g / cc, about 0.4 to about 0.9 g / cc, about 0.5 to about 0.9 g / cc, about 0.6 to about 0.9 g / cc, or about 0.65 to about 0.9 g / cc84. The system of any one of claims 63 to 83, wherein the macroporous hydroprocessing catalyst has a macropore peak position that is at about 1200 A or greater than 1200 A, at aboutT-12086-W0011300 A or greater than 1300 A, at about 1400 A or greater than 1400 A, at about 1500 A or greater than 1500 A, at about 1600 A or greater than 1600 A, at about 1700 A or greater than 1700 A, at about 1800 A or greater than 1800 A, at about 1900 A or greater than 1900 A, at about 2000 A or greater than 2000 A, at about 2100 A or greater than 2100 A, at about 2200 A or greater than 2200 A, at about 2300 A or greater than 2300 A, at about 2400 A or greater than 2400 A, at about 2500 A or greater than 2500 A, at about 2600 A or greater than 2600 A, at about 2700 A or greater than 2700 A, at about 2800 A or greater than 2800 A, at about 2900 A or greater than 2900 A, at about 3000 A or greater than 3000 A, at about 1200 A to about 5000 A, at about 1500 A to about 5000 A, at about 1700 A to about 5000 A, at about 2000 A to about 5000 A, at about 2000 A to about 4000 A, and / or at about 2000 A to about 3000 A.

85. The system of any one of claims 63 to 84, wherein the macroporous hydroprocessing catalyst has a macropore volume of at least about 0.05 cc / g, at least about 0.10 cc / g, at least about 0.20 cc / g, at least about 0.30 cc / g, at least about 0.40 cc / g, at least about 0.50 cc / g, at least about 0.60 cc / g, at least about 0.70 cc / g, at least about 0.80 cc / g, at least about 0.90 cc / g, at least about 1.0 cc / g, at least about 1.1 cc / g, at least about 1.2 cc / g, at least about 1.3 cc / g, at least about 1.4 cc / g, at least about 1.5 cc / g, at least about 1.6 cc / g, at least about 1.7 cc / g, at least about 1.8 cc / g, at least about 1.9 cc / g, about 0.10 to about 2.0 cc / g, about 0.10 to about 1.9 cc / g, about 0.10 to about 1.8 cc / g, about 0.10 to about 1.7 cc / g, about 0.10 to about 1.6 cc / g, about 0.10 to about 1.5 cc / g, about 0.20 to about 1.6 cc / g, about 0.20 to about 1.5 cc / g, or about 0.50 to about 1.5 cc / g.

86. The system of any one of claims 63 to 85, wherein the macroporous hydroprocessing catalyst has a total pore volume of at least about 0.50 cc / g, at least about 0.60 cc / g, at least about 0.70 cc / g, at least about 0.80 g / cc, at least about 0.9 g / cc, at least about 1.0 cc / g, at least about 1.5 cc / g, at least about 2.0 cc / g, at least about 2.50 cc / g, at least about 3.0 cc / g, about 0.50 to about 3.0 cc / g, about 1.0 to about 3.0 cc / g, about 1.0 to about 2.9 cc / g, about 1.0 to about 2.8 cc / g, about 1.0 to about 2.7 cc / g, about 1.0 to about 2.6 cc / g, about 1.0 to about 2.5 cc / g, or about 1.0 to about 2.5 cc / g.

87. The system of any one of claims 63 to 86, wherein the at least one contaminant in the nonpretreated feedstock is present in an amount of less than about 2000 ppm; less than about 1500 ppm, less than about 1000 ppm; less than about 900 ppm; less than about 800 ppm; less than about 700 ppm; less than about 600 ppm; less than about 500 ppm; less than about 400 ppm; less than about 300 ppm; less than about 200 ppm; or less than about 100 ppm88. The system of any one of claims 63 to 87, wherein the at least one contaminant comprises at least one liquid and / or at least one solid.T-12086-W00189. The system of any one of claims 63 to 88, wherein the at least one contaminant is selected from at least one of nitrogen, phosphorus, and at least one metal.

90. The system of any one of claims 63 to 89, wherein the at least one contaminant is selected from at least one of a Group I, II, and transition metals, optionally, at least one of K, Ca, Mg, Ba, Si, Na, Fe, Si.

91. The system of any one of claims 63 to 90, wherein the at least one reactor is selected from an ebullating-bed (EB) reactor, a slurry-bed reactor, and an up-flow reactor (UFR).

92. The system of any one of claims 63 to 91, wherein the at least one contaminant is removed in the first stage via deposition on or impregnation in the catalyst and removing at least a portion of the catalyst from the first stage.

93. The system of claim 92, wherein a portion of the catalyst is removed periodically.

94. The system of claim 92 or 93, wherein a portion of the catalyst is removed in a liquid product.

95. The system of any one of claims 63 to 94, wherein the hydroprocessing comprises at least one of i) heating from about 500 °F to about 800°F; ii) pressure is about 300 psig to about 3000 psig; iii) liquid hourly space velocity (LHSV) at about 0.1 h'1to about 3.0 h’1; iv) hydrogencontaining gas flow rate of about 2000 SCF / bbl to about 10000 SCF / bbl.

96. The system of claim 65 or 67, wherein the hydroprocessing in the first stage comprises at least one of i) heating from about 580 °F to about 780°F; ii) pressure is about 300 psig to about 3000 psig; iii) liquid hourly space velocity (LHSV) at about 0.1 h'1to about 3.0 h’1; iv) hydrogen-containing gas flow rate of about 2500 SCF / bbl to about 10000 SCF / bbl.

97. The system of any one of claims 65, 67 and 96, wherein the hydroprocessing in the second stage comprises at least one of i) heating from about 500 °F to about 800°F; ii) pressure is about 300 psig to about 3000 psig; iii) liquid hourly space velocity (LHSV) at about 0.1 h'110about 3.0 h’1; iv) hydrogen-containing gas flow rate of about 2000 SCF / bbl to about 10000 SCF / bbl.

98. The system of any one of claims 65, 67 and 96 to 97, wherein the hydroprocessing further comprises adding a sulfiding agent to maintain a ratio of H2S to the non-pretreated feedstock at about 100 ppm or greater.

99. The system of any one of claims 63 to 98, wherein hydroprocessing further comprises at least one hydrotreating catalyst.

100. The system of any one of claims 63 to 99, wherein a partial conversion of oxygen occurs in the first stage.T-12086-W001101. The system of any one of claims 63 to 100, further comprising a separation stage for separating i) gaseous product(s) from ii) liquid(s) and solid(s).

102. The system of claim 101, wherein the separation stage substantially separates the liquid(s) from the solid(s) in ii).

103. The system of claim 101 or 102, wherein the second stage is configured for hydrotreating the liquid(s) from ii).

104. The system of claim 101 or 102, wherein the separation stage comprises at least one of a filtration system, a centrifuge system, an electrostatic precipitation system, a settling system, and an evaporation system.

105. The system of any one of claims 101 to 104, wherein the separation stage comprises at least one of a dead-end filter, a cross-flow filter, and a filter press.

106. The system of any one of claims 63 to 104, wherein the non-pretreated lipid feedstock comprises plant oil(s).

107. The system of claim 106, wherein the plant oil(s) comprises greater than about 50 ppm N and greater than about 100 ppm combined phosphorus and at least one metal contaminant.

108. The system of claim 106 or 107, wherein the plant oil(s) being used after pressing and / or solvent extraction from a plant and / or plant seeds.

109. The system of any one of claims 63 to 108, wherein the non-pretreated lipid feedstock comprises triglycerides.

110. The system of claim 109, wherein the non-pretreated lipid feedstock comprises greater than about 90% triglycerides and has greater than about 5% oxygen.

111. The system of any one of claims 63 to 110, wherein the non-pretreated lipid feedstock further comprises other sources of lipids.

112. The system of claim 111, wherein the other sources of lipids comprise at least one of animal fats, used cooking oil, waste grease, and a combination thereof.

113. The system of any one of claims 63 to 112, wherein the non-pretreated feedstock comprises plastic pyrolysis-oil.

114. The system of any one of claims 63 to 112, wherein hydroprocessing comprises hydrogenation of the olefins of triglycerides (7g) to obtain hydrogenated triglycerides (HTg) and the hydrogenated triglycerides are transformed by hydrogenolysis into fatty acids ( 4), and waxes.T-12086-W001115. The system of any one of claims 63 to 113, wherein hydroprocessing further comprises hydrodeoxygenation (HDO), decarbonylation (DCO), decarboxylation (DCO2), hydrocracking, isomerization, dehydrogenation, and / or aromatization.

116. The system of claim 65 or 67, wherein the second stage further comprises at least one catalyst selected from at least one of a hydrotreating catalyst for removing at least one contaminant and an isodewaxing catalyst to improve pour point and cloud point.

117. The system of claim 116, wherein the second stage has at least three types of catalysts comprising hydrotreating catalyst, a hydrogenation catalyst, and an isomerization catalyst.

118. The system of claim 116 or 117, wherein the second stage has a first layer having the hydrotreating catalyst; a second layer having the hydrogenation catalyst; and a third layer having an isomerization catalyst.

119. The system of claim 118, wherein the second stage has a first layer having about 5% to about 20% of the hydrotreating catalyst; a second layer having about 3% to about 10% of the hydrogenation catalyst; and a third layer having an isomerization catalyst.

120. The system of any one of claims 118 to 119, wherein the first layer substantially eliminates contaminants; the second layer converts CO to methane; and the third layer substantially converts n-paraffins into iso-paraffins.

121. The system of any one of claims 63 to 120, wherein product(s) from the first stage comprise liquid product(s) that are fed into the second stage and solid product(s).

122. The system of any one of claim 121, wherein a portion of the liquid product(s) from the first stage is fed back to the first stage.

123. The system of any one of claims 121 to 122, wherein at least a portion of the solid product(s) is recovered.

124. The system of claim 123, wherein if the solid(s) contains the macroporous hydroprocessing catalyst, the solids are washed to remove salt(s) and recycled.

125. The system of claim 123 or 124, wherein the washed solid(s) are added to the nonpretreated lipid feedstock and fed to the first stage.

126. The system of any one of claims 63 to 125, further comprising separating and fractionating to separate gaseous products from renewable product(s).

127. The process of any one of claims 1 to 62, wherein the non-pretreated lipid feedstock is at least partially treated via a physical treatment process.T-12086-W001128. The process of claim 127, wherein the physical treatment processes comprise at least one of cold pressing, solvent extraction, decanting, and / or filtration.

129. The system of any one of claims 63 to 126, wherein the non-pretreated lipid feedstock is at least partially treated via a physical treatment process.

130. The system of claim 129, wherein the physical treatment processes comprise at least one of cold pressing, solvent extraction, decanting, and / or filtration.

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