Process for producing renewable products from bio-supplied raw materials

Abstract

A process for producing renewable products from bio-supply materials, wherein the bio-supply materials are brought into contact with a hydrogenation catalyst under hydrogenation conditions, and the bio-supply materials contain at least about 10% by weight of C 20+ It contains one or more bio-components having a certain content, and the hydrogenation conversion catalyst includes a hydrogenation isomerization catalyst.

Description

[Technical Field]

[0001] Cross-reference of related applications This application relates to and claims priority to U.S. Provisional Patent Application No. 63 / 471,911, filed on June 8, 2023, entitled "PROCESS TO MAKE A RENEWABLE PRODUCT FROM BIOFEEDSTOCK," and the entire disclosure thereof is incorporated herein by reference.

[0002] This specification describes a process for the hydrogenation of bio-supply materials to produce renewable products such as renewable base oils and / or process fluids. [Background technology]

[0003] The use of renewable resources has attracted significant attention and effort in the progress of developing alternatives to fossil fuels. The diversity, availability, and versatility of various bio-supply materials, particularly certain lipid sources, have been of great interest, leading to the development and commercial use of multiple biofuel technologies. The enduring economic benefits and the desire to reduce the use of fossil fuels have motivated improvements to existing technologies and the development of new processes for producing renewable fuels and other renewable products using renewable bio-supply materials.

[0004] Renewable fuels (biofuels) and other products are considered important for reducing carbon and greenhouse emissions. Bio-products derived from food are typically made from food sources produced on cultivated land, while bio-products derived from non-food sources are typically produced from lignocellulosic biomass such as forestry residues or agricultural residues and waste. Typical bio-supply materials in the food source category include a wide variety of lipids (e.g., vegetable oils including used cooking oil, seed oils, animal fats, waste oils, algal oils, etc.). Typical non-food source supplies include wood, grass, algae, crop by-products, and municipal solid waste. Renewable products derived from non-food sources are sometimes preferable to similar bio-products derived from food sources, but continuous improvements in hydrogenation conversion processes for all supply sources for producing renewable products are needed. [Overview of the Initiative]

[0005] The present invention relates to a process for producing renewable products from bio-supply materials, such as feed containing bio-components of biological origin. A variety of renewable products can be produced, including diesel, aviation fuel and other fuels and distillates, as well as base oils or their components and process fluids.

[0006] In one embodiment, a process is provided for producing a renewable product from a biosupply, the process comprising contacting the biosupply with a hydrogenation catalyst under hydrogenation conditions, wherein the biosupply contains at least about 10% by weight of C 20+ It contains one or more bio-components having a certain content, and the hydrogenation conversion catalyst includes a hydrogenation isomerization catalyst.

[0007] In another embodiment, the use of an isomerization catalyst for producing a renewable product is described, wherein the hydrogenation catalyst contains at least about 10% by weight of C 20+ A bio-supply raw material containing one or more bio-components, or an intermediate product derived from a bio-supply raw material, is brought into contact with a bio-supply raw material under hydrogenation conversion conditions to produce a renewable product, the hydrogenation conversion including hydrogenation isomerization.

[0008] In some embodiments, products such as base oils, lubricating oils, and / or process fluids may be produced according to the process.

[0009] Unless mutually exclusive, features described in relation to any aspect or embodiment described herein may be applied mutatis mutandis to any other aspect and / or embodiment. Furthermore, unless mutually exclusive, features described herein may be applied to any aspect / embodiment and / or combined with any other features described herein. [Modes for carrying out the invention]

[0010] While this specification illustrates exemplary embodiments of one or more aspects, the disclosed processes can be carried out using any number of techniques. This disclosure is not limited to exemplary or specific embodiments, including any exemplary designs and embodiments described herein, any drawings, and any techniques illustrated herein, but can be modified within the entire scope of the claims and equivalents set forth herein.

[0011] The following descriptions of embodiments provide non-limiting representative examples, with reference to numerical values ​​to further describe the features and teachings of various aspects of the present invention. It should be understood that the embodiments described may be implemented separately from or in combination with other embodiments described herein. Those skilled in the art will be able to learn and understand other described aspects of the present invention by reviewing the descriptions of embodiments. The descriptions of embodiments are intended to facilitate understanding of the present invention so that other practical forms, though not specifically covered, that fall within the scope of the ability of those skilled in the art to read the descriptions of embodiments are understood to be consistent with the application of the present invention.

[0012] Unless otherwise indicated, the following terms have the meanings defined herein.

[0013] The term "hydrogenation" refers to a process or step carried out in the presence of hydrogen for the hydrocracking, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrification, hydrodemetallation, hydrodechlorination, hydrodecarbonylation, and / or hydrodearomatication of hydrocarbons or biomass feedstocks, and / or for the hydrogenation of unsaturated compounds in the feedstocks. Depending on the type of hydrogenation and reaction conditions, the products of the hydrogenation may have, for example, improved aromatic content, oxygen content, viscosity, viscosity index, saturated fatty acid content, low-temperature flow properties and other low-temperature properties, as well as volatility.

[0014] The term "hydrogenation treatment" refers to a process or step carried out in the presence of hydrogen for the hydrogenation, dehydrogenation, denitrification, deoxygenation, demetallation, and / or dearomatication of components of the feedstock, and / or hydrogenation of unsaturated compounds in the feedstock.

[0015] As used herein, the term “biofedible material” refers to biocomponent feedstocks obtained from or derived from biosources. Exemplary biofedible materials include lipids, pyrolysis oils, and biomass-derived feedstocks. Triglycerides are components of some biofedible materials, such as lipids. Biofedible materials typically have a boiling range suitable for producing diesel, aviation fuel, or other fuels, distillates, base oils, and / or process fluids thereof. In the case of some biofedible materials containing triglycerides, such feedstocks have an “apparent” boiling temperature range (based on the GC elution time of the triglyceride peak according to the Simdist method ASTM D-2887) suitable for producing diesel, aviation fuel, or other fuels, or distillates thereof. The boiling range (or apparent boiling range) of a biofedible material may also be suitable for producing base oils or components thereof. Suitable bio-supply materials are those that, upon hydrogenation, produce hydrocarbons having boiling points in the range of approximately 250°F (121°C) to approximately 900°F (482°C), for example, approximately 300°F (149°C) to approximately 900°F (482°C), or approximately 250°F (121°C) to approximately 800°F (427°C). The apparent boiling point range of lipids before hydrogenation may, in some cases, be higher than 900°F, but upon hydrogenation, such lipids are converted to hydrocarbons having lower boiling temperatures or temperature ranges as described herein. In some cases, for example, typical lipids after hydrogenation contain hydrocarbon molecules with a maximum boiling point of approximately 900°F (482°C) and suitable carbon number and hydrocarbon chain length for the applications described herein. Generally, at least one bio-supply material, or its bio-component, used in the process contains at least approximately 10% by weight of C 20+ It contains [a certain amount].

[0016] As used herein, the term “bio-component feed” refers to feedstock derived from bio-component-containing sources, such as vegetable oils or fats, animal oils or fats, fish oils or fats, or algal oils or fats. Such feedstocks are generally hydrogenation products derived from biosources. In some embodiments, preferred bio-component feedstocks may have boiling points in the range of about 250°F (121°C) to about 900°F (482°C) at atmospheric pressure, for example, about 300°F (149°C) to about 900°F (482°C), about 400°F to about 900°F (about 204°C to about 482°C), about 500°F to about 900°F (about 260°C to about 482°C), about 600°F (316°C) to about 900°F (482°C), or about 700°F (371°C) to about 900°F (482°C). The bio-component feedstock may have a 90% distillation temperature of less than about 1000°F (538°C), less than 900°F (482°C), less than 800°F (427°C), less than 700°F (371°C), or less than about 650°F (343°C). In some embodiments, the bio-component feedstock has a 90% distillation temperature in the range of about 550°F (288°C) to about 750°F (399°C), for example, about 550°F (288°C) to about 700°F (371°C), or about 600°F (316°C) to about 700°F (371°C). The 90% distillation temperature can be determined according to ASTM D-2887. In some embodiments, the biocomponent feed 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 (204°C) to about 600°F (316°C). The 5% distillation temperature can be determined according to ASTM D2887. In some embodiments, the biocomponent feed has a 90% distillation temperature in the range of about 550°F (about 288°C) to about 750°F (about 399°C), and a 5% distillation temperature in the range of about 250°F (121°C) to about 600°F (316°C). In some embodiments, the biocomponent feed has a 90% distillation temperature in the range of about 550°F (288°C) to about 700°F (371°C) and a 5% distillation temperature in the range of about 300°F (149°C) to about 600°F (316°C).In some embodiments, the bio-component feed has a 90% distillation temperature higher than about 600°F (316°C), for example, between about 605°F (318°C) and about 675°F (357°C), and a 5% distillation temperature lower than about 600°F (316°C), for example, between about 540°F (282°C) and about 580°F (304°C). In some embodiments, the bio-component feed has a 90% distillation temperature in the range of about 600°F (316°C) or higher and about 700°F (371°C), and a 5% distillation temperature in the range of about 400°F (204°C) or lower and about 600°F (316°C). In some cases, for example, in the case of a typical lipid after hydrogenation, the upper boiling point of about 900°F (482°C) includes hydrocarbon molecules having a number of carbon atoms suitable for the applications described herein.

[0017] The term “renewable products” is used herein to refer to products produced entirely or partially from non-fossil fuel sources. Suitable raw materials for producing renewable products generally originate from materials of biological origin. Renewable products may comprise one or more renewable components, for example, products derived from feedstocks from two or more biological sources.

[0018] As used herein, the term “Fischer-Tropsch feed” refers to synthetic feedstock produced via the Fischer-Tropsch process and generally having a 90% distillation temperature of less than about 1350°F (732°C), or less than about 1100°F (593°C), or less than about 1000°F (538°C), or less than about 900°F (482°C), or less than about 800°F (427°C), or less than about 750°F (399°C), or less than about 700°F (371°C). In some embodiments, the Fischer-Tropsch feed has a 90% distillation temperature in the range of about 550°F (288°C) to about 750°F (399°C), for example, about 550°F (288°C) to about 700°F (371°C), or about 600°F (316°C) to about 700°F (371°C). The 90% distillation temperature can be determined according to ASTM D2887. In some embodiments, the Fischer-Tropsch feed 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 340°F (171°C) to about 600°F (316°C), or about 340°F (171°C) to about 500°F (260°C), or about 340°F (171°C) to about 400°F (204°C). The 5% distillation temperature can be determined according to ASTM D-2887. In some embodiments, the Fischer-Tropsch feed has a 90% distillation temperature in the range of about 550°F (288°C) to about 750°F (399°C) and a 5% distillation temperature in the range of about 250°F (121°C) to about 600°F (316°C). In some embodiments, the Fischer-Tropsch feed has a 90% distillation temperature in the range of about 550°F (288°C) to about 700°F (371°C) and a 5% distillation temperature in the range of about 300°F (149°C) to about 600°F (316°C). In some embodiments, the Fischer-Tropsch feed has a 90% distillation temperature in the range of about 600°F (316°C) to about 700°F (371°C) and a 5% distillation temperature in the range of about 340°F (171°C) to about 600°F (316°C).In some embodiments, the Fischer-Tropsch fledger has a 90% distillation temperature in the range of about 600°F (316°C) to about 700°F (371°C) and a 5% distillation temperature in the range of about 340°F (171°C) to about 500°F (260°C). In some embodiments, the Fischer-Tropsch fledger has a 90% distillation temperature in the range of about 600°F (316°C) to about 700°F (371°C) and a 5% distillation temperature in the range of about 340°F (171°C) to about 400°F (204°C). In some embodiments, the "Fischer-Tropsch fledger" may have a boiling point in the range of about 250°F (121°C) to about 900°F (482°C) at atmospheric pressure, for example, about 250°F (121°C) to about 800°F (427°C).

[0019] The term "diesel fuel" is used herein to refer to hydrocarbon products having a boiling point in the range of approximately 300°F to approximately 800°F (approximately 149°C to approximately 427°C) at atmospheric pressure.

[0020] The term “fossil fuel components” is used herein to refer to components that are produced entirely or partially from fossil fuel sources.

[0021] The term “process fluid” is used herein to generally refer to a fluid used as a working fluid or other fluid within a process or device, including devices used in chemical, electrical, and / or mechanical processes, but not part of the final or intermediate products produced by the process or device. Examples of process fluids, but not limited to, include drilling fluids, transformer fluids, thermal oils, working fluids, transmission fluids and / or gear oils, metalworking fluids, or combinations thereof.

[0022] The term "active source" means a reagent or precursor material that can supply at least one element in a form that can react and be incorporated into a molecular sieve structure. The terms "source" and "active source" may be used interchangeably herein.

[0023] The terms “molecular sieve” and “zeolite” are synonymous and include (a) intermediates, (b) final or target molecular sieves, and molecular sieves produced by (1) direct synthesis or (2) post-crystallization treatment (secondary modification). In secondary synthesis techniques, target materials can be synthesized from intermediate materials by heteroatomic lattice substitution or other techniques. For example, aluminosilicates can be synthesized from intermediate borosilicates by post-crystallization heteroatomic lattice substitution of Al with respect to B. Such techniques are publicly known and are described, for example, in U.S. Patent No. 6,790,433 of CYChen and Stacey Zones, issued on September 14, 2004.

[0024] The terms "*MRE molecular sieve," "EUO molecular sieve," and "MTT molecular sieve" include all molecular sieves and their isotypes assigned to the International Zeolite Association framework, as described in Atlas of Zeolite Framework Types, eds. Ch. Baerlocher, LBMcCusker and DHOlson, Elsevier, 6th revised edition, 2007 and the Database of Zeolite Structures on the International Zeolite Association website (http: / / www.iza-online.org).

[0025] The SiO2 / Al2O3 ratio (SAR) is determined by ICP elemental analysis. An infinite (∞) SAR indicates that the zeolite contains no aluminum, i.e., the molar ratio of silica to alumina is infinite. In this case, the molecular sieve is essentially composed of silica.

[0026] As used herein, the term “pour point” refers to the temperature at which oil begins to flow under controlled conditions. The pour point can be determined by ASTM D5950.

[0027] As used herein, “cloud point” refers to the temperature at which an oil sample begins to cloud when cooled under specific conditions. The cloud point can be measured according to ASTM D5773.

[0028] "Group 2, 8, 9, and 10 metals" refers to elemental metals (multiple selections) selected from Groups 2, 8, 9, and 10 of the periodic table, and / or metallic compounds containing such metals (multiple selections). "Group 6 metals" refers to elemental metals (multiple selections) selected from Group 6 of the periodic table, and / or metallic compounds containing such metals (multiple selections).

[0029] The term "periodic table" refers to the IUPAC periodic table of elements as of December 1, 2018.

[0030] Unless otherwise specified, the "feed rate" of the feed material supplied to the catalytic reaction zone is expressed herein as the volume of feed material per volume of catalyst per hour, which is in reciprocal units of hours (h). -1 This is sometimes called the liquid hourly space velocity (LHSV).

[0031] For the purposes of this specification and the appended claims, unless otherwise indicated, all numbers and other numerical values ​​used herein to express quantities, percentages, or proportions should be understood in all cases to be modified by the term “approximately.” Therefore, unless otherwise indicated, the numerical parameters shown in the following specification and the appended claims are approximations and may vary depending on the desired characteristics to be obtained. Note that, as used herein and in the appended claims, the singular forms “a,” “an,” and “the” include multiple references unless explicitly and clearly limited to one. As used herein, the term “comprising” and its grammatical variations are intended to be non-exclusive, such that the enumeration of items in a list does not exclude other similar items that may be substituted for or added to the enumerated items. As used herein, the term “comprising” means including the element or process specified following the term, but none of such elements or processes are exhaustive, and one embodiment may include other elements or processes.

[0032] Unless otherwise specified, any enumeration of elements, materials, or other genera of elements from which individual components or mixtures of components can be selected is intended to include all possible sub-genus combinations of the listed components and their mixtures. Furthermore, all numerical ranges shown herein include their upper and lower limits.

[0033] Where standard tests are referred to herein, unless otherwise stated, the version of the test referenced is the current version as of the date of this patent application.

[0034] The patentable scope is defined by the claims and may include other examples that would be appropriate to a person skilled in the art. Such other examples are intended to be included in the claims if they have structural elements that are not different from the language of the claims, or if they contain equivalent structural elements that are not substantially different from the language of the claims. To the extent that is not inconsistent with this specification and in the jurisdictions where permitted, all references made herein are incorporated herein by reference.

[0035] The biosupply materials described herein include or consist of biocomponent feedstocks. In some embodiments, the biosupply material includes, essentially consists of, or consists of biocomponent feedstocks. In some embodiments, the biocomponent feedstocks constitute at least about 5% by weight of the biosupply material, for example, at least about 10% by weight, at least about 20% by weight, at least about 30% by weight, at least about 40% by weight, at least about 50% by weight, at least about 60% by weight, at least about 70% by weight, at least about 80% by weight, at least about 90% by weight, at least about 95% by weight, at least about 98% by weight, or at least about 99% by weight of the biosupply material. In some embodiments, the biocomponent feedstocks constitute 5% to 100% by weight of the biosupply material, for example, 10% to 100% by weight, 50% to 100% by weight, or 80% to 100% by weight, or 95% to 100% by weight of the biosupply material.

[0036] In some embodiments, the biosupply material includes, essentially consists of, or comprises a biocomponent feed. For example, the biocomponent feed may constitute at least about 5% by weight of the biosupply material, such as at least about 10% by weight, at least about 20% by weight, at least about 30% by weight, at least about 40% by weight, at least about 50% by weight, at least about 60% by weight, at least about 70% by weight, at least about 80% by weight, at least about 90% by weight, at least about 95% by weight, at least about 98% by weight, or at least about 99% by weight. In some embodiments, the Fischer-Tropsch feed may constitute 5% to 100% by weight of the biosupply material, for example, 10% to 100% by weight, 50% to 100% by weight, 80% to 100% by weight, or 95% to 100% by weight of the biosupply material.

[0037] In some embodiments, the bio-feed is a mixed feed that includes a bio-component feed in combination with another feed, such as a mixed feed, or also includes a Fischer-Tropsch feed. For example, the mixed feed may include a mixed feed selected from diesel fuel, vacuum diesel fuel, long residue, vacuum residue, atmospheric distillates, heavy fuels, oils, waxes and paraffins, spent oil, de-asphalt residue or crude oil, charges resulting from a thermal or catalytic conversion process, or a combination thereof. In some embodiments, the mixed feed is selected from whole crude oil, reduced crude oil, vacuum column residue, cycle oil, synthetic crude oil, diesel fuel, reduced-pressure diesel fuel, Fluorine oil, Fischer-Tropsch derivative wax, lubricating oil stock, heating oil, heavy neutral feedstock, hydrotreated diesel fuel, hydrocracked diesel fuel, hydrotreated lubricating oil raffinate, bright stock, lubricating oil stock, synthetic oil, high-pour-point polyolefins (e.g., polyolefins having a pour point of about 0°C or higher); ordinary alpha-olefin wax, slack wax, degreasing wax, microcrystalline wax, residue fractions from atmospheric distillation processes, solvent-deasphaltized petroleum residues, shale oil, cycle oil, petroleum wax, slack wax, and waxes produced in chemical plant processes. In some embodiments, the feedstock is a mixed feedstock comprising a bio-component feedstock and a Fischer-Tropsch feedstock. In some embodiments, the feedstock is a mixed feedstock comprising a bio-component feedstock, a Fischer-Tropsch feedstock, and a mixed feedstock (e.g., the mixed feedstock described above). Mixed feedstocks, mixed feeds, and / or biofeedstocks may also include regeneration products and / or intermediate process fluids. As previously stated, such biofeedstocks or biocomponents are generally hydrogenation products derived from biosources, and the biocomponents are hydrogenated by themselves or together with other feedstock components.

[0038] In some embodiments, the feedstock is a mixed feedstock comprising a biocomponent feedstock and a mixed feedstock, the mixed feedstock comprising at least about 5% by weight of the biocomponent feedstock and up to about 95% by weight of the mixed feedstock components, for example, at least about 10% by weight of the biocomponent feedstock and up to about 90% by weight of the mixed feedstock components, at least about 50% by weight of the biocomponent feedstock and up to about 50% by weight of the mixed feedstock components, at least about 80% by weight of the biocomponent feedstock and up to about 20% by weight of the mixed feedstock components, or at least about 95% by weight of the biocomponent feedstock and up to about 5% by weight of the mixed feedstock components.

[0039] Fischer-Tropsch feeds (if used) typically have a paraffin content of at least about 90% by weight, for example, at least about 95% by weight, or at least about 97.5% by weight. Fischer-Tropsch (FT) feeds typically contain only very small amounts of olefins and cycloparaffins, for example, less than about 1.0% by weight of olefins, or less than about 0.5% by weight of olefins, and / or less than about 1.0% by weight of cycloparaffins, less than about 0.5% by weight of cycloparaffins, or less than about 0.1% by weight of cycloparaffins. In some embodiments, FT feeds have a sulfur (S) content of less than about 50 ppm, for example, less than about 20 ppm. In some embodiments, FT feeds have a nitrogen (N) content of less than about 50 ppm, for example, less than about 20 ppm. In some embodiments, FT feeds have a metal content of less than about 10 ppm, for example, less than about 5 ppm. The paraffin and cycloparaffin content of the FT feedstock can be determined by GC-FIMS analysis, as described in “Diesel Fuel Analysis by GC-FIMS: Normal Paraffins, Isoparaffins and Cycloparaffins”, Briker, Y., et al., Energy Fuels 2001, 15, 4, 996-1002. The nitrogen content of the FT feedstock can be determined according to ASTM D3228-20. The sulfur content of the FT feedstock can be determined according to ASTM D4629. The metal content of the FT feedstock can be measured by inductively coupled plasma atomic emission spectroscopy (ICP-AES).

[0040] In some embodiments, the feedstock is a mixed feedstock comprising a combination of Fischer-Tropsch (FT) feedstock and a mixed feedstock, the mixed feedstock comprising at least about 5 wt% of FT feedstock and up to about 95 wt% of mixed feedstock, for example, at least about 10 wt% of FT feedstock and up to about 90 wt% of mixed feedstock, at least about 50 wt% of FT feedstock and up to about 50 wt% of mixed feedstock, at least about 80 wt% of FT feedstock and up to about 20 wt% of mixed feedstock, or at least about 95 wt% of FT feedstock and up to about 5 wt% of mixed feedstock.

[0041] In some embodiments, the bio-supply raw materials include, essentially consist of, or comprise bio-component feedstocks. Vegetable oils and fats include vegetable oils such as rapeseed (canola) oil, soybean oil, coconut oil, sunflower oil, palm oil, palm kernel oil, peanut oil, linseed oil, colza oil, tall oil, corn oil, castor oil, jatropha oil, jojoba oil, olive oil, linseed oil, hemp seed oil, cottonseed oil, camelina oil, safflower oil, mustard oil, carinata oil, cuphea oil, carcass oil, cranbe oil, babassu oil, animal fat, and rice bran oil. Animal oils and fats, as well as other sources, include beef fat (tallow), pork fat (lard), turkey fat, fish fat / oil, and chicken fat, yellow and brown fats including algae and fish fat / oil, milk fat, and sewage sludge.

[0042] In certain embodiments, the biosupply material includes or is a biocomponent feed selected from carinata oil, rapeseed oil, peanut oil, mustard oil, animal fat, rice bran oil, carnauba wax, or a combination thereof. However, the biosupply material or biocomponent may be obtained from plant families selected from Brassicaceae (formerly Cruciferaceae), Limnanthaceae, Simmondsiaceae, Tropaeolacae, Olocaceae, Copernicia, or a combination thereof.

[0043] In some embodiments, the bio-component feed may include feed components selected from vegetable oils and animal fats that contain or are essentially derived from triglycerides and free fatty acids (FFAs). In some embodiments, the bio-feed raw materials include or are bio-component feed selected from lipids containing triglycerides and free fatty acids, vegetable oils, seed oils, and animal fats. For example, preferred bio-component feeds may be selected from canola oil, corn oil, soybean oil, castor oil, camelina oil, palm oil, and combinations thereof.

[0044] In some embodiments, the triglycerides and FFAs include aliphatic hydrocarbon chains having 6 to 32 carbon atoms in their structure (e.g., 6 to 22, 24, 26, 28, 30, or 32 carbon atoms; 8 to 22, 24, 26, 28, 30, or 32 carbon atoms; 10 to 22, 24, 26, 28, 30, or 32 carbon atoms; 12 to 22, 24, 26, 28, 30, or 32 carbon atoms; 14 to 22, 24, 26, 28, 30, or 32 carbon atoms; 16 to 22, 24, 26, 28, 30, or 32 carbon atoms; and / or 18 to 22, 24, 26, 28, 30, or 32 carbon atoms). In some embodiments, the biocomponent feedstock may include a triglyceride having general formula (1), [ka]

[0045] In the formula, R, R 1 , and R 2 R is an aliphatic hydrocarbon chain having 6 to 32 carbon atoms (e.g., 6 to 24, 8 to 24, 12 to 24, 16 to 32, 16 to 24, 18 to 24, 20 to 24, 6 to 20, 8 to 20, 10 to 20, 6 to 18, 8 to 18, 10 to 18, or 6 to 16, 8 to 16, 10 to 16 carbon atoms). In some embodiments, R, R 1 , and R 2is, independently, branched or unbranched, substituted or unsubstituted, fully saturated or contains one or more (e.g., 1 to 4, 1 to 3 or 1 or 2) unsaturated carbon-carbon bonds. In some embodiments, R, R 1 and R 2 are unsubstituted. In some embodiments, R, R 1 and R 2 are, independently, fully saturated or contain one or more (e.g., 1 to 4, 1 to 3 or 1 or 2) unsaturated carbon-carbon bonds. In some embodiments, R, R 1 and R 2 are unbranched.

[0046] The biofeedstock or bio-component feedstock component can include a free fatty acid (FFA) having an aliphatic hydrocarbon tail (substituent) of 6 to 32 carbon atoms, such as, for example, 6, 8, 10, 12, 14, 16, or 18 to 24 carbon atoms, 6, 8, 10, 12, 14, 16, 18, or 20 to 32 carbon atoms, 6, 8, 10, or 12 to 20 carbon atoms, 6, 8, 10, or 12 to 18 carbon atoms, and / or 6, 8, or 10 to 16 carbon atoms. The FFA can include an unsaturated or saturated aliphatic hydrocarbon tail. The FFA can include an unbranched or branched aliphatic hydrocarbon tail.

[0047] The biofeedstock can include or be a bio-component feedstock, and the biofeedstock includes one or more bio-components having a C 20+ content of at least about 10 wt%. In some cases, the C 20+ content of the biofeedstock and / or its bio-components can be less than about 80 wt%, 70 wt%, 60 wt%, 50 wt%, 40 wt%, 30 wt% or 20 wt%. Also, the C 20+The content may be approximately 20% by weight, 30% by weight, 40% by weight, 50% by weight, 60% by weight, over 70% by weight, or a combination thereof. In some cases, the content range of the biosupply raw material or biocomponent may be in the range of approximately 10-80% by weight, 10-70% by weight, 10-60% by weight, 10-50% by weight, 10-40% by weight, 20-80% by weight, 30-80% by weight, 40-80% by weight, 50-80% by weight, 20-70% by weight, 20-60% by weight, 20-50% by weight, 20-40% by weight, 30-80% by weight, 30-70% by weight, 30-60% by weight, 30-50% by weight, 40-80% by weight, 40-70% by weight, 40-60% by weight, 50-80% by weight, 50-70% by weight, or 60-80% by weight. 20+ It may contain a certain amount.

[0048] C of bio-supplied raw materials and / or their bio-components 20+ In addition to the content, the C content of the bio-supplied raw materials or their bio-components. 16 The content may be approximately 70% by weight, 60% by weight, 50% by weight, 40% by weight, 30% by weight, 20% by weight, 10% by weight, 8% by weight, 5% by weight, 2% by weight, or less than 1% by weight. In addition, the C of the bio-supplied raw materials or their bio-components. 16+ The content may be approximately 1% by weight, 2% by weight, 5% by weight, 8% by weight, more than 10% by weight, or a combination thereof. C of the bio-supply raw material or its bio-components. 16 The content may range from approximately 0-70% by weight, 0-60% by weight, 0-50% by weight, 0-40% by weight, 5-70% by weight, 5-60% by weight, 5-50% by weight, 5-40% by weight, 10-70% by weight, 10-60% by weight, 10-50% by weight, 10-40% by weight, 20-70% by weight, 20-60% by weight, 20-50% by weight, or 20-40% by weight.

[0049] C of bio-supplied raw materials and / or their bio-components 20+ In addition to the content, as well as the limitations or scope of C mentioned above. 16 In addition to or separately from the content of the bio-supply raw materials or their bio-components, C 18The content may be approximately 70% by weight, 60% by weight, 50% by weight, 40% by weight, 30% by weight, 20% by weight, 10% by weight, or less than 5% by weight. C of the bio-supply raw material or its bio-components. 18 The content may be approximately 5% by weight, 10% by weight, 20% by weight, 30% by weight, 40% by weight, 50% by weight, over 60% by weight, or a combination thereof. C of the bio-supply raw material or its bio-components. 18 The content may range from approximately 0-70% by weight, 0-60% by weight, 0-50% by weight, 0-40% by weight, 5-70% by weight, 5-60% by weight, 5-50% by weight, 5-40% by weight, 10-70% by weight, 10-60% by weight, 10-50% by weight, 10-40% by weight, 20-70% by weight, 20-60% by weight, 20-50% by weight, or 20-40% by weight.

[0050] C of bio-supplied raw materials and / or their bio-components 20+ In addition to the content, as well as the limitations or scope of C mentioned above. 16 and / or C 18 In addition to or separately from the content of the bio-supply raw materials or their bio-components, C 20 The content may be approximately 70% by weight, 60% by weight, 50% by weight, 40% by weight, 30% by weight, 20% by weight, 10% by weight, or less than 5% by weight. C of the bio-supply raw material or its bio-components. 20+ The content may be approximately 5% by weight, 10% by weight, 20% by weight, 30% by weight, 40% by weight, 50% by weight, over 60% by weight, or a combination thereof. C of the bio-supply raw material or its bio-components. 20 The content may range from approximately 0-70% by weight, 0-60% by weight, 0-50% by weight, 0-40% by weight, 5-70% by weight, 5-60% by weight, 5-50% by weight, 5-40% by weight, 10-70% by weight, 10-60% by weight, 10-50% by weight, 10-40% by weight, 20-70% by weight, 20-60% by weight, 20-50% by weight, or 20-40% by weight.

[0051] C of bio-supplied raw materials and / or their bio-components 20+ In addition to the content, as well as the limitations or scope of C mentioned above. 16 , C 18and / or C 20 In addition to or separately from the content, the biocomponent C 22+ The content may be approximately 70% by weight, 60% by weight, 50% by weight, 40% by weight, 30% by weight, 20% by weight, 10% by weight, or less than 5% by weight. In addition, the C of the bio-supply raw material or its bio-components. 22+ The content may be approximately 5% by weight, 10% by weight, 20% by weight, 30% by weight, 40% by weight, 50% by weight, over 60% by weight, or a combination thereof. C of the bio-supply raw material or its bio-components. 22+ The content may range from approximately 0-70% by weight, 0-60% by weight, 0-50% by weight, 0-40% by weight, 5-70% by weight, 5-60% by weight, 5-50% by weight, 5-40% by weight, 10-70% by weight, 10-60% by weight, 10-50% by weight, 10-40% by weight, 20-70% by weight, 20-60% by weight, 20-50% by weight, or 20-40% by weight.

[0052] C of bio-supplied raw materials and / or their bio-components 20+ In addition to the content, as well as the limitations or scope of C mentioned above. 16 , C 18 , C 20 and / or C 22+ In addition to or separately from the content, C of the bio-supply raw materials and / or their bio-components. 24+ The content may be approximately 70% by weight, 60% by weight, 50% by weight, 40% by weight, 30% by weight, 20% by weight, 10% by weight, or less than 5% by weight. C of the bio-supply raw material or its bio-components. 24+ The content may be approximately 5% by weight, 10% by weight, 20% by weight, 30% by weight, 40% by weight, 50% by weight, over 60% by weight, or a combination thereof. C of the bio-supply raw material or its bio-components. 24+ The content may range from approximately 0-70% by weight, 0-60% by weight, 0-50% by weight, 0-40% by weight, 5-70% by weight, 5-60% by weight, 5-50% by weight, 5-40% by weight, 10-70% by weight, 10-60% by weight, 10-50% by weight, 10-40% by weight, 20-70% by weight, 20-60% by weight, 20-50% by weight, or 20-40% by weight.

[0053] In some cases, the C of bio-supply raw materials and / or their bio-components 20 ~C 32 The content may be at least about 10% by weight, or 15% by weight, or 20% by weight, or 30% by weight, or 40% by weight, or 50% by weight, or 60% by weight, or 70% by weight, or 80% by weight, or about 10-80% by weight, or 15-80% by weight, or 20-80% by weight, or 30-80% by weight, or 40-80% by weight, or 50-80% by weight, or 60-80% by weight, or 70-80% by weight.

[0054] Generally, C of bio-supply raw materials and / or their bio-components 20+ In addition to the content, the bio-component C 16 The content is approximately 0-70% by weight, and the bio-component C 18 The content can be approximately 0-70% by weight, and the biocomponent C 20 The content can be approximately 0-70% by weight, and the biocomponent C 22 The content can be approximately 0-70% by weight, and the biocomponent C 22+ The content can be approximately 0-70% by weight, and the biocomponent C 24 The content can be approximately 0-70, 60, 50, or 40% by weight, and the biocomponent C 24+ The content may be approximately 0-70, 60, 50, or 40% by weight, or a combination thereof.

[0055] Generally, bio-supply materials may contain or be bio-component supplies, and bio-supply materials may contain at least about 10% by weight of C 20+ It contains one or more bio-components having a certain content. For example, suitable bio-components may include carinata oil, rapeseed oil, peanut oil, mustard oil, animal fat, rice bran wax, carnauba wax, or a combination thereof. In some embodiments, the bio-component feed is typically high C 20+It may contain one or more other bio-components that are not present in the specified amount, for example, such bio-components may include canola oil, corn oil, soybean oil, castor oil, camelina oil, palm oil, or combinations thereof.

[0056] The biocomponent feed may have an oxygenated content of at least about 0.5% by weight relative to the total weight of the biocomponent feed, for example, at least about 1.0% by weight, at least about 2.0% by weight, at least about 3.0% by weight, at least about 4.0% by weight, or at least about 5.0% by weight relative to the total weight of the biocomponent feed. The biocomponent feed may have an oxygenated content of, for example, up to about 15% by weight relative to the total weight of the biocomponent feed, or up to about 10% by weight relative to the total weight of the biocomponent feed, or up to about 5% by weight relative to the total weight of the biocomponent feed. In some embodiments, the biocomponent feed has an oxygenated content in the range of about 1 to 15% by weight relative to the total weight of the biocomponent feed, for example, in the range of about 5 to 15% by weight, or about 10 to 15% by weight relative to the total weight of the biocomponent feed. The oxygenated content of the biocomponent feed may be measured by neutron activation analysis according to, for example, ASTM E385-90 (2002).

[0057] The bio-component feedstock may be hydrogenated, for example, with a hydrogenation isomerization / hydrogenation dewaxing catalyst before contact with a hydrogenation conversion catalyst for further hydrogenation treatment. In some cases, the bio-component feedstock may have a sulfur (S) content of less than about 200 ppm, e.g., less than about 100 ppm, less than about 50 ppm, or less than about 20 ppm. In some cases, the bio-component feedstock may have a nitrogen (N) content of less than about 50 ppm, e.g., less than about 20 ppm, or less than about 10 ppm. In some cases, the hydrogenated bio-component feedstock may typically have an oxygenated content of about 0% by weight, or less than about 2% by weight, or less than 5% by weight. The nitrogen content of the bio-component feedstock can be determined according to ASTM D4629. The sulfur content of the bio-component feedstock can be determined according to ASTM D2622.

[0058] Hydrogenation catalysts may include hydrogenation catalysts and / or hydrogenation isomerization catalysts, and may include noble metal catalysts as hydrogenation catalysts. In some cases, hydrogenation catalysts may include base metal catalysts or combinations of base metal and noble metal catalysts. Base metal catalysts typically include base metals selected from Mo, Ni, W, Co, and combinations thereof, or Mo, or combinations of Mo and Ni. Similarly, noble metal catalysts typically include noble metals selected from Pt, Pd, or combinations thereof.

[0059] As used herein, the term “hydrogen isomerization catalyst” refers to a catalyst that promotes the isomerization of the skeletal structure of hydrocarbon molecules. In some embodiments, suitable hydrogen isomerization catalysts include catalysts containing zeolites such as SSZ-91, SSZ-32, and SSZ-32x. Other hydrogen isomerization catalysts may also be suitable, for example, catalysts based on zeolite ZSM-48, and / or combinations of ZSM-48 with other hydrogen isomerization catalysts. Combinations of suitable hydrogen isomerization catalysts based on the same or different zeolite supports may also be used.

[0060] The hydrogenation isomerization catalyst may include, but is not limited to, zeolite SSZ-91, or zeolite SSZ-91 in an amount of about 5 to about 95% by weight relative to the total weight of the hydrogenation isomerization catalyst, or zeolite SSZ-91 in an amount of about 10 to about 95% by weight, about 20 to about 90% by weight, or zeolite SSZ-91 in an amount of about 25 to about 85% by weight, or zeolite SSZ-91 in an amount of about 30 to about 80% by weight, or zeolite SSZ-91 in an amount of about 35 to about 75% by weight, or zeolite SSZ-91 in an amount of about 35 to about 65% by weight, or zeolite SSZ-91 in an amount of about 35 to about 55% by weight, or zeolite SSZ-91 in an amount of about 45 to about 75% by weight, or zeolite SSZ-91 in an amount of about 55 to about 75% by weight, relative to the total weight of the hydrogenation isomerization catalyst.

[0061] The hydrogenation isomerization catalyst may further include a metal modifier, for example, selected from metals of Group 2, Group 8, Group 9, and Group 10 or combinations thereof. In some embodiments, the metal modifier is selected from metals of Group 8, Group 9, or Group 10 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 hydrogenation isomerization catalyst includes platinum, palladium, or combinations thereof. Base metals such as Mo, Ni, W, Co, and combinations thereof may be included in the catalyst.

[0062] The hydrogenation isomerization catalyst contains about 0.05 to about 10% by weight, 5% by weight, or 2.0% by weight of a metal modifier (e.g., selected from metals of groups 2, 8, 9, and 10, or metals of group 8, 9, or 10, e.g., metals of group 10, e.g., platinum) relative to the total weight of the hydrogenation isomerization catalyst, for example, about 0.1 to about 1.5% by weight, or about 0.2 to about 1.5% by weight, or about 0.1 to about 1% by weight relative to the total weight of the hydrogenation isomerization catalyst. In some cases, for example, if a base metal is included, the metal content is higher, for example, at least about 5% by weight, or 10% by weight, or 15% by weight, or 20% by weight, or 25% by weight, or at least about 30% by weight, or about 2% by weight, or in the range of 5% to about 25% by weight, or 30% by weight.

[0063] Hydrogenation isomerization catalysts may further contain oxide binders. Suitable oxide binders include inorganic oxides, and for example, oxide binders may be selected from alumina, silica, ceria, titania, tungsten oxide, zirconia, and combinations thereof. Hydrogenation isomerization catalysts may contain oxide binders containing alumina. Suitable alumina are commercially available, for example, Catapal® alumina and Pural® alumina from Sasol®, or Versal® alumina from UOP®. Generally, alumina can be any alumina known to be used as a catalyst-based matrix material. For example, alumina may be boehmite, bayerite, γ-alumina, η-alumina, θ-alumina, δ-alumina, χ-alumina, or mixtures thereof. The hydrogenation isomerization catalyst may contain approximately 5 to approximately 95% by weight of an oxide binder relative to the total weight of the hydrogenation isomerization catalyst, for example, approximately 5 to approximately 80% by weight of an oxide binder, approximately 10 to approximately 70% by weight of an oxide binder, and approximately 20 to approximately 70% by weight of an oxide binder, for example, approximately 25 to approximately 65% ​​by weight of an oxide binder relative to the total weight of the hydrogenation isomerization catalyst.

[0064] The hydrogenation isomerization catalyst may contain approximately 5 to approximately 95% by weight of zeolite SSZ-91, approximately 0.05 to approximately 2.0% by weight of group 8 to 10 metals, and approximately 5 to approximately 95% by weight of oxide binder based on the total weight of the hydrogenation isomerization catalyst. The hydrogenation isomerization catalyst may contain approximately 30 to approximately 80% by weight of zeolite SSZ-91, approximately 0.1 to approximately 1.5% by weight of group 8 to 10 metals, and approximately 20 to approximately 70% by weight of oxide binder based on the total weight of the hydrogenation isomerization catalyst.

[0065] Zeolite SSZ-91 and a method for manufacturing zeolite SSZ-91 are described in US-A-9920260, which is incorporated herein by reference in its entirety. Zeolite SSZ-91 is also known as SSZ-91 molecular sieve.

[0066] Zeolite SSZ-91 has an SiO2 / Al2O3 molar ratio (SAR) of 40 to 220. In some embodiments, zeolite SSZ-91 has an SiO2 / Al2O3 molar ratio (SAR) of 40 to 200, for example, 70 to 200, 80 to 200, 70 to 180, 80 to 180, 70 to 160, 80 to 160, 70 to 140, 80 to 140, 100 to 160, 100 to 140, or 120 to 140. The SAR is determined by inductively coupled plasma (ICP) elemental analysis.

[0067] Zeolite SSZ-91 is composed of polytype 6 at least 70% of the total ZSM-48 type material present in the product. The proportion of polytype 6 in the total ZSM-48 type material present in the product was determined by DIFFaX simulation and described by Lobo and Koningsveld in J.Am.Chem.Soc.2012,124,13222-13230, where failures were adjusted for three different failure probabilities. Note that the expression "at least X%" includes the case where no other ZSM-48 polytypes are present in the structure, i.e., the material is 100% polytype 6. The structure of polytype 6 is described by Lobo and Koningsveld (J.Am.Chem.Soc.2002,124,13222-13230). reference In some embodiments, the SSZ-91 material is composed of polytype 6, with at least 80% of the total ZSM-48 type material present in the product. In some embodiments, the SSZ-91 material is composed of polytype 6, with at least 90% of the total ZSM-48 type material present in the product. The polytype 6 structure is given the framework code *MRE by the Structure Commission of the International Zeolite Association.

[0068] Zeolite SSZ-91 has a morphology characterized by being a polycrystalline aggregate containing microcrystals having an average aspect ratio in the range of 1 to 8 collectively. In some embodiments, zeolite SSZ-91 has a morphology characterized by being a polycrystalline aggregate containing microcrystals having an average aspect ratio in the range of 1 to 6, for example, 1 to 5, 1 to 4, or 1 to 3 collectively.

[0069] In some embodiments, zeolite SSZ-91 has a morphology characterized as a polycrystalline aggregate having a diameter of about 100 nm to 1.5 μm, and each aggregate comprises an aggregate of microcrystals having an average aspect ratio in the range of 1 to 8 collectively. In some embodiments, zeolite SSZ-91 has a morphology characterized as a polycrystalline aggregate having a diameter of about 100 nm to 1.5 μm, and each aggregate comprises an aggregate of microcrystals having an average aspect ratio in the range of 1 to 6, for example, 1 to 5, 1 to 4, or 1 to 3 collectively. As used herein, the term diameter refers to the shortest length of the short end of each microcrystal being examined.

[0070] Zeolite SSZ-91 is a substantially phase-pure material. As used herein, the term “substantially phase-pure material” means that the material contains no zeolite phases other than the zeolite phase belonging to the ZSM-48 family of zeolites, or contains them in amounts that do not have a measurable effect on the material's selectivity, or in amounts that cause a material disadvantage to the material's selectivity. Two common phases that cocrystallize with SSZ-91 are EUO-type molecular sieves, e.g., EU-1, as well as magadiite and kenyaite. These additional phases may exist as separate phases or may grow together with the SSZ-91 phase.

[0071] Zeolite SSZ-91 may contain an amount of EUO-type molecular sieve phase ranging from 0 to 7 wt% of the total zeolite SSZ-91 product. In some embodiments, zeolite SSZ-91 contains an amount of EUO-type molecular sieve phase ranging from 0 to 5.0 wt%, for example, 0 to 4.0 wt%, or 0 to 3.5 wt%. In some embodiments, zeolite SSZ-91 contains an amount of EUO-type molecular sieve phase ranging from 0.1 to 7.0 wt%, for example, 0.1 to 5.0 wt%, 0.1 to 4.0 wt%, or 0.1 to 3.5 wt%. In some embodiments, the zeolite SSZ-91 includes 0-7% by weight of EU-1, for example, 0-5.0% by weight of EU-1, 0-4.0% by weight of EU-1, 0-3.5% by weight of EU-1, 0.1-7.0% by weight of EU-1, 0.1-5.0% by weight of EU-1, 0.1-4.0% by weight of EU-1, 0.1-3.5% by weight of EU-1, 0.1-2% by weight of EU-1, or 0.1-1% by weight of EU-1.

[0072] It is known that the ratio of powder XRD peak intensities changes linearly as a function of the weight fractions of any two phases in a mixture: (Iα / Iβ) = (RIRα / RIRβ) * (xα / xβ). Here, the RIR (Ratio of Reference Intensities) parameter can be found in The International Centre for Diffraction Data's Powder Diffraction File (PDF) database (http: / / www.icdd.com / products / ). Therefore, the weight percentage of the EUO phase in zeolite SSZ-91 can be calculated by measuring the ratio between the peak intensity of the EUO phase and the peak intensity of the SSZ-91 phase.

[0073] In general, zeolite SSZ-91 has a molar ratio (SAR) of silicon dioxide (SiO2) to aluminum oxide (Al2O3) of 40 to 220, may contain at least 70% polytype 6 of the entire ZSM-48 type material, may contain 0 to 7.0 wt% of EUO type molecular sieve phase, and zeolite SSZ-91 has a morphology characterized by a polycrystalline aggregate containing crystallites having an overall average aspect ratio of 1 to 8. In some embodiments, zeolite SSZ-91 has a molar ratio (SAR) of silicon dioxide (SiO2) to aluminum oxide (Al2O3) of 40 to 220, may contain at least 70% polytype 6 of the entire ZSM-48 type material, may contain 0 to 4.0 wt% of EUO type molecular sieve phase, and zeolite SSZ-91 has a morphology characterized by a polycrystalline aggregate containing crystallites having an overall average aspect ratio of 1 to 8. Zeolite SSZ-91 has a molar ratio (SAR) of silicon dioxide (SiO2) to aluminum oxide (Al2O3) of 40 to 220, may contain at least 70% polytype 6 of the entire ZSM-48 type material, may contain 0 to 3.5 wt% of EUO type molecular sieve phase, and is characterized as a polycrystalline aggregate containing crystallites having an overall average aspect ratio of 1 to 8. Zeolite SSZ-91 has a molar ratio (SAR) of silicon dioxide (SiO2) to aluminum oxide (Al2O3) of 40 to 200, may contain at least 70% polytype 6 of the entire ZSM-48 type material, may contain 0 to 4.0 wt% of EUO type molecular sieve phase, and is characterized as a polycrystalline aggregate containing crystallites having an overall average aspect ratio of 1 to 8. In some embodiments, zeolite SSZ-91 has a molar ratio (SAR) of silicon dioxide (SiO2) to aluminum oxide (Al2O3) of 70 to 200, contains at least 70% polytype 6 of the entire ZSM-48 type material, contains 0 to 4.0 wt% of EUO type molecular sieve phase, and is characterized as a polycrystalline aggregate containing crystallites having an average aspect ratio of 1 to 6 overall.Zeolite SSZ-91 has a molar ratio (SAR) of silicon dioxide (SiO2) to aluminum oxide (Al2O3) of 80 to 200, may contain at least 70% polytype 6 of the entire ZSM-48 type material, may contain 0.1 to 7.0 wt% of EUO type molecular sieve phase, and is characterized as a polycrystalline aggregate containing crystallites having an average aspect ratio of 1 to 6 overall. Zeolite SSZ-91 has a molar ratio (SAR) of silicon dioxide (SiO2) to aluminum oxide (Al2O3) of 80 to 200, may contain at least 70% polytype 6 of the entire ZSM-48 type material, may contain 0.1 to 4.0 wt% EU-1, and is characterized as a polycrystalline aggregate containing crystallites having an average aspect ratio of 1 to 6 overall. Zeolite SSZ-91 has a molar ratio (SAR) of silicon dioxide (SiO2) to aluminum oxide (Al2O3) of 80 to 200, may contain at least 70% polytype 6 of the entire ZSM-48 type material, may contain 0.1 to 4.0 wt% EUO-type molecular sieve phase, and is characterized as a polycrystalline aggregate containing crystallites having an average aspect ratio of 1 to 6 overall. Zeolite SSZ-91 has a molar ratio (SAR) of silicon dioxide (SiO2) to aluminum oxide (Al2O3) of 80 to 160, may contain at least 70% polytype 6 of the entire ZSM-48 type material, and may contain 0.1 to 4.0 wt% of EUO type molecular sieve phase. Zeolite SSZ-91 is characterized as a polycrystalline aggregate containing crystallites with an overall average aspect ratio of 1 to 6.Zeolite SSZ-91 has a molar ratio (SAR) of silicon dioxide (SiO2) to aluminum oxide (Al2O3) of 70 to 160, may contain at least 70% polytype 6 of the entire ZSM-48 type material, may contain 0.1 to 4.0 wt% of EUO type molecular sieve phase, and is characterized as a polycrystalline aggregate containing crystallites having an average aspect ratio of 1 to 6 overall. Zeolite SSZ-91 has a molar ratio (SAR) of silicon dioxide (SiO2) to aluminum oxide (Al2O3) of 70 to 200, may contain at least 80% polytype 6 of the entire ZSM-48 type material, may contain 0.1 to 4.0 wt% of EUO type molecular sieve phase, and is characterized as a polycrystalline aggregate containing crystallites having an average aspect ratio of 1 to 6 overall. Zeolite SSZ-91 has a molar ratio (SAR) of silicon dioxide (SiO2) to aluminum oxide (Al2O3) of 80 to 200, may contain at least 80% polytype 6 of the entire ZSM-48 type material, may contain 0.1 to 4.0 wt% of EUO type molecular sieve phase, and is characterized as a polycrystalline aggregate containing crystallites having an overall average aspect ratio of 1 to 6. Zeolite SSZ-91 has a molar ratio (SAR) of silicon dioxide (SiO2) to aluminum oxide (Al2O3) of 80 to 200, may contain at least 80% polytype 6 of the entire ZSM-48 type material, may contain 0.1 to 7.0 wt% of EUO type molecular sieve phase, and is characterized as a polycrystalline aggregate containing crystallites having an overall average aspect ratio of 1 to 4. Zeolite SSZ-91 has a molar ratio (SAR) of silicon dioxide (SiO2) to aluminum oxide (Al2O3) of 80 to 200, may contain at least 80% polytype 6 of the entire ZSM-48 type material, and may contain 0.1 to 4.0 wt% of EUO type molecular sieve phase. Zeolite SSZ-91 is characterized as a polycrystalline aggregate containing crystallites having an average aspect ratio of 1 to 4 overall.Zeolite SSZ-91 has a molar ratio (SAR) of silicon dioxide (SiO2) to aluminum oxide (Al2O3) of 80 to 160, may contain at least 80% polytype 6 of the entire ZSM-48 type material, and may contain 0.1 to 4.0 wt% of EUO type molecular sieve phase. Zeolite SSZ-91 is characterized as a polycrystalline aggregate containing crystallites having an overall average aspect ratio of 1 to 4. In some embodiments, zeolite SSZ-91 has a molar ratio (SAR) of silicon dioxide (SiO2) to aluminum oxide (Al2O3) of 100 to 140, contains at least 80% polytype 6 of the entire ZSM-48 type material, contains 0.1 to 4.0 wt% EU-1 type molecular sieve phase, and zeolite SSZ-91 has a morphology characterized by a polycrystalline aggregate containing crystallites having an overall average aspect ratio of 1 to 4.

[0074] Zeolite SSZ-91 synthesized as described herein can be characterized by its XRD pattern. The powder XRD lines in Table 1 are representative of zeolite SSZ-91 in its as-synthesized state. Slight variations in the diffraction pattern may be due to variations in the molar ratio of framework species in a particular sample due to changes in the lattice constant. Furthermore, sufficiently small crystals affect the shape and intensity of the peaks, leading to significant peak broadening. Slight changes in the diffraction pattern may also be due to variations in the organic compounds used in preparation or variations in the Si / Al molar ratio from sample to sample. Sintering may also cause slight shifts in the XRD pattern. Despite these small perturbations, the fundamental crystal lattice structure remains unchanged. [Table 1]

[0075] The X-ray diffraction pattern lines in Table 2 represent the calcined SSZ-91. [Table 2]

[0076] The powder X-ray diffraction patterns shown herein were collected using standard techniques. The radiation was CuK α It was radiation. The height and position of the peak were read from the relative intensity of the peak as a function of 2θ (where θ is the Bragg angle) (after adjusting for background), and the interplanar spacing d corresponding to the recorded line could be calculated.

[0077] Zeolite SSZ-91 can be used as-synthesized, but is usually heat-treated (calcined). The term "as-synthesized" refers to zeolite SSZ-91 in its form after crystallization and before the removal of SDA cations. SDA can be removed by thermal treatment (e.g., calcination) at a temperature that can be easily determined by a person skilled in the art to remove SDA from molecular sieves, for example, in an oxidizing atmosphere (e.g., air, gas with oxygen partial pressure greater than 0 kPa). SDA can also be removed by ozonation and photodegradation techniques (e.g., exposing SDA-containing molecular sieve products to light or electromagnetic radiation having wavelengths shorter than visible light under conditions sufficient to selectively remove organic compounds from molecular sieves), as described in U.S. Patent No. 6,960,327.

[0078] Next, the zeolite SSZ-91 can be calcined in steam, air, or an inert gas at a temperature in the range of 200°C to 800°C for a period of time ranging from 1 hour to several days, for example, 1 to 48 hours. Typically, the extraskeletal cations (e.g., Na) are converted by ion exchange. + It is desirable to remove the ions and replace them with hydrogen, ammonium, or any desired metal ions.

[0079] If the formed molecular sieve is an intermediate molecular sieve, the target molecular sieve (e.g., zeolite SSZ-91) can be achieved using post-synthesis techniques such as heteroatom lattice substitution techniques. The target molecular sieve (e.g., zeolite SSZ-91) can also be achieved by removing heteroatoms from the lattice using known techniques such as acid leaching.

[0080] Zeolite SSZ-91 produced by the processes disclosed herein can be formed into a wide variety of physical shapes. Zeolite SSZ-91 may be in the form of a powder, granules, or molded products such as extruded products having a particle size sufficient to pass through a 2-mesh (Tyler) screen and be retained on a 400-mesh (Tyler) screen. When the catalyst is molded, for example by extrusion with an organic binder, zeolite SSZ-91 may be extruded before, after, or partially after drying.

[0081] Zeolite SSZ-91 can be compounded with other materials that are resistant to the temperatures and other conditions used in organic conversion processes. Such matrix materials include active and inactive materials, synthetic or natural molecular sieves, and inorganic materials such as clay, silica, and metal oxides. Examples and uses of such materials are disclosed in U.S. Patents 4,910,006 and 5,316,753.

[0082] Hydrogenation isomerization catalysts, such as zeolite SSZ-91, may be in their as-synthesized form or in a calcined form. In some embodiments, the hydrogenation isomerization catalyst is formed from calcined zeolite SSZ-91. In some embodiments, the hydrogenation isomerization catalyst comprises zeolite SSZ-91 and a molecular sieve selected from group 2, 8, 9, or 10 metals (e.g., group 8-10 metals such as Pt).

[0083] In some embodiments, the hydrogenation isomerization catalyst is formed by compositing molecular sieve zeolite SSZ-91 (in its as-synthesized or calcined form) with an oxide binder such as alumina. In some embodiments, compositing molecular sieve zeolite SSZ-91 (in its as-synthesized or calcined form) with an oxide binder involves mixing molecular sieves selected from the zeolite SSZ-91 (in its as-synthesized or calcined form) with the oxide binder and extruding the product. The mixture of molecular sieves and oxide binder can be formed into particles or extruded products having a wide range of physical shapes and dimensions. In some embodiments, the extruded products or particles may be dried and calcined before filling with metal. In some embodiments, the extruded products or particles are impregnated with a metal, for example, a group 2, 8, 9, or 10 metal (e.g., a group 8-10 metal such as Pt), and then dried and calcined. In some embodiments, the extruded material or particles are dried and calcined before being filled with metal.

[0084] Hydrogenation isomerization catalysts can be prepared by: compositing molecular sieves (such as zeolite SSZ-91) with an oxide binder to form an extruded base; impregnating the extruded base with an impregnation solution containing a metal, such as a group 2, 8, 9, or 10 metal (e.g., a group 8-10 metal such as Pt), to form a metal-supported extruder; drying the metal-supported extruder; and calcining the dried metal-supported extruded product.

[0085] Hydrogenation isomerization catalysts can be formed by impregnating molecular sieves (such as zeolite SSZ-91) with a solution containing a metal, e.g., a group 2, 8, 9, or 10 metal (e.g., a group 8-10 metal such as Pt). In some embodiments, the hydrogenation isomerization catalyst can be formed by impregnating calcined molecular sieves with a solution containing a group 2, 8, 9, or 10 metal (e.g., a group 8-10 metal such as Pt). In some embodiments, the hydrogenation isomerization catalyst is formed by impregnating an extruded base containing molecular sieves and an oxide binder. In some embodiments, the extruded base is exposed to an impregnation solution containing a metal (e.g., a group 2, 8, 9, or 10 metal (e.g., a group 8-10 metal such as Pt)) for 0.1 to 10 hours (e.g., immersed in the impregnation solution).

[0086] The extruded base may be dried (for example, at a temperature in the range of approximately 100°F (38°C) to approximately 300°F (149°C) for approximately 0.1 to approximately 10 hours) and fired (at a temperature in the range of approximately 390°F (199°C) to approximately 1200°F (649°C), or at a temperature in the range of approximately 600°F (316°C) to approximately 1200°F (649°C) for approximately 0.1 to approximately 10 hours) before impregnation.

[0087] An extruded base can be formed by compositing molecular sieves (such as zeolite SSZ-91), and the oxide binder is dried and calcined before impregnation. To form a metal-supported extruded material, the dried and calcined extruded base may be impregnated with an impregnation solution, and then dried and calcined again to form a hydrogenation isomerization catalyst.

[0088] For example, an impregnated extruded base containing zeolite SSZ-91 can be dried at a temperature in the range of about 100°F (38°C) to about 300°F (149°C) for about 0.1 to about 10 hours. The dried metal-filled extruded can be calcined at a temperature in the range of about 600°F (316°C) to about 1200°F (649°C) for about 0.1 to about 10 hours. In some embodiments, calcination is carried out in air.

[0089] A process for hydrogenating bio-supply materials involves contacting the bio-supply materials with a hydrogenation catalyst under hydrogenation conditions. Hydrogenation occurs in the presence of hydrogen and may include hydrogenation isomerization and / or hydrogenation treatment and hydrogenation isomerization processes. Hydrogenation may also include other processes, such as hydrogenocracking.

[0090] Hydrogenation may be carried out in the presence of a hydrogenation catalyst containing SSZ-91. In some embodiments, the hydrogenation isomerization catalyst contains SSZ-91. The biosupply may consist only of renewable biocomponents and / or exclude or intentionally omit fossil fuel components. The biosupply may be used on its own, i.e., fossil fuel components or other non-biofsupply components are not added with the biosupply.

[0091] This process generally involves at least about 10% by weight of C 20+ The bio-supply material utilizes one or more bio-components having a certain content, and the hydrogen conversion catalyst includes a hydrogenation isomerization catalyst. In some cases, the bio-supply material contains at least about 10% by weight of C 20 ~C 24 It may contain one or more bio-components having a certain content. However, it is not limited to the C content of the bio-components. 20 ~C 24 The content may be at least about 15% by weight, or 20% by weight, or 30% by weight, or 40% by weight, or 50% by weight.

[0092] The process may also be a single-step process, for example, in which intermediate and / or final products are not removed between steps or between catalyst beds. In some embodiments, the process may be advantageously carried out in a single reactor. Alternatively, the process may be carried out in two or more reactors connected in series, for example, a first reactor or catalyst section comprising a hydrogenation section and reactor, or a catalyst section, and a section or reactor downstream of the first reactor or catalyst section comprising a hydrogenation isomerization section. All products from the hydrogenation section may be sent to the hydrogenation isomerization section or sent directly thereto, i.e., no intermediate products are removed between sections. A separate hydrocracking catalyst may not be necessary or used in the process to produce the regenerative product. Those skilled in the art will understand that various reactor configurations and catalyst packing arrangements are possible according to the present invention.

[0093] Hydrogenation conversion conditions typically involve temperatures ranging from approximately 300°F to 800°F (149°C to 427°C); pressures ranging from approximately 15 to 3000 psig (0.10 to 20.68 MPa gauge); and a duration of approximately 0.1 to 20 hours. -1 The supply rate of bio-supply materials in the LHSV range; and approximately 1,000 or 1,500 or 2,000 to approximately 10,000 standard cubic feet H2 (supply 1 m 3 Approximately 180 to 1800m 3 This may include the supply rate of hydrogen and bio-supply materials in the ratio of H2).

[0094] In some cases, the hydrogenation isomerization conditions may include temperatures in the range of approximately 300°F to approximately 800°F (149°C to 427°C), for example, temperatures of approximately 550°F to approximately 700°F (288°C to 371°C). The hydrogenation isomerization conditions may include pressures in the range of approximately 15 to approximately 3000 psig (0.10 to 20.68 MPa gauge), for example, pressures of approximately 100 to approximately 2500 psig (0.69 to 17.24 MPa). The hydrogenation isomerization conditions may last approximately 0.1 to approximately 20 hours. -1 Speeds within the LHSV range, for example, approximately 0.1 to 5 hours. -1This may include the rate at which bio-supply materials are supplied to a reactor containing a hydrogenation isomerization catalyst for LHSV.

[0095] In some cases, the hydrogenation isomerization conditions are approximately 1,000, 1,500, or 2,000 per barrel of feedstock to approximately 10,000 standard cubic feet of H2 (1 m³ of feedstock). 3 Approximately 180 to 1800m 3 H2), for example, approximately 2500 to 5000 scfH2 per barrel of raw material (1 m³ of raw material). 3 Approximately 440-890m 3 It may contain hydrogen and bio-supplied raw materials supplied to the reactor in the ratio of H2.

[0096] In some embodiments, the hydrogenation isomerization conditions are as follows: temperature in the range of approximately 300°F (149°C), or 325°F (163°C), or 350°F (177°C), or 375°F (191°C), or 390°F (199°C) to approximately 800°F (427°C), for example, approximately 550°F to approximately 750°F (288°C to 399°C), or 570°F to approximately 675°F (299°C to 357°C); pressure in the range of approximately 15 to approximately 3000 psig (0.10 to 20.68 MPa gauge), for example, approximately 100 to approximately 2500 psig (0.69 to 17.24 MPa); and approximately 0.1 to approximately 20 hours. - 1LHSV, for example, approximately 0.1 to 5 hours - Feeding rate of feedstock to the reactor containing a hydrogenation isomerization catalyst in the range of 1 LHSV; approximately 1,000, or 1,500, or 2,000 per barrel of feedstock to approximately 10,000 standard cubic feet H2 (1 m³ of feedstock). 3 Approximately 180 to 1800m 3 H2, for example, approximately 2500 to 5000 scfH2 per barrel of raw material (1 m³ of supply material) 3 Approximately 440-890m 3 Hydrogen and bio-supplied raw materials are supplied to the reactor in the ratio of H2).

[0097] The process can generally be used to provide a variety of renewable products. In some cases, renewable products such as base oils, base oil components, lubricants, process fluids, or combinations thereof may be produced. Other products may also be produced during the process. Process fluids that may be produced, but are not limited to these, include drilling fluids, transformer fluids, thermal oils, working fluids, transmission fluids, metalworking fluids, or combinations thereof.

[0098] By contacting a bio-supply material with a hydrogenation isomerization catalyst according to the process, a base oil or component thereof may be provided that has an increased ratio of isoparaffin to normal paraffin compared to a hydrogenated bio-supply material. In some embodiments, contacting a bio-supply material with a hydrogenation isomerization catalyst under hydrogenation isomerization conditions provides a base oil or component thereof that exhibits a lower cloud point and lower pour point compared to a hydrogenated bio-supply material.

[0099] In some embodiments, contacting a bio-supply material with a hydrogenation-isomerization catalyst under hydrogenation-isomerization conditions provides a base oil or component exhibiting a lower cloud point and a lower pour point compared to the cloud point and pour point of the hydrogenated bio-supply material, wherein the base oil exhibits a cloud point at least 2°C, 4°C, 6°C, 8°C, or 10°C lower than the cloud point of the hydrogenated bio-supply material, and / or a pour point at least 2°C, 4°C, 6°C, 8°C, or 10°C lower than the pour point of the hydrogenated bio-supply material, or a cloud point at least 20°C lower than the cloud point of the hydrogenated bio-supply material, and / or a pour point at least 20°C lower than the pour point of the hydrogenated bio-supply material, or a cloud point at least 30°C lower than the cloud point of the hydrogenated bio-supply material, and / or a pour point at least 30°C lower than the pour point of the hydrogenated bio-supply material.

[0100] In some cases, the base oil product or its components may meet the specifications for Group III+ base oils, for example, the specifications for base oils having a VI greater than 130. However, base oils may be produced having a pour point of -10°C, -15°C, -20°C, -25°C, -30°C, -33°C, or -35°C, or -38°C or lower, and / or a viscosity at 100°C of 1.5, or 1.6, or 1.7, or 1.8 cSt or higher, and / or a VI greater than or equal to 105, or 107, or 109, or 113, or 117, or 121, or 125, or 129, or a combination thereof.

[0101] The bio-supply material may be brought into contact with the hydrogenation catalyst under hydrogenation conditions before contacting the bio-supply material with the hydrogenation isomerization catalyst. In some embodiments, the hydrogenation treatment conditions are: temperature in the range of about 300°F (149°C), or 325°F (163°C), or 350°F (177°C), or 375°F (191°C), or 390°F to about 800°F (199°C to 427°C), for example, about 500°F (260°C) or 550°F (288°C) to about 750°F (399°C), or 590°F to about 675°F (310°C to 357°C); pressure in the range of about 15 to about 3000 psig (0.10 to 20.68 MPa gauge), for example, about 100 to about 2500 psig (0.69 to 17.24 MPa); and about 0.1 to about 20 hours. - 1LHSV, for example, approximately 0.1 to 5 hours - Feeding rate of feedstock to the reactor containing a hydrogenation isomerization catalyst in the range of 1 LHSV; approximately 1,000, or 1,500, or 2,000 per barrel of feedstock to approximately 10,000 standard cubic feet H2 (1 m³ of feedstock). 3 Approximately 180 to 1800m 3 H2), for example, approximately 2500 to 5000 scfH2 per barrel of raw material (supply 1 m³ 3 Approximately 440-890m 3 It contains hydrogen and bio-supplied raw materials supplied to the reactor in the ratio of H2.

[0102] Hydrogenation catalysts generally comprise a refractory inorganic oxide support and a Group 6 metal modifier and / or Group 8-10 metal modifiers. The oxide support is also referred to herein as the binder. The support for the hydrogenation catalyst may be prepared from or contain alumina, silica, silica / alumina, titania, magnesia, zirconia, or combinations thereof. The hydrogenation catalyst support may comprise amorphous materials, crystalline materials, or combinations thereof. Examples of amorphous materials include, but are not limited to, amorphous alumina, amorphous silica, and amorphous silica-alumina.

[0103] The hydrogenation support may contain amorphous alumina. When a combination of silica and alumina is used, the distribution of silica and alumina in the support may be uniform or non-uniform. In some embodiments, the support may include silica, silica / alumina, or an alumina gel in which an alumina-based material is dispersed. The support may also contain refractory materials other than alumina or silica, such as other inorganic oxides or clay particles, provided that such materials do not adversely affect the hydrogenation activity of the final catalyst or cause harmful decomposition of the feedstock.

[0104] Silica and / or alumina may constitute at least about 90% by weight of the support of the hydrogenation catalyst. The support may be at least substantially entirely silica, or entirely alumina.

[0105] In some cases, the Group 8-10 metal modifier(s) of the hydrogenation catalyst may include Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, or a combination thereof. The Group 8-10 metal modifier of the hydrogenation catalyst may include Group 9 metals, Group 10 metals, or a combination thereof. The Group 8-10 metal modifier of the hydrogenation catalyst may include Co and / or Ni, or may be Co and / or Ni. The Group 8-10 metal modifier of the hydrogenation catalyst may include Ni, or may be Ni. The Group 8-10 metal modifier of the hydrogenation catalyst may include Co and Ni. The Group 8-10 metal modifier may be an oxide, a hydroxide, or a salt. In some cases, the Group 8-10 metal modifier is a salt. The amount of Group 8-10 metal modifier in a hydrogenation catalyst is generally 0.1-20% by weight (e.g., 1.0 or 2.0-10%) based on the bulk dry weight of the catalyst, calculated as metal oxides. The Group 6 metal modifier in a hydrogenation catalyst may be selected from Cr, Mo, W, and combinations thereof. The Group 6 metal modifier in a hydrogenation catalyst may contain or be Mo. The Group 6 metal modifier may be an oxide, an oxo acid, or an ammonium salt of an oxo or polyoxo anion. The amount of Group 6 metal modifier in a hydrogenation catalyst is generally 5-50% by weight (e.g., 10-40% or 15-30%) based on the bulk dry weight of the catalyst, calculated as metal oxides. In some cases, the hydrogenation catalyst contains Ni and Mo.

[0106] Group 8-10 and / or Group 6 metal modifiers for hydrogenation catalysts can be dispersed on an inorganic oxide support. Many methods are known in the art for depositing Group 8-10 and / or Group 6 metals, or compounds containing such metals, onto a support, and such methods include, but are not limited to, ion exchange, impregnation, and coprecipitation. In some embodiments, impregnation of the support with Group 8-10 and Group 6 metal modifiers can be carried out at a controlled pH value. Group 8-10 and Group 6 metal modifiers can be added to the impregnation solution as metal salts, such as halide salts and / or amine complexes and / or mineral acid salts. Other examples of metal salts that can be used include nitrates, carbonates, and bicarbonates, as well as carboxylates such as acetates, citrates, and formates.

[0107] Optionally, the impregnated carrier may be left with the impregnation solution for a period of time ranging from approximately 2 to approximately 24 hours. After impregnating the oxide carrier with a group 8-10 metal modifier and / or a group 6 metal modifier, the impregnated carrier can be dried and / or calcined. After the hydrogenation catalyst has been dried and calcined, the prepared catalyst can be reduced with hydrogen or sulfurized with a sulfur-containing compound, as is commonly done in the art, and then used, for example, in a reactor located upstream of a hydrogenation isomerization reactor.

[0108] Example 1 A simulated feedstock to reproduce a typical carinata oil composition was prepared using 3.2% by weight of nC16, 39.8% by weight of nC18, 11.7% by weight of nC20, 43.4% by weight of nC22, and 1.9% by weight of nC24.

[0109] When this simulated hydrogenated Carinata oil is supplied onto an SSZ-91 zeolite catalyst at 2.0 LHSV (space velocity per hour of liquid), 650°F, and 1000 psig, it exhibits a pour point of -39°C (ASTM D97), a highly desirable viscosity index of 138 (VI, ASTM D2270-04), and a KV100 of 2.09 cSt (ASTM D445-06, dynamic viscosity at 100°C, unit cSt or mm²). 2A process fluid product of ( / s) was obtained. Typical pour point specifications for process fluids in this viscosity range are 30 °C or lower, and in some cases, -35 °C or lower. The yield of the process fluid was 40.3 wt%. Without limitation, the remaining liquid product can be used to produce renewable fuel or used as a component thereof.

[0110] To avoid misunderstanding, this application is directed to the subject matter recited in the following numbered items.

[0111] 1. A process for making renewable products from a biofeedstock, the process comprising contacting the biofeedstock with a hydroconversion catalyst under hydroconversion conditions, the biofeedstock comprising at least about 10 wt% of C 20+ containing one or more bio-components, the hydroconversion catalyst comprising a hydroisomerization catalyst, the process.

[0112] 2. The process of item 1, wherein the biofeedstock comprises at least about 10 wt% of C 20 ~C 32 containing one or more bio-components.

[0113] 3. The C of the bio-component 20 ~C 32 content is at least about 10 wt%, or 15 wt%, or 20 wt%, or 30 wt%, or 40 wt%, or 50 wt%, or 60 wt%, or 70 wt%, or 80 wt%, or about 10 - 80 wt%, or 15 - 80 wt%, or 20 - 80 wt%, or 30 - 80 wt%, or 40 - 80 wt%, or 50 - 80 wt%, or 60% - 80 wt%, or 70 - 80 wt% range, the process of item 1 or 2.

[0114] 4. The C of the bio-component 20+ content is about 80 wt%, 70 wt%, 60 wt%, or 50 wt%, 40 wt%, less than 30 wt%, or 20 wt%, or the C of the bio-component20+ The content is more than about 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, or 70 wt%, or a combination thereof, or the C of the bio-component 20+ The content is in the range of about 10 - 80 wt%, 10 - 70 wt%, 10 - 60 wt%, 10 - 50 wt%, 10 - 40 wt%, 20 - 80 wt%, 30 - 80 wt%, 40 - 80 wt%, 50 - 80 wt%, 20 - 70 wt%, 20 - 60 wt%, 20 - 50 wt%, 20 - 40 wt%, 30 - 80 wt%, 30 - 70 wt%, 30 - 60 wt%, 30 - 50 wt%, 40 - 80 wt%, 40 - 70 wt%, 40 - 60 wt%, 50 - 80 wt%, 50 - 70 wt%, or 60 - 80 wt%, and the process according to any one of items 1 - 3

[0115] 5. The C of the bio-component 16 The content is about 0 - 70 wt%, and the C of the bio-component 18 The content is about 0 - 70 wt%, and the C of the bio-component 20 The content is about 0 - 70 wt%, and the C of the bio-component 22 The content is about 0 - 70 wt%, and the C of the bio-component 22+ The content is about 0 - 70 wt%, and the C of the bio-component 24 The content is about 0 - 70, or 60, or 50, or 40 wt%, and the C of the bio-component 24+ The content is about 0 - 70, or 60, or 50, or 40 wt%, or a combination thereof, and the process according to any one of items 1 - 4

[0116] 6. The bio-feedstock contains only renewable bio-components, and the process according to any one of items 1 - 3

[0117] 7. Fossil fuel components are not used together with the bio-feedstock of the process, and the process according to any one of items 1 - 4

[0118] 8. The process described in any of items 1 to 5, wherein the process is a single-stage process or a two-stage process.

[0119] 9. The process described in item 6, wherein the single-step process is carried out in a single reactor.

[0120] 10. The process according to item 6, wherein the single-step process is carried out in two or more reactors connected in series, the first reactor comprising a hydrogenation section, and the reactor downstream of the first reactor comprising a hydrogenation isomerization section.

[0121] 11. The process according to any one of items 1 to 8, wherein the renewable product comprises a base oil, a base oil component, a process fluid, or a combination thereof.

[0122] 12. The process described in item 9, wherein the process fluid is a drilling fluid, a transformer fluid, a thermal oil, a working fluid, a transmission fluid and / or a gear oil, a metalworking fluid, or a combination thereof.

[0123] 13. The process according to any one of items 1 to 10, wherein the hydrogenation catalyst comprises zeolite SSZ-91, SSZ-32, SSZ-32x, ZSM-48, or a combination thereof.

[0124] 14. The process according to any one of items 1 to 11, wherein the hydrogenation isomerization catalyst comprises SSZ-91.

[0125] 15. The process according to any one of items 1 to 12, wherein the hydrogenation catalyst is a noble metal catalyst, a combination of a base metal catalyst and a noble metal catalyst, or includes such a catalyst.

[0126] 16. The process according to any one of items 1 to 13, wherein the hydrogenation catalyst comprises a base metal catalyst and a noble metal catalyst.

[0127] 17. The process described in any of items 13 to 14, wherein the base metal is selected from Mo, Ni, W, Co and combinations thereof.

[0128] 18. The process according to any one of items 13 to 15, wherein the base metal is Mo, or a combination of Mo and Ni.

[0129] 19. The process described in any of items 12 to 15, wherein the precious metal is selected from Pt, Pd, and combinations thereof.

[0130] 20. The process according to any one of items 1 to 17, wherein the process includes a hydrogenation section and a hydrogen isomerization section, and all or part of the product from the hydrogenation section is passed directly through the hydrogen isomerization section.

[0131] 21. The process according to any one of items 1 to 18, wherein the renewable product includes an intermediate distillation product, a base oil product, or a combination thereof.

[0132] 22. The process according to item 19, wherein the renewable product comprises naphtha, kerosene, jet fuel, diesel fuel, base oil, or a combination thereof.

[0133] 23. A process according to any of items 1 to 20, wherein a hydrocracking catalyst is not used to produce the renewable product.

[0134] 24. The above hydrogenation conversion conditions are, Temperatures in the range of approximately 300°F to approximately 800°F (149°C to 427°C), Pressure in the range of approximately 15 to 3000 psig (0.10 to 20.68 MPa gauge), Approximately 0.1~20h -1 The supply rate of bio-supply raw materials within the LHSV range. Approximately 1,000 to 10,000 standard cubic feet H2 (1 m³ of supply material) per barrel of bio-supply raw material. 3 Approximately 180 to 1800m 3The ratio of hydrogen (H2) to bio-supply raw materials, The process described in any of items 1 through 21, including or a combination thereof.

[0135] 25. The process according to item 22, wherein the hydrogenation conversion conditions are hydrogenation treatment or hydrogenation isomerization.

[0136] 26. The process according to any one of items 1 to 22, wherein the hydrogenation catalyst comprises zeolite SSZ-91 and group 8-10 metals.

[0137] 27. The process according to any one of items 1 to 24, wherein the hydrogenation catalyst comprises zeolite SSZ-91, and the zeolite SSZ-91, in its calcined form, has substantially the X-ray diffraction pattern shown in the following table: [Table 3]

[0138] 28. The process according to any one of items 1 to 25, wherein the hydrogenation catalyst comprises zeolite SSZ-91 having a silicon dioxide to aluminum oxide ratio of 40-220, or 70-160, or 80-160, or 80-140, or 100-160.

[0139] 29. The process according to any one of items 1 to 26, wherein the hydrogenation catalyst comprises a zeolite SSZ-91 having polytype 6 that accounts for at least about 80% of the total ZSM-48 type material present in the zeolite SSZ-91, or a zeolite SSZ-91 having polytype 6 that accounts for at least about 90% of the total ZSM-48 type material present in the zeolite SSZ-91.

[0140] 30. The process according to any one of items 1 to 27, wherein the hydrogenation catalyst comprises zeolite SSZ-91, and the zeolite SSZ-91 comprises 0.1 to 4.0% by weight of an EUO-type molecular sieve phase.

[0141] 31. The process according to any one of items 1 to 28, wherein the hydrogenation catalyst comprises 0.1 to 4.0 wt% of EU-1 in zeolite SSZ-91.

[0142] 32. The process according to any one of items 1 to 29, wherein the hydrogenation catalyst comprises zeolite SSZ-91 having a form characterized as a polycrystalline aggregate containing microcrystals having an average aspect ratio of 1 to 4 collectively.

[0143] 33. The hydrogenation catalyst is A molar ratio of silicon dioxide to aluminum oxide of 40-220 or 70-160. A morphology characterized as a polycrystalline aggregate containing microcrystals having an average aspect ratio in the range of 1 to 4. The zeolite SSZ-91 contains at least about 80% polytype 6 of the total ZSM-48 type material, and 0.1 to 4.0 wt% EUO type molecular sieve phase. A process according to any of items 1 to 30, comprising zeolite SSZ-91 having the following characteristics.

[0144] 34. The process according to any one of items 1 to 31, wherein the hydrogenation catalyst comprises about 5 to about 95% by weight of zeolite SSZ-91 and about 0.05 to about 2.0% by weight of a metal modifier.

[0145] 35. The process according to any one of items 1 to 32, wherein the bio-supply raw materials include, or are, a bio-component supply selected from lipids, vegetable oils, seed oils, and animal fats, which include triglycerides and free fatty acids or combinations thereof.

[0146] 36. The process described in any of items 1 to 33, wherein the bio-supply raw material or bio-component is obtained from a plant family selected from Brassicaceae (formerly Cruciferaceae), Limnanthaceae, Simmondsiaceae, Tropaeolacae, Olocaceae, or a combination thereof.

[0147] 37. The process according to any one of items 1 to 34, wherein the bio-supply raw materials include, or are, bio-component supplies selected from, canola oil, corn oil, soybean oil, castor oil, camelina oil, palm oil, rapeseed oil, soybean oil, colza oil, tall oil, sunflower oil, hemp seed oil, olive oil, linseed oil, coconut oil, castor oil, peanut oil, palm oil, mustard oil, carinata oil, carnauba wax, rice oil, cottonseed oil, animal fat, yellow and brown fats, lard, whale oil, milk fats, fish oil, algal oil, sewage sludge, cuphea oil, camelina oil, jatropha oil, carcass oil, babassu oil, palm kernel oil, cranbe oil, etc.

[0148] 38. The process according to items 1 to 35, wherein the bio-supply raw materials include or are bio-component supplies selected from carinata oil, rapeseed oil, peanut oil, mustard oil, animal fat, carnauba wax, rice bran oil, or a combination thereof.

[0149] 39. The process according to any one of items 1 to 36, wherein the process produces a base oil exhibiting a lower cloud point compared to the cloud point of the hydrogenated bio-supply material.

[0150] 40. Base oil or base oil component produced in accordance with any of the processes described in items 1 to 37.

[0151] 41. The base oil described in item 40, wherein the base oil is a group III+ base oil having more than 130 VI.

[0152] 42. The base oil according to item 40 or 41, wherein the base oil has a pour point of -10°C, -15°C, -20°C, -25°C, -30°C, -33°C, -35°C, or -38°C or lower, a viscosity at 100°C of 1.5, 1.6, 1.7, or 1.8 cSt or higher, and a viscosity of VI of 105, 107, 109, 113, 117, 121, 125, or 129 or higher, or a combination thereof.

[0153] 43. Use of base oil components as described in item 40 for the manufacture of base oil or lubricating oil.

[0154] The present invention is not limited to the embodiments described above, and it is understood that various modifications and improvements can be made without departing from the concepts described herein. Except where mutually exclusive, each feature can be used individually or in combination with other features, and this disclosure extends to and includes all combinations and partial combinations of one or more features described herein.

[0155] The foregoing description of one or more embodiments of the present invention is primarily illustrative and may be modified, and it will be recognized that such modifications still incorporate the essence of the present invention. In determining the scope of the present invention, refer to the following claims.

[0156] For the purposes of U.S. patent practice and, where permitted, in other patent offices, any patents and publications referenced in the above description of the present invention are incorporated herein by reference to the extent that any information contained herein is consistent with and / or supplements the above disclosures.

Claims

1. A process for producing renewable products from bio-supply materials, the process comprising contacting the bio-supply materials with a hydrogenation catalyst under hydrogenation conditions, wherein the bio-supply materials contain at least about 10% by weight of C ２０＋ The process comprising one or more bio-components having a certain content, wherein the hydrogenation conversion catalyst comprises a hydrogenation isomerization catalyst.

2. The aforementioned bio-supply raw material contains at least about 10% by weight of C ２０ ~C ３２ The process according to claim 1, comprising one or more bio-components having a certain content.

3. The C of the biocomponent ２０ ~C ３２ The process according to claim 1 or 2, wherein the content is in the range of at least about 10% by weight, or 15% by weight, or 20% by weight, or 30% by weight, or 40% by weight, or 50% by weight, or 60% by weight, or 70% by weight, or 80% by weight, or about 10-80% by weight, or 15-80% by weight, or 20-80% by weight, or 30-80% by weight, or 40-80% by weight, or 50-80% by weight, or 60-80% by weight, or 70-80% by weight.

4. The C of the biocomponent ２０＋ The content is approximately 80% by weight, 70% by weight, 60% by weight, 50% by weight, 40% by weight, 30% by weight, or less than 20% by weight of the biocomponent C ２０＋ The content is approximately 20% by weight, 30% by weight, 40% by weight, 50% by weight, 60% by weight, or more than 70% by weight, or a combination thereof, or C ２０＋ The process according to any one of claims 1 to 3, wherein the content is in the range of approximately 10-80% by weight, 10-70% by weight, 10-60% by weight, 10-50% by weight, 10-40% by weight, 20-80% by weight, 30-80% by weight, 40-80% by weight, 50-80% by weight, 20-70% by weight, 20-60% by weight, 20-50% by weight, 20-40% by weight, 30-80% by weight, 30-70% by weight, 30-60% by weight, 30-50% by weight, 40-80% by weight, 40-70% by weight, 40-60% by weight, 50-80% by weight, 50-70% by weight, or 60-80% by weight.

5. The C of the bio-component １６ content is about 0 to 70% by weight, and the C of the bio-component １８ content is about 0 to 70% by weight, and the C of the bio-component ２０ content is about 0 to 70% by weight, and the C of the bio-component ２２ content is about 0 to 70% by weight, and the C of the bio-component ２２＋ content is about 0 to 70% by weight, and the C of the bio-component ２４ content is about 0 to 70, or 60, or 50, or 40% by weight, and the C of the bio-component ２４＋ content is about 0 to 70, or 60, or 50, or 40% by weight, or a combination thereof. The process according to any one of claims 1 to 4

6. The process according to any one of claims 1 to 3, wherein the bio-supply raw material comprises only renewable bio-components.

7. The process according to any one of claims 1 to 4, wherein fossil fuel components are not used together with the bio-supplied raw materials of the process.

8. The process according to any one of claims 1 to 5, wherein the process is a single-stage process or a two-stage process.

9. The process according to claim 6, wherein the single-step process is carried out in a single reactor.

10. The process according to claim 6, wherein the single-step process is carried out in two or more reactors connected in series, the first reactor comprising a hydrogenation section, and the reactor downstream of the first reactor comprising a hydrogenation isomerization section.

11. The process according to any one of claims 1 to 8, wherein the renewable product comprises a base oil, a base oil component, a process fluid, or a combination thereof.

12. The process according to claim 9, wherein the process fluid is a drilling fluid, a transformer fluid, a thermal oil, a working fluid, a transmission fluid and / or a gear oil, a metalworking fluid, or a combination thereof.

13. The process according to any one of claims 1 to 10, wherein the hydrogenation catalyst comprises zeolite SSZ-91, SSZ-32, SSZ-32x, ZSM-48, or a combination thereof.

14. The process according to any one of claims 1 to 11, wherein the hydrogenation isomerization catalyst comprises SSZ-91.

15. The process according to any one of claims 1 to 12, wherein the hydrogenation catalyst is a noble metal catalyst, a combination of a base metal catalyst and a noble metal catalyst, or comprises the same.

16. The process according to any one of claims 1 to 13, wherein the hydrogenation catalyst comprises a base metal catalyst and a noble metal catalyst.

17. The process according to any one of claims 13 to 14, wherein the base metal is selected from Mo, Ni, W, Co and combinations thereof.

18. The process according to any one of claims 13 to 15, wherein the base metal is Mo, or a combination of Mo and Ni.

19. The process according to any one of claims 12 to 15, wherein the precious metal is selected from Pt, Pd, and combinations thereof.

20. The process according to any one of claims 1 to 17, wherein the process comprises a hydrogenation section and a hydrogen isomerization section, and all or part of the product from the hydrogenation section is passed directly through the hydrogen isomerization section.

21. The process according to any one of claims 1 to 18, wherein the renewable product comprises an intermediate distillation product, a base oil product, or a combination thereof.

22. The process according to claim 19, wherein the renewable product comprises naphtha, kerosene, jet fuel, diesel fuel, base oil, or a combination thereof.

23. The process according to any one of claims 1 to 20, wherein no hydrocracking catalyst is used to produce the renewable product.

24. The aforementioned hydrogenation conversion conditions are, Temperatures in the range of approximately 300°F to approximately 800°F (149°C to 427°C), Pressure in the range of approximately 15 to approximately 3000 psig (gauge pressure of 0.10 to 20.68 MPa), Approximately 0.1 to approximately 20 hours －１ The supply rate of bio-supply raw materials within the LHSV range. Approximately 1,000 to 10,000 standard cubic feet H per barrel of bio-supply raw material. ２ (Supply 1m ３ Approximately 180 to 1800 meters ３ H ２ ) the ratio of hydrogen and bio-supply raw material supply rate, The process according to any one of claims 1 to 21, including or a combination thereof.

25. The process according to claim 22, wherein the hydrogenation conversion conditions are hydrogenation treatment or hydrogenation isomerization.

26. The process according to any one of claims 1 to 22, wherein the hydrogenation catalyst comprises zeolite SSZ-91 and group 8 to 10 metals.

27. The process according to any one of claims 1 to 24, wherein the hydrogenation catalyst comprises zeolite SSZ-91, and the zeolite SSZ-91, in its calcined form, has substantially the X-ray diffraction pattern shown in the following table: Table 1

28. The process according to any one of claims 1 to 25, wherein the hydrogenation catalyst comprises a zeolite SSZ-91 having a silicon dioxide to aluminum oxide ratio of 40 to 220, or 70 to 160, or 80 to 160, or 80 to 140, or 100 to 160.

29. The process according to any one of claims 1 to 26, wherein the hydrogenation catalyst comprises zeolite SSZ-91, and the zeolite SSZ-91 contains at least about 80% of the total ZSM-48 type material polytype 6, or the zeolite SSZ-91 contains at least about 90% of the total ZSM-48 type material polytype 6.

30. The process according to any one of claims 1 to 27, wherein the hydrogenation catalyst comprises zeolite SSZ-91, and the zeolite SSZ-91 comprises 0.1 to 4.0% by weight of an EUO-type molecular sieve phase.

31. The process according to any one of claims 1 to 28, wherein the hydrogenation catalyst comprises 0.1 to 4.0% by weight of zeolite SSZ-91 containing EU-1.

32. The process according to any one of claims 1 to 29, wherein the hydrogenation catalyst comprises a zeolite SSZ-91 having a form characterized as a polycrystalline aggregate containing microcrystals having an average aspect ratio of 1 to 4 collectively.

33. The aforementioned hydrogenation conversion catalyst A molar ratio of silicon dioxide to aluminum oxide of 40-220 or 70-160. A morphology characterized as a polycrystalline aggregate containing microcrystals having an average aspect ratio in the range of 1 to 4 collectively. The zeolite SSZ-91 contains at least about 80% of the total ZSM-48 type material, polytype 6, and 0.1 to 4.0% by weight of EUO type molecular sieve phase. A process according to any one of claims 1 to 30, comprising zeolite SSZ-91 having the following characteristics.

34. The process according to any one of claims 1 to 31, wherein the hydrogenation catalyst comprises about 5 to about 95% by weight of zeolite SSZ-91 and about 0.05 to about 2.0% by weight of a metal modifier.

35. The process according to any one of claims 1 to 32, wherein the bio-supply raw material comprises or is a bio-component supply selected from lipids containing triglycerides and free fatty acids, vegetable oils, seed oils, animal fats, or a combination thereof.

36. The process according to any one of claims 1 to 33, wherein the bio-supply raw material or bio-component is obtained from a plant family selected from Brassicaceae (formerly Cruciferaceae), Limnanthaceae, Simmondsiaceae, Tropaeolaceae, Olocaceae, or a combination thereof.

37. The process according to any one of claims 1 to 34, wherein the bio-supply raw materials include, or are, a bio-component supply selected from canola oil, corn oil, soybean oil, castor oil, camelina oil, palm oil, rapeseed oil, soybean oil, colza oil, tall oil, sunflower oil, hemp seed oil, olive oil, linseed oil, coconut oil, castor oil, peanut oil, palm oil, mustard oil, carinata oil, carnauba wax, rice oil, cottonseed oil, animal fat, yellow and brown fats, lard, whale oil, milk fat, fish oil, algal oil, sewage sludge, cuphea oil, camelina oil, jatropha oil, carcass oil, babassu oil, palm kernel oil, cranbe oil, and the like.

38. The process according to any one of claims 1 to 35, wherein the bio-supply raw material comprises or is a bio-component feed selected from carinata oil, rapeseed oil, peanut oil, mustard oil, animal fat, carnauba wax, rice bran oil, or a combination thereof.

39. The process according to any one of claims 1 to 36, wherein the process produces a base oil exhibiting a lower cloud point compared to the cloud point of the hydrogenated bio-supply material.

40. A base oil or base oil component produced according to the process described in any one of claims 1 to 37.

41. The base oil according to claim 40, wherein the base oil is a group III+ base oil having VI greater than 130.

42. The base oil according to claim 40 or 41, wherein the base oil has a pour point of -10°C, -15°C, -20°C, -25°C, -30°C, -33°C, -35°C, or -38°C or lower, a viscosity at 100°C of 1.5, 1.6, 1.7, or 1.8 cSt or higher, a VI of 105, 107, 109, 113, 117, 121, 125, or 129 or higher, or a combination thereof.

43. Use of the base oil component according to claim 40 for manufacturing a base oil or lubricating oil.

Images