Bimetallic SSZ-91 catalysts for renewable applications
The use of SSZ-91 molecular sieve with Pt and Ru or Pt and Re catalysts addresses the tolerance issues of noble metals to CO and CO2 in biofeedstocks, improving catalyst performance and yield in hydroconversion processes.
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- CHEVRON USA INC
- Filing Date
- 2025-10-31
- Publication Date
- 2026-05-07
AI Technical Summary
Current hydroconversion processes for biofeedstocks face challenges with noble metal catalysts having low tolerance to reaction byproducts like CO and CO2, leading to reduced catalyst performance and yield loss, while base metal catalysts offer lower activity and selectivity.
A process using a hydroisomerization catalyst comprising SSZ-91 molecular sieve and catalytically active metals Pt and Ru or Pt and Re to convert biofeedstocks into renewable products, reducing CO and CO2 generation and improving catalyst performance.
The process enhances catalyst activity and selectivity, decreases cloud point, and increases yield of renewable products like diesel and base oils, while extending catalyst life and reducing deactivation.
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Abstract
Description
T-11794-W001BIMETALLIC SSZ-91 CATALYSTS FOR RENEWABLE APPLICATIONSFIELD OF THE INVENTION
[0001] Process of making a renewable product by hydroisomerization of a biofeedstock.BACKGROUND
[0002] The use of renewable resources has garnered significant attention and effort in the drive to develop fossil fuel alternatives. The variety, availability, and versatility of various biofeedstocks has been of great interest, particularly certain lipid sources, leading to the development and commercial use of a number of bio-based fuel technologies. Ongoing economic interests, and the desire to reduce fossil fuel use, have provided incentives for improvements in existing technologies, and the development of new processes for utilizing renewable biofeedstocks to produce renewable fuels and other renewable products.
[0003] Renewable fuels (biofuels) and other products are seen as being important to reduce carbon and greenhouse emissions. Bioproducts derived from food are products typically made from food sources produced on arable land, while bioproducts derived from non-food sources are typically produced from lignocellulosic biomass like forestry residuals or agricultural residues and waste. Typical biofeedstocks in the food source category include a wide variety of lipids (e.g., vegetable oil, including used cooking oil, seed oils, animal fats, waste oils, algae oils, and the like). Typical non-food source feedstocks include wood, grasses, algae, crop byproduct, municipal solid waste, and the like. While renewable products derived from non-food sources are sometimes preferred over similar bioproducts derived from food sources, there remains an ongoing need for improvements in hydroconversion processes for all feedstock sources to produce renewable products.
[0004] Current dewaxing processes for producing products from hydrocarbonaceous feedstocks generally use base metal dewaxing catalysts, particularly in single stage hydroprocessing applications. Base metal dewaxing catalysts typically have low activity and selectivity, however, leading to higher product yield loss. While higher activity and selectivity can be achieved using noble metal catalysts than base metal catalysts, noble metal catalysts tend to have lower tolerance to reaction byproducts from biofeedstocks, such as CO and CO?. It would be a significant advantage if the higher activity and selectivity of noble metal catalysts could be maintained or improved while also providing improved tolerance to reaction byproducts such as CO and / or CO?.
[0005] A continuing need exists to improve hydroconversion catalysts and processing of (bio)feedstocks containing oxygen and in providing renewable products from such feedstocks.SUMMARY OF THE INVENTION
[0006] This disclosure relates to processes for making renewable products from biofeedstocks, e.g., feeds containing biocomponents of biological origin, and, in particular, renewable products producedT-11794-W001 during hydroconversion of biofeedstocks. Various renewable products may be produced, including diesel, aviation and other fuels and distillates, as well as base oils or components thereof, and process fluids.
[0007] The hydroconversion of biofeedstocks to produce renewable products generally produces water and carbon oxide byproducts, such as CO and CO2, in addition to the main renewable products of interest. The generation of CO and CO2 is undesirable since it lowers the yield of desirable renewable products and may lead to reduced catalyst performance or poisoning. While efforts have been made to reduce the carbon oxide content, the solutions generally provide a compromised solution. For example, the use of base metal hydrotreating catalysts to lower CO and CO2 content by lowering decarbonylation and decarboxylation selectivity also sacrifices catalyst deoxygenation capability. A need thereof exists for alternative catalyst systems that reduce or avoid such problems.
[0008] Noble metal dewaxing catalysts provide the potential for higher activity and selectivity than base metal catalysts. Noble metal catalysts tend to have little tolerance to reaction byproducts from biofeedstocks, such as CO and CO2, however. It would be desirable for improved noble metal catalysts and associated processes could be provided for making renewable products from biofeedstocks.
[0009] Described herein is a process for making renewable products from a biofeedstock. The process generally comprises contacting a renewable biofeedstock with a hydroisomerization catalyst under hydroisomerization conditions. The hydroisomerization catalyst comprises an SSZ-91 molecular sieve and the catalytically active metals Pt and Ru or Pt and Re.
[0010] In some embodiments, products such as middle distillates, including naphtha, kerosene, jet fuel, and diesel fuel may be produced using the process. Other products such as base oils, lubricating oils, and / or process fluids may also be made according to the process. Certain performance characteristics may be improved by using the process, such as a decrease in cloud point or an increase in yield of renewable diesel product. In some cases, the process may also provide a reduced level of catalyst deactivation / increased catalyst life.
[0011] Except where mutually exclusive, a feature described in relation to any aspect or embodiment described herein may be applied mutatis mutandis to any other aspect and / or embodiment.Furthermore, except where mutually exclusive, any feature described herein may be applied to any aspect / embodiment and / or combined with any other feature described herein.DETAILED DESCRIPTION
[0012] Although illustrative embodiments of one or more aspects are provided herein, the disclosed processes may be implemented using any number of techniques. The disclosure is not limited to the illustrative or specific embodiments, any drawings, and any techniques illustrated herein, including any exemplary designs and embodiments illustrated and described herein, and may be modified within the scope of the appended claims along with their full scope of equivalents.T-11794-W001
[0013] The following description of embodiments provides non-limiting representative examples referencing numerals to particularly describe features and teachings of different aspects of the invention. The embodiments described should be recognized as capable of implementation separately, or in combination, with other embodiments from the description of the embodiments. A person of ordinary skill in the art reviewing the description of embodiments is able to learn and understand the different described aspects of the invention. The description of embodiments should facilitate understanding of the invention such that other implementations, not specifically covered but within the ability of a person of skill in the art having read the description of embodiments, will be understood as being consistent with an application of the invention.
[0014] Unless otherwise indicated, the following terms have the meanings as defined hereinbelow.
[0015] The term "hydroconversion" refers to processes or steps performed in the presence of hydrogen for the hydrocracking, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallation, hydrodechlorination, hydrodecarboxylation, hydrodecarbonylation and / or hydrodearomatization of a hydrocarbon or biomass feedstock, and / or for the hydrogenation of unsaturated compounds in the feedstock. Depending on the type of hydroprocessing and the reaction conditions, products of hydroprocessing may have improved aromatic content, oxygen content, viscosities, viscosity indices, saturates content, cold flow and other low temperature properties, and volatilities, for example.
[0016] The term "hydrotreating" refers to processes or steps performed in the presence of hydrogen for the hydrodesulfurization, hydrodenitrogenation, hydrodeoxygenation, hydrodemetallation, and / or hydrodearomatization of components of a feedstock, and / or for the hydrogenation of unsaturated compounds in the feedstock.
[0017] The term "biofeedstock" as used herein refers to biocomponent feeds that are from or are derived from a biological source. Exemplary biofeedstocks include lipids, pyrolysis oils, biomass derived feeds, and the like. Triglycerides are a component of some biofeedstocks, such as lipids. The hydroprocessed biofeedstock typically has a boiling range suitable for producing renewable products, including, e.g., diesel, aviation or other fuel, distillate, base oil, and / or process fluid therefrom. In the case of some biofeedstocks comprising triglycerides, such feedstocks have an "apparent" boiling temperature range (based on the GC elution time of the triglyceride peaks according to Simdist method ASTM D-2887) suitable for producing a diesel, aviation or other fuel, or distillate therefrom. The biofeedstock boiling range (or apparent boiling range) may also be suitable for producing a base oil or a component thereof. Suitable biofeedstocks are those which, upon hydrotreating, result in hydrocarbons with a boiling point range of about 250°F (121°C) to about 900°F (482°C), for example about 300°F (149°C) to about 900°F (482°C), or about 250°F (121°C) to about 800°F (427°C). While the apparent boiling range of the lipids before hydrotreatment may, in some cases, be higher than 900°F, uponT-11794-W001 hydrotreatment, such lipids are converted into hydrocarbons having lower boiling temperatures or temperature ranges, as described herein. In some cases, e.g., for typical lipids after hydrotreating, an upper boiling point of about 900°F (482°C) includes hydrocarbon molecules having a number of carbon atoms and chain length making them suitable for the applications described herein. In general, at least one biofeedstock, or a biocomponent thereof, used in the process typically has a Cie+ content of at least about 10 wt.%.
[0018] The term "biocomponent feed" as used herein refers to a feedstock derived from a biocomponent-containing source, such as a plant-based oil or fat, an animal-based oil or fat, a fish-based oil or fat, or algae-based oil or fat. Such feedstocks are generally hydrotreated products derived from biological sources. In some embodiments, suitable biocomponent feeds may have a boiling point range of about 250°F (121°C) to about 900°F (482°C), 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) at atmospheric pressure. The biocomponent feed may have a 90 % distillation temperature of less than about 1000°F (538°C), or 900°F (482°C), or 800°F (427°C) or 700°F (371°C), or less than about 650°F (343°C). In some embodiments, the biocomponent 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 may be determined in accordance with 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 (about 204°C) to about 600°F (316°C). The 5 % distillation temperature may be determined in accordance with ASTM D 2887. 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 biocomponent feed has a 90% distillation temperature which is greater than about 600°F (316°C), for example from about 605°F (about 318°C) to about 675°F (357°C), and a 5% distillation temperature which is less than about 600°F (316°C), for example from about 540°F (282°C) to about 580°F (304°C). In some embodiments, the biocomponent feed has a 90 % distillation temperature in the range of equal to or greater than about 600°F (316°C) to about 700°F (371°C) and a 5 % distillation temperature in the range of about 400°F (204°C) to equal to or less than about 600°F (316°C). In some cases, e.g., for typical lipids after hydrotreating, an upper boiling point of about 900°F (482°C) includes hydrocarbon molecules having a number of carbon atoms that makes them suitable for the applications described herein.T-11794-W001
[0019] The term "renewable product" is used herein to refer to a product produced wholly or in-part from a non-fossil fuel source. Suitable feedstocks to produce renewable products are generally derived from materials of biological origin. Renewable products may comprise one or more renewable components, e.g., products derived from feedstocks from more than one biological source.
[0020] The term "Fischer-Tropsch feed" as used herein refers to refer to a synthetic feedstock produced via a 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 may be determined in accordance with ASTM D 2887. 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 may be determined in accordance with 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 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 500°F (260°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 400°F (204°C). In some embodiments, a "Fischer-Tropsch feed" may have boiling points in the range of about 250°F (121°C) to about 900°F (482°C), for example about 250°F (121°C) to about 800°F (427°C) at atmospheric pressure.
[0021] The term "diesel fuel" is used herein to refer to a hydrocarbon product having boiling points in the range of about 300°F to about 800°F (about 149°C to about 427°C) at atmospheric pressure.
[0022] The term "fossil fuel component" is used herein to refer to a component produced wholly or inpart from a fossil fuel source.T-11794-W001
[0023] The term "process fluid" is used herein to refer to a fluid used as a working or other fluid in a process or device that is not generally part of a final or intermediate product made by the process or device, including devices used in chemical, electrical, and / or mechanical processes. While not limited thereto, process fluid examples include drilling fluids, transformer fluids, thermal oils, hydraulic fluids, transmission fluids and / or gear oils, metal working fluids, or a combination thereof.
[0024] The term "active source" means a reagent or precursor material capable of supplying at least one element in a form that can react, and which can be incorporated into the molecular sieve structure. The terms "source" and "active source" can be used interchangeably herein.
[0025] The term "molecular sieve" and "zeolite" are synonymous and include (a) intermediate and (b) final or target molecular sieves and molecular sieves produced by (1) direct synthesis or (2) postcrystallization treatment (secondary modification). Secondary synthesis techniques allow for the synthesis of a target material from an intermediate material by heteroatom lattice substitution or other techniques. For example, an aluminosilicate can be synthesized from an intermediate borosilicate by post-crystallization heteroatom lattice substitution of the Al for B. Such techniques are known, for example as described in U.S. Patent No. 6,790,433 to C.Y. Chen and Stacey Zones, issued September 14, 2004.
[0026] The terms "*MRE-type molecular sieve", "EUO-type molecular sieve" and "MTT-type molecular sieve" includes all molecular sieves and their isotypes that have been assigned the International Zeolite Association framework, as described in the Atlas of Zeolite Framework Types, eds. Ch. Baerlocher, L.B. McCusker and D.H. Olson, Elsevier, 6threvised edition, 2007 and the Database of Zeolite Structures on the International Zeolite Association's website (http: / / www.iza-online.org). As is known, the framework code *MRE, including ZSM-48 zeolites, are not codes for one material but for a family of materials with different degrees of disorder. Other materials with *MRE topology are ZBM-30, EU-2, EU-11, COK-8, and IZM-1.
[0027] SiO ALOs Ratio (SAR): determined by ICP elemental analysis. A SAR of infinity (°°) represents the case where there is no aluminum in the zeolite, i.e., the mole ratio of silica to alumina is infinity. In that case, the molecular sieve is comprised essentially of silica.
[0028] As used herein, the term "pour point" refers to the temperature at which an oil will begin to flow under controlled conditions. The pour point may be determined by ASTM D5950.
[0029] As used herein, "cloud point" refers to the temperature at which a sample begins to develop a haze as the oil is cooled under specified conditions. Cloud point may be determined by ASTM D5773.
[0030] "Group 2, 7, 8, 9 and 10 metals" refers to elemental metal(s) selected from Groups 2, 8, 9 and 10 of the Periodic Table of the Elements and / or to metal compounds comprising such metal(s). "Group 6 metals" refers to elemental metal(s) selected from Group 6 of the Periodic Table of the Elements and / or to metal compounds comprising such metal(s).T-11794-W001
[0031] The term "Periodic Table" refers to the version of IUPAC Periodic Table of the Elements dated 1 December 2018.
[0032] Unless otherwise specified, the "feed rate" of a feedstock being fed to a catalytic reaction zone is expressed herein as the volume of feed per volume of catalyst per hour, which may be referred to as liquid hourly space velocity (LHSV) with units of reciprocal hours (h1).
[0033] For the purposes of this specification and appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that can vary depending upon the desired properties sought to be obtained. It is noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the," include plural references unless expressly and unequivocally limited to one referent. As used herein, the term "include" and its grammatical variants are intended to be non-limiting, such that recitation of items in a list is not to the exclusion of other like items that can be substituted or added to the listed items. As used herein, the term "comprising" means including elements or steps that are identified following that term, but any such elements or steps are not exhaustive, and an embodiment can include other elements or steps.
[0034] Unless otherwise specified, the recitation of a genus of elements, materials, or other components, from which an individual component or mixture of components can be selected, is intended to include all possible sub-generic combinations of the listed components and mixtures thereof. In addition, all number ranges presented herein are inclusive of their upper and lower limit values.
[0035] If a standard test is mentioned herein, unless otherwise stated, the version of the test to be referred to is the most recent at the time of filing this patent application.
[0036] The patentable scope is defined by the claims, and can include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims. To an extent not inconsistent herewith, and in jurisdictions where permitted, all citations referred to herein are hereby incorporated by reference.
[0037] Biofeedstocks described herein comprise or are a biocomponent feed. In some embodiments, the biofeedstock comprises, consists essentially of, or consists of a biocomponent feed. In some embodiments, the biocomponent feed constitutes at least about 5 wt.% of the biofeedstock, for example, at least about 10 wt.%, at least about 20 wt.%, at least about 30 wt.%, at least about 40 wt.%, at least about 50 wt.%, at least about 60 wt.%, at least about 70 wt.%, at least about 80 wt.%, at leastT-11794-W001 about 90 wt.%, at least about 95wt.%, at least about 98 wt.%, or at least about 99 wt.% of the biofeedstock. In some embodiments, the biocomponent feed constitutes 5 wt.% to 100 wt.% of the biofeedstock, for example 10 wt.% to 100 wt.%, 50 wt.% to 100 wt.%, 80 wt.% to 100 wt.%, or 95 wt.% to 100 wt.% of the biofeedstock.
[0038] In some embodiments, the biofeedstock comprises, consists essentially of, or consists of a biocomponent feed. For example, the biocomponent feed may constitute at least about 5 wt.% of the biofeedstock, such as at least about 10 wt.%, at least about 20 wt.%, at least about 30 wt.%, at least about 40 wt.%, at least about 50 wt.%, at least about 60 wt.%, at least about 70 wt.%, at least about 80 wt.%, at least about 90 wt.%, at least about 95 wt.%, at least about 98 wt.%, or at least about99 wt.% of the biofeedstock. In some embodiments, the Fischer-Tropsch feed may constitute 5 wt.% to100 wt.% of the biofeedstock, for example 10 wt.% to 100 wt.%, 50 wt.% to 100 wt.%, 80 wt.% to 100 wt.%, or 95 wt.% to 100 wt.% of the biofeedstock.
[0039] In some embodiments, the biofeedstock is a blended feedstock comprising a biocomponent feed, or also comprising a Fischer-Tropsch feed, in combination with another feedstock, such as a blend feed. For example, the blended feedstock may comprise a blend feed selected from gas oils, vacuum gas oils, long residues, vacuum residues, atmospheric distillates, heavy fuels, oils, waxes and paraffins, used oils, deasphalted residues or crudes, charges resulting from thermal or catalytic conversion processes, or a combination thereof. In some embodiments, the blend feed is selected from whole crude petroleum, reduced crudes, vacuum tower residua, cycle oils, synthetic crudes, gas oils, vacuum gas oils, foots oils, Fischer-Tropsch derived waxes, lubricating oil stocks, heating oils, heavy neutral feeds, hydrotreated gas oils, hydrocracked gas oils, hydrotreated lubricating oil raffinates, brightstocks, lubricating oil stocks, synthetic oils, high pour point polyolefins (for example, polyolefins having a pour point of about 0°C or above); normal alpha olefin waxes, slack waxes, deoiled waxes, microcrystalline waxes, residuum fractions from atmospheric pressure distillation processes, solvent-deasphalted petroleum residua, shale oils, cycle oils, petroleum wax, slack wax, and waxes produced in chemical plant processes. In some embodiments, the feedstock is a blended feedstock comprising a biocomponent feed and a Fischer-Tropsch feed. In some embodiments, the feedstock is a blended feedstock comprising a biocomponent feed, a Fischer-Tropsch feed and a blend feed (for example, a blend feed, supra). The blended feedstock, blend feed, and / or biofeedstock may also comprise a recycled product and / or intermediate process stream. As previously noted, such biofeedstocks or biocomponents are generally hydrotreated products derived from biological sources, wherein the biocomponents are hydrotreated by themselves or hydrotreated together with other feedstock components.
[0040] In some embodiments, the feedstock is a blended feedstock comprising a biocomponent feed and a blend feed, where the blended feedstock comprises at least about 5 wt.% of the biocomponent feed and up to about 95 wt.% of a blend feed component, for example, at least about 10 wt.% of theT-11794-W001 biocomponent feed and up to about 90 wt.% of a blend feed component, at least about 50 wt.% of the biocomponent feed and up to about 50 wt.% of a blend feed component, at least about 80 wt.% of the biocomponent feed and up to about 20 wt.% of a blend feed component, or at least about 95 wt.% of the biocomponent feed and up to about 5 wt.% of a blend feed component.
[0041] The Fischer-Tropsch feed (if used) will typically have a paraffin content of at least about90 wt.%, for example, at least about 95 wt.%, or at least about 97.5 wt.%. The Fischer-Tropsch (FT) feed typically comprises only very minor amounts of olefins and cycloparaffins, for example, less than about 1.0 wt.% olefin, or less than about 0.5 wt.% olefin, and / or less than about 1.0 wt.% cycloparaffin, less than about 0.5 wt.% cycloparaffin, or less than about 0.1 wt.% cycloparaffin. In some embodiments, the FT feed has a sulfur (S) content of less than about 50 ppm, for example less than about 20 ppm. In some embodiments, the FT feed has a nitrogen (N) content of less than about 50 ppm, for example less than about 20 ppm. In some embodiments, the FT feed has a metal content of less than about 10 ppm, for example less than about 5 ppm. The paraffin content and cylcoparaffin content of the FT feed may 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 feed may be determined in accordance with ASTM D3228-20. The sulfur content of the FT feed may be determined in accordance with ASTM D4629. The metal content of the FT feed may be measured by inductively coupled plasma atomic emission spectroscopy (ICP-AES).
[0042] In some embodiments, the feedstock is a blended feedstock comprising a Fischer-Tropsch (FT) feed in combination with a blend feed, where the blended feedstock comprises at least about 5 wt.% of the FT feed and up to about 95 wt.% of a blend feed, for example at least about 10 wt.% of the FT feed and up to about 90 wt.% of a blend feed, at least about 50 wt.% of the FT feed and up to about 50 wt.% of a blend feed, at least about 80 wt.% of the FT feed and up to about 20 wt.% of a blend feed, or at least about 95 wt.% of the FT feed and up to about 5 wt.% of a blend feed.
[0043] In some embodiments, the biofeedstock comprises, consists essentially of or consists of a biocomponent feed. Plant-based oils and fats include vegetable oils and fats, 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, flaxseed oil, hempseed oil, cottonseed oil, camelina oil, safflower oil, mustard oil, carinata oil, cuphea oil, curcas oil, crambe oil, babassu oil, tallow oil, and rice bran oil. Animal oils and fats, and other sources, include beef fat (tallow), hog fat (lard), turkey fat, fish fat / oil, and chicken fat), yellow and brown greases, including algae and fish fats / oils, fats in milk, sewage sludge, and the like.
[0044] In certain embodiments, the biofeedstock comprises or is a biocomponent feed selected from carinata oil, rapeseed oil, peanut oil, mustard oil, tallow, rice bran wax, carnauba wax, or a combination thereof. While not limited thereto, the biofeedstock or biocomponent may be obtained from a plantT-11794-W001 family selected from Brassicaceae (formerly Cruciferaceae), Limnanthaceae, Simmondsiaceae, Tropaeolaceae, Olocaceae, Copernicia, or a combination thereof.
[0045] In some embodiments, the biocomponent feed may include feed components selected from vegetable oils and animal fats comprising, or consisting essentially of, triglycerides and free fatty acids (FFA). In some embodiments, the biofeedstock comprises or is a biocomponent feed selected from lipids, vegetable oils, seed oils, and animal fats which comprise triglycerides and free fatty acids. For example, suitable biocomponent feeds may be selected from canola oil, corn oil, soy oils, castor oil, camelina oil, palm oil and a combination thereof. The biofeedstock may comprise an oxygen-containing compound or an oxygen-containing compound derived from a biofeedstock.
[0046] In some embodiments, the triglycerides and FFAs contain aliphatic hydrocarbon chains in their structure having 6-32 carbon atoms (for example, 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 feed may comprise triglycerides having the general formula (1):
[0047] where R, R1and R2are independently aliphatic hydrocarbon chains having from 6-32 carbon atoms (for example, 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, R1and R2are independently branched or un-branched, substituted or unsubstituted, completely saturated or contain one or more (for example 1-4, 1-3 or 1 or 2) unsaturated carbon-carbon bonds. In some embodiments, R, R1and R2are unsubstituted. In some embodiments, R, R1and R2are independently completely 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, R1and R2are un-branched.
[0048] The biofeedstock or biocomponent feed component may comprise free fatty acids (FFAs) having aliphatic hydrocarbon tails (substituent groups) of 6 to 32 carbon atoms, 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, and the like. The FFAs may comprise unsaturated or saturated aliphatic hydrocarbon tails. The FFAs may comprise unbranched or branched aliphatic hydrocarbon tails.T-11794-W001
[0049] The biofeedstock may comprise or be a biocomponent feed wherein the biofeedstock comprises one or more biocomponents having a C20+ content of at least about 10 wt.%. In some cases, the C20+ content of the biofeedstock and / or a biocomponent thereof may be less than about 80 wt.%, 70 wt.%, 60 wt.%, 50 wt.%, 40 wt.%, 30 wt.%, or 20 wt.%. The Cie+ content of the biofeedstock or a biocomponent may also be greater about 20 wt.%, 30 wt.%, 40 wt.%, 50 wt.%, 60 wt.%, or 70 wt.%, or a combination thereof. In some cases, a content range for the biofeedstock or a biocomponent may include a Cie+ content in the range of about 10 to 80 wt.%, 10 to 70 wt.%, 10 to 60 wt.%, 10 to 50 wt.%, 10 to 40 wt.%, 20 to 80 wt.%, 30 to 80 wt.%, 40 to 80 wt.%, 50 to 80 wt.%, 20 to 70 wt.%, 20 to 60 wt.%,20 to 50 wt.%, 20 to 40 wt.%, 30 to 80 wt.%, 30 to 70 wt.%, 30 to 60 wt.%, 30 to 50 wt.%, 40 to 80 wt.%,40 to 70 wt.%, 40 to 60 wt.%, 50 to 80 wt.%, 50 to 70 wt.%, or 60 to 80 wt.%.
[0050] In addition to the Cie+ content of the biofeedstock and / or a biocomponent thereof, and in addition to or separate from the Cie content limits or ranges noted hereinabove, the Cis content of the biofeedstock or a biocomponent thereof may be less than about 70 wt.%, 60 wt.%, 50 wt.%, 40 wt.%, 30 wt.%, 20 wt.%, 10 wt.%, or 5 wt.%. The Cis content of the biofeedstock or a biocomponent thereof may be greater than about 5 wt.%, 10 wt.%, 20 wt.%, 30 wt.%, 40 wt.%, 50 wt.%, or 60 wt.%, or a combination thereof. The Cis content of the biofeedstock or a biocomponent thereof may be in the range of about 0 to 70 wt. %, 0 to 60 wt.%, 0 to 50 wt.%, 0 to 40 wt.%, 5 to 70 wt. %, 5 to 60 wt.%, 5 to 50 wt.%, 5 to 40 wt.%, 10 to 70 wt. %, 10 to 60 wt.%, 10 to 50 wt.%, 10 to 40 wt.%, 20 to 70 wt. %, 20 to 60 wt.%, 20 to 50 wt.%, or 20 to 40 wt.%.
[0051] In addition to the Cis+ content of the biofeedstock and / or a biocomponent thereof, and in addition to or separate from the Cis content limits or ranges noted hereinabove, the C20 content of the biofeedstock or a biocomponent thereof may be less than about 70 wt.%, 60 wt.%, 50 wt.%, 40 wt.%, 30 wt.%, 20 wt.%, 10 wt.%, or 5 wt.%. The C20 content of the biofeedstock or a biocomponent thereof may be greater than about 5 wt.%, 10 wt.%, 20 wt.%, 30 wt.%, 40 wt.%, 50 wt. %, or 60 wt.%, or a combination thereof. The C20 content of the biofeedstock or a biocomponent thereof may be in the range of about 0 to 70 wt. %, 0 to 60 wt.%, 0 to 50 wt.%, 0 to 40 wt.%, 5 to 70 wt. %, 5 to 60 wt.%, 5 to 50 wt.%, 5 to 40 wt.%, 10 to 70 wt. %, 10 to 60 wt.%, 10 to 50 wt.%, 10 to 40 wt.%, 20 to 70 wt. %, 20 to 60 wt.%, 20 to 50 wt.%, or 20 to 40 wt.%.
[0052] In addition to the Ci6+ content of the biofeedstock and / or a biocomponent thereof, and in addition to or separate from the Cis, and / or C20 content limits or ranges noted hereinabove, the C22+ content of the biocomponent may be less than about 70 wt.%, 60 wt.%, 50 wt.%, 40 wt.%, 30 wt.%, 20 wt.%, 10 wt.%, or 5 wt.%. The C22+ content of the biofeedstock and / or a biocomponent thereof may be greater than about 5 wt.%, 10 wt.%, 20 wt.%, 30 wt.%, 40 wt.%, 50 wt.%, or 60 wt.%, or a combination thereof. The C22+ content of the biofeedstock and / or a biocomponent thereof may be in the range of about 0 to 70 wt. %, 0 to 60 wt.%, 0 to 50 wt.%, 0 to 40 wt.%, 5 to 70 wt. %, 5 to 60 wt.%,T-11794-W0015 to 50 wt.%, 5 to 40 wt.%, 10 to 70 wt. %, 10 to 60 wt.%, 10 to 50 wt.%, 10 to 40 wt.%, 20 to 70 wt. %, 20 to 60 wt.%, 20 to 50 wt.%, or 20 to 40 wt.%.
[0053] In addition to the Cie+ content of the biofeedstock and / or a biocomponent thereof, and in addition to or separate from the Cis, C20, and / or C22+ content limits or ranges noted hereinabove, the C24+ content of the biofeedstock and / or a biocomponent thereof may be less than about 70 wt.%, 60 wt.%, 50 wt.%, 40 wt.%, 30 wt.%, 20 wt.%, 10 wt.%, or 5 wt.%. The C24+ content of the biofeedstock and / or a biocomponent thereof may be greater than about 5 wt.%, 10 wt.%, 20 wt.%, 30 wt.%, 40 wt.%, 50 wt.%, or 60 wt.%, or a combination thereof. The C24+ content of the biofeedstock and / or a biocomponent thereof may be in the range of about 0 to 70 wt. %, 0 to 60 wt.%, 0 to 50 wt.%, 0 to 40 wt.%, 5 to 70 wt. %, 5 to 60 wt.%, 5 to 50 wt.%, 5 to 40 wt.%, 10 to 70 wt. %, 10 to 60 wt.%, 10 to 50 wt.%, 10 to 40 wt.%, 20 to 70 wt. %, 20 to 60 wt.%, 20 to 50 wt.%, or 20 to 40 wt.%.
[0054] In some cases, the Cis to C32 content of the biofeedstock and / or a biocomponent thereof may be 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 in the range of about 10 to 80 wt.%, or 15 to 80 wt.%, or 20 to 80 wt.%, or 30 to 80 wt.%, or 40 to 80 wt.%, or 50 to 80 wt.%, or 60% to 80 wt.%, or 70 to 80 wt. %.
[0055] In general, and in addition to the Cis+ content of the biofeedstock and / or a biocomponent thereof, the Cis content of the biocomponent is about 0 to 70 wt.%; the Cis content of the biocomponent may be about 0 to 70 wt.%; the C20 content of the biocomponent may be about 0 to 70 wt.%; the C22 content of the biocomponent may be about 0 to 70 wt.%; the C22+ content of the biocomponent may be about 0 to 70 wt.%; the C2 content of the biocomponent may be about 0 to 70, 60, 50, or 40 wt.%; and the C24+ content of the biocomponent may be about 0 to 70, 60, 50, or 40 wt.%, or a combination thereof.
[0056] In general, the biofeedstock may comprise or be a biocomponent feed wherein the biofeedstock comprises one or more biocomponents having a Cis+ content of at least about 10 wt.%. Suitable biocomponents may include, e.g., carinata oil, rapeseed oil, peanut oil, mustard oil, tallow, rice bran wax, carnauba wax, or a combination thereof. In some embodiments, the biocomponent feed is or may comprise one or more other biocomponents that typically do not have a higher carbon chain length content (e.g., C20+ content), such as biocomponents that may include canola oil, corn oil, soy oils, castor oil, camelina oil, palm oil, combinations thereof, and the like.
[0057] The biocomponent feed may have an oxygenate content of at least about 0.5 wt.% by total weight of the biocomponent feed, for example, at least about 1.0 wt.%, at least about 2.0 wt.%, at least about 3.0 wt.%, at least about 4.0 wt.%, or at least about 5.0 wt.% by total weight of the biocomponent feed. The biocomponent feed may, e.g., have an oxygenate content of up to about 15 wt.% by total weight of the biocomponent feed, or up to about 10 wt.% by total weight of the biocomponent feed, or up to about 5 wt.% by total weight of the biocomponent feed. In some embodiments, theT-11794-W001 biocomponent feed has an oxygenate content in the range of about 1-15 wt.% by total weight of the biocomponent feed, for example, in the range of about 5-15 wt.%, or about 10-15 wt.%, by total weight of the biocomponent feed. The oxygenate content of the biocomponent feed may be measured by neutron activation analysis, for example, in accordance with ASTM E385-90(2002).
[0058] The biocomponent feed may be hydrotreated prior to being contacted with a hydroconversion catalyst for further hydroprocessing, e.g., with the hydroisomerization / hydrodewaxing catalyst. In some cases, the biocomponent feed may have a sulfur (S) content of less than about 200 ppm, for example less than about 100 ppm, less than about 50 ppm or less than about 20 ppm. In some cases, the biocomponent feed may have a nitrogen (N) content of less than about 50 ppm, for example less than about 20 ppm, or less than about 10 ppm. In some cases, the hydrotreated biocomponent feed may have an oxygenate content that is typically about 0 wt.%, or, alternatively, of less than about 2 wt.%, or 5 wt.%. The nitrogen content of the biocomponent feed may be determined in accordance with ASTM D4629. The sulfur content of the biocomponent feed may be determined in accordance with ASTM D2622.
[0059] In general, biofeedstock hydroprocessing process uses a hydroconversion catalyst that may comprise a hydrotreating catalyst and / or a hydroisomerization catalyst and may include a noble or precious metal catalyst as the hydroconversion catalyst. In some cases, the hydroconversion catalyst may include a base metal catalyst, or a combination of a base metal catalyst and a noble or precious metal catalyst. The combination of a base metal catalyst and a noble metal catalyst may be used in some cases. While not limited thereto, the base metal catalyst typically includes a base metal such as Mo, Ni, W, Co, and combinations thereof, or Mo, or a combination of Mo and Ni. Similarly, while not limited thereto, the noble or precious metal catalyst may include a noble metal such as Pt, Pd, or a combination thereof.
[0060] The term "hydroisomerization catalyst" as used herein refers to a catalyst that facilitates the skeletal isomerization of hydrocarbon molecules. In some embodiments, suitable hydroisomerization catalysts include catalysts comprising zeolite SSZ-91, SSZ-32, SSZ-32x, and the like. Other hydroisomerization catalysts may also be suitable, including, e.g., catalysts based on zeolite ZSM-48 and / or combinations of ZSM-48 with other hydroisomerization catalysts. Combinations of suitable hydroisomerization catalysts based on the same or different zeolite supports may also be used.
[0061] While not limited thereto, the hydroisomerization catalyst may comprise a support material including a zeolite and / or non-zeolite support. Suitable zeolites include any generally known in the art, e.g., zeolite SSZ-91, SSZ-32, SSZ-32x, and / or another suitable zeolite supports. Suitable non-zeolite supports are not particularly limited and include any known in the art, such as silica and / or alumina based supports. In some cases, the catalyst may comprise from about 5 to about 95 wt.% zeolite (e.g., SSZ-91, SSZ-32, SSZ-32x, or a combination thereof) by total weight of the catalyst, or from about 10 toT-11794-W001 about 95 wt.% zeolite, from about 20 to about 90 wt.% zeolite, or from about 25 to about 85 wt.% zeolite, or from about 30 to about 80 wt.% zeolite, or from about 35 to about 75 wt.% zeolite, or from about 35 to about 65 wt.% zeolite, or from about 35 to about 55 wt.% zeolite, or from about 45 to about 75 wt.% zeolite, or from about 55 to about 75 wt.% zeolite by total weight of the catalyst.
[0062] The hydroisomerization catalyst may further comprise a metal modifier, for example a metal modifier selected from Group 2, 7, 8, 9 and 10 metals or combinations thereof. In some embodiments, the metal modifier is selected from Group 8, 9 or 10 metals and combinations thereof, for example the metal modifier may be selected from Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt and combinations thereof. In some embodiments, the metal modifier is selected from Group 10 metals and combinations thereof. In some embodiments, the hydroisomerization catalyst comprises platinum, palladium, or a combination thereof. In some cases, the catalyst may be a noble metal catalyst. Base metals, such as Mo, Ni, W, Co, and combinations thereof, may be included in the catalyst.
[0063] The hydroisomerization catalyst may comprise from about 0.05 to about 10 wt.%, or 5 wt.% or 2.0 wt.% of a metal modifier (e.g., selected from Group 2, 8, 9 and 10 metals, or a Group 8, 9 or 10 metal, for example a Group 10 metal such as platinum) by total weight of the catalyst, for example, about 0.1 to about 1.5 wt.%, or about 0.2 to about 1.5 wt.%, or about 0.1 to about 1 wt.%, by total weight of the catalyst. In some cases, e.g., where base metals are included, the metal content may be higher, e.g., at least about 5 wt.%, or 10 wt.%, or 15 wt.% or 20 wt.%, or 25 wt.%, or at least about 30 wt.%, or in the range of about 2 wt. % or 5 wt.% to about 25 wt.% or 30 wt.%.
[0064] The hydroisomerization catalyst may further comprise an oxide binder. Suitable oxide binders include an inorganic oxide, e.g., the oxide binder may be selected from alumina, silica, ceria, titania, tungsten oxide, zirconia, and combinations thereof. The catalyst may comprise an oxide binder comprising alumina. Suitable aluminas are commercially available, including, e.g., Catapal® aluminas and Pural® aluminas from Sasol® or Versal® aluminas from UOP®. In general, the alumina can be any alumina known for use as a matrix material in a catalyst base. For example, the alumina can be boehmite, bayerite, y-alumina, r]-alumina, 0-alumina, 8-alumina, %-alumina, or a mixture thereof. The catalyst may comprise from about 5 to about 95 wt.% oxide binder by total weight of the catalyst, for example about 5 to about 80 wt.% oxide binder, about 10 to about 70 wt.% oxide binder, about 20 to about 70 wt.% oxide binder, for example about 25 to about 65 wt.% oxide binder by total weight of the catalyst.
[0065] The hydroisomerization catalyst may comprise from about 5 to about 95 wt.% zeolite SSZ-91, from about 0.05 to about 2.0 wt.% of a Group 8-10 metal; and from about 5 to about 95 wt.% oxide binder by total weight of the catalyst. The catalyst may comprise from about 30 to about 80 wt.% zeolite SSZ-91, from about 0.1 to about 1.5 wt.% of a Group 8-10 metal; and from about 20 to about 70 wt.% oxide binder by total weight of the catalyst.T-11794-W001
[0066] Zeolite SSZ-91 and methods for making zeolite SSZ-91 are described in US-A-9920260 which is incorporated herein by reference in its entirety. Zeolite SSZ-91 may also be referred to as SSZ-91 molecular sieve.
[0067] Zeolite SSZ-91 has a SiC / ALCh mole ratio (SAR) of 40 to 220. In some embodiments, zeolite SSZ-91 has a SiO AhCh mole 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.
[0068] Zeolite SSZ-91 is composed of at least 70% polytype 6 of the total ZSM-48-type material present in the product. The proportion of polytype 6 of the total ZSM-48-type material present in the product is determined by DIFFaX simulation and as described by Lobo and Koningsveld in J. Am. Chem. Soc. 2012, 124, 13222-13230, where the disorder was tuned by three distinct fault probabilities. It should be noted the phrase "at least X%" includes the case where there are no other ZSM-48 polytypes present in the structure, i.e., the material is 100% polytype 6. The structure of polytype 6 is as described by Lobo and Koningsveld. (See, J. Am. Chem. Soc. 2002, 124, 13222-13230). In some embodiments, the SSZ-91 material is composed of at least 80% polytype 6 of the total ZSM-48-type material present in the product. In some embodiments, the SSZ-91 material is composed of at least 90% polytype 6 of the total ZSM 48-type material present in the product. The polytype 6 structure has been given the framework code *MRE by the Structure Commission of the International Zeolite Association.
[0069] Zeolite SSZ-91 has a morphology characterized as polycrystalline aggregates comprising crystallites collectively having an average aspect ratio in the range of 1 to 8. In some embodiments, Zeolite SSZ-91 has a morphology characterized as polycrystalline aggregates comprising crystallites collectively having an average aspect ratio in the range of 1 to 6, for example 1 to 5, 1 to 4 or 1 to 3.
[0070] In some embodiments, zeolite SSZ-91 has a morphology characterized as polycrystalline aggregates having a diameter of between about 100 nm and 1.5 pm, each of the aggregates comprising a collection of crystallites collectively having an average aspect ratio in the range of 1 to 8. In some embodiments, zeolite SSZ-91 has a morphology characterized as polycrystalline aggregates having a diameter of between about 100 nm and 1.5 pm, each of the aggregates comprising a collection of crystallites collectively having an average aspect ratio in the range of 1 to 6, for example 1 to 5, 1 to 4 or 1 to 3. As used herein, the term diameter refers to the shortest length on the short end of each crystallite examined.
[0071] Zeolite SSZ-91 is a substantially phase pure material. As used herein, the term "substantially phase pure material" means the material is completely free of zeolite phases other than those belonging to the ZSM-48 family of zeolites, or are present in quantities that have less than a measurable effect on, or confer less than a material disadvantage to, the selectivity of the material. Two common phases that co-crystalize with SSZ-91 are EUO-type molecular sieves such as EU-1, as well as Magadiite and Kenyaite.T-11794-W001These additional phases may be present as separate phases or may be intergrown with the SSZ-91 phase.
[0072] Zeolite SSZ-91 may comprise an EUO-type molecular sieve phase in an amount in the range of 0 to 7 wt.% by weight of the total zeolite SSZ-91 product. In some embodiments, zeolite SSZ-91 comprises an EUO-type molecular sieve phase in an amount in the range of 0 to 5.0 wt.%, for example, 0 to4.0 wt.%, or 0 to 3.5 wt.%. In some embodiments, zeolite SSZ-91 comprises an EUO-type molecular sieve phase in an amount in the range of 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, zeolite SSZ-91 comprises 0 to 7 wt.% EU-1, for example 0 to 5.0 wt.% EU-1, 0 to 4.0 wt.% EU-1, 0 to 3.5 wt.% EU-1, 0.1 to 7.0 wt.% EU-1, 0.1 to 5.0 wt.% EU-1, 0.1 to 4.0 wt.% EU-1, 0.1 to 3.5 wt.% EU-1, 0.1 to 2 wt.% EU-1, or 0.1 to 1 wt.% EU-1.
[0073] It is known that the ratio of powder XRD peak intensities varies linearly as a function of weight fractions for any two phases in a mixture: (la / ip) = (RIRa / RIRP)* (xa / xP), where the RIR (Reference Intensity Ratio) parameters can be found in The International Centre for Diffraction Data's Powder Diffraction File (PDF) database (http: / / www.icdd.com / products / ). The weight percentage of the EUO phase in zeolite SSZ-91 may therefore be calculated by measuring the ratio between the peak intensity of the EUO phase and that of the SSZ-91 phase.
[0074] In general, zeolite SSZ-91 may comprise a silicon oxide (SiO2) to aluminum oxide (AI2O3) mole ratio (SAR) of 40 to 220; at least 70% polytype 6 of the total ZSM-48-type material; 0 to 7.0 wt.% of an EUO-type molecular sieve phase; wherein the zeolite SSZ-91 has a morphology characterized as polycrystalline aggregates comprising crystallites collectively having an average aspect ratio of between 1 and 8. In some embodiments, zeolite SSZ-91 comprises a silicon oxide (SiO2) to aluminum oxide (AI2O3) mole ratio (SAR) of 40 to 220; at least 70% polytype 6 of the total ZSM-48-type material; 0 to 4.0 wt.% of an EUO-type molecular sieve phase; wherein the zeolite SSZ-91 has a morphology characterized as polycrystalline aggregates comprising crystallites collectively having an average aspect ratio of between 1 and 8. Zeolite SSZ-91 may comprise a silicon oxide (SiO2) to aluminum oxide (AI2O3) mole ratio (SAR) of 40 to 220; at least 70% polytype 6 of the total ZSM-48-type material; 0 to 3.5 wt.% of an EUO-type molecular sieve phase; wherein the zeolite SSZ-91 has a morphology characterized as polycrystalline aggregates comprising crystallites collectively having an average aspect ratio of between 1 and 8. Zeolite SSZ-91 may comprise a silicon oxide (SiO2) to aluminum oxide (AI2O3) mole ratio (SAR) of 40 to 200; at least 70% polytype 6 of the total ZSM-48-type material; 0 to 4.0 wt.% of an EUO-type molecular sieve phase; wherein the zeolite SSZ-91 has a morphology characterized as polycrystalline aggregates comprising crystallites collectively having an average aspect ratio of between 1 and 8. In some embodiments, zeolite SSZ-91 comprises a silicon oxide (SiO2) to aluminum oxide (AI2O3) mole ratio (SAR) of 70 to 200; at least 70% polytype 6 of the total ZSM-48-type material; 0 to 4.0 wt.% of an EUO-type molecular sieve phase; wherein the zeolite SSZ-91 has a morphology characterized as polycrystallineT-11794-W001 aggregates comprising crystallites collectively having an average aspect ratio of between 1 and 6. Zeolite SSZ-91 may comprise a silicon oxide (SiOz) to aluminum oxide (AI2O3) mole ratio (SAR) of 80 to 200; at least 70% polytype 6 of the total ZSM-48-type material; 0.1 to 7.0 wt.% of an EUO-type molecular sieve phase; wherein the zeolite SSZ-91 has a morphology characterized as polycrystalline aggregates comprising crystallites collectively having an average aspect ratio of between 1 and 6. Zeolite SSZ-91 may comprise a silicon oxide (SiOz) to aluminum oxide (AI2O3) mole ratio (SAR) of 80 to 200; at least 70% polytype 6 of the total ZSM-48-type material; 0.1 to 4.0 wt.% of an EUO-type molecular sieve phase; wherein the zeolite SSZ-91 has a morphology characterized as polycrystalline aggregates comprising crystallites collectively having an average aspect ratio of between 1 and 6. Zeolite SSZ-91 may comprise a silicon oxide (SiO2> to aluminum oxide (AI2O3) mole ratio (SAR) of 80 to 200; at least 70% polytype 6 of the total ZSM-48-type material; 0.1 to 4.0 wt.% EU-1; wherein the zeolite SSZ-91 has a morphology characterized as polycrystalline aggregates comprising crystallites collectively having an average aspect ratio of between 1 and 6. Zeolite SSZ-91 may comprise a silicon oxide (SiC>2) to aluminum oxide (AI2O3) mole ratio (SAR) of 80 to 200; at least 70% polytype 6 of the total ZSM-48-type material; 0.1 to 4.0 wt.% of an EUO-type molecular sieve phase; wherein the zeolite SSZ-91 has a morphology characterized as polycrystalline aggregates comprising crystallites collectively having an average aspect ratio of between 1 and 6. Zeolite SSZ-91 may comprise a silicon oxide (SiO2> to aluminum oxide (AI2O3) mole ratio (SAR) of 80 to 160; at least 70% polytype 6 of the total ZSM-48-type material; 0.1 to 4.0 wt.% of an EUO-type molecular sieve phase; wherein the zeolite SSZ-91 has a morphology characterized as polycrystalline aggregates comprising crystallites collectively having an average aspect ratio of between 1 and 6. Zeolite SSZ-91 may comprise a silicon oxide (SiO2) to aluminum oxide (AI2O3) mole ratio (SAR) of 70 to 160; at least 70% polytype 6 of the total ZSM-48-type material; 0.1 to 4.0 wt.% of an EUO-type molecular sieve phase; wherein the zeolite SSZ-91 has a morphology characterized as polycrystalline aggregates comprising crystallites collectively having an average aspect ratio of between 1 and 6. Zeolite SSZ-91 may comprise a silicon oxide (SiOz) to aluminum oxide (AI2O3) mole ratio (SAR) of 70 to 200; at least 80% polytype 6 of the total ZSM-48-type material; 0.1 to 4.0 wt.% of an EUO-type molecular sieve phase; wherein the zeolite SSZ-91 has a morphology characterized as polycrystalline aggregates comprising crystallites collectively having an average aspect ratio of between 1 and 6. Zeolite SSZ-91 may comprise a silicon oxide (SiO2> to aluminum oxide (AI2O3) mole ratio (SAR) of 80 to 200; at least 80% polytype 6 of the total ZSM-48-type material; 0.1 to 4.0 wt.% of an EUO-type molecular sieve phase; wherein the zeolite SSZ-91 has a morphology characterized as polycrystalline aggregates comprising crystallites collectively having an average aspect ratio of between 1 and 6. Zeolite SSZ-91 may comprise a silicon oxide (SiO2) to aluminum oxide (AI2O3) mole ratio (SAR) of 80 to 200; at least 80% polytype 6 of the total ZSM-48-type material; 0.1 to 7.0 wt.% of an EUO-type molecular sieve phase; wherein the zeolite SSZ-91 has a morphology characterized as polycrystalline aggregates comprising crystallites collectively havingT-11794-W001 an average aspect ratio of between 1 and 4. Zeolite SSZ-91 may comprise a silicon oxide (SiOz) to aluminum oxide (AI2O3) mole ratio (SAR) of 80 to 200; at least 80% polytype 6 of the total ZSM-48-type material; 0.1 to 4.0 wt.% of an EUO-type molecular sieve phase; wherein the zeolite SSZ-91 has a morphology characterized as polycrystalline aggregates comprising crystallites collectively having an average aspect ratio of between 1 and 4. Zeolite SSZ-91 may comprise a silicon oxide (SiCh) to aluminum oxide (AI2O3) mole ratio (SAR) of 80 to 160; at least 80% polytype 6 of the total ZSM-48-type material; 0.1 to 4.0 wt.% of an EUO-type molecular sieve phase; wherein the zeolite SSZ-91 has a morphology characterized as polycrystalline aggregates comprising crystallites collectively having an average aspect ratio of between 1 and 4. In some embodiments, zeolite SSZ-91 comprises a silicon oxide (SiOz) to aluminum oxide (AI2O3) mole ratio (SAR) of 100 to 140; at least 80% polytype 6 of the total ZSM-48-type material; 0.1 to 4.0 wt.% of an EUO-type molecular sieve phase; wherein the zeolite SSZ-91 has a morphology characterized as polycrystalline aggregates comprising crystallites collectively having an average aspect ratio of between 1 and 4. Zeolite SSZ-91 may comprise a silicon oxide (SiOz) to aluminum oxide (AI2O3) mole ratio (SAR) of 100 to 140; at least 80% polytype 6 of the total ZSM-48-type material; 0.1 to 4.0 wt.% of EU-1; wherein the zeolite SSZ-91 has a morphology characterized as polycrystalline aggregates comprising crystallites collectively having an average aspect ratio of between 1 and 4.
[0075] Zeolite SSZ-91 synthesized as described herein can be characterized by XRD pattern. The powder XRD lines of Table 1 are representative of as-synthesized zeolite SSZ-91. Minor variations in the diffraction pattern can result from variations in the mole ratios of the framework species of the particular sample due to changes in lattice constants. In addition, sufficiently small crystals will affect the shape and intensity of peaks, leading to significant peak broadening. Minor variations in the diffraction pattern can also result from variations in the organic compound used in the preparation and from variations in the Si / AI mole ratio from sample to sample. Calcination can also cause minor shifts in the XRD pattern. Notwithstanding these minor perturbations, the basic crystal lattice structure remains unchanged.TABLE 1Characteristic Peaks for As- Synthesized SSZ-912-Theta(a)d-spacing (nm) Relative lntensity(b)7.55 1.170 W8.71 1.015 W12.49 0.708 W15.12 0.586 W21.18 0.419 VS22.82 0.390 VS24.62 0.361 W26.39 0.337 WT-11794-W00129.03 0.307 W31.33 0.285 W(a)± 0.20(b)The powder XRD patterns provided are based on a relative intensity scale in which the strongest line in the X-ray pattern is assigned a value of 100: W = weak (> 0 to < 20); M = medium (> 20 to < 40); S = strong (> 40 to < 60); VS = very strong (> 60 to < 100).
[0076] The X-ray diffraction pattern lines of Table 2 are representative of calcined SSZ-91.TABLE 2Characteristic Peaks for Calcined SSZ-912-Theta,a)d-spacing (nm) Relative lntensity(b)7.67 1.152 M8.81 1.003 W12.61 0.701 W15.30 0.579 W21.25 0.418 VS23.02 0.386 VS24.91 0.357 W26.63 0.334 W29.20 0.306 W31.51 0.284 W(a)± 0.20|b)The powder XRD patterns provided are based on a relative intensity scale in which the strongest line in the X-ray pattern is assigned a value of 100: W = weak (> 0 to < 20); M = medium (> 20 to < 40); S = strong (> 40 to < 60); VS = very strong (> 60 to < 100).
[0077] The powder X-ray diffraction patterns presented herein were collected by standard techniques. The radiation was CuKaradiation. The peak heights and the positions, as a function of 20 where 0 is the Bragg angle, were read from the relative intensities of the peaks (adjusting for background), and d, the interplanar spacing corresponding to the recorded lines, can be calculated.
[0078] Zeolite SSZ-91 can be used as-synthesized, but typically will be thermally treated (calcined). The term "as-synthesized" refers to the zeolite SSZ-91 in its form after crystallization, prior to removal of the SDA cation. The SDA can be removed by thermal treatment (e.g., calcination), for example in an oxidative atmosphere (e.g., air, gas with an oxygen partial pressure of greater than 0 kPa) at a temperature readily determinable by one skilled in the art sufficient to remove the SDA from the molecular sieve. The SDA can also be removed by ozonation and photolysis techniques (e.g., exposing the SDA-containing molecular sieve product to light or electromagnetic radiation that has a wavelength shorter than visible light under conditions sufficient to selectively remove the organic compound from the molecular sieve) as described in U.S. Patent No. 6,960,327.T-11794-W001
[0079] Zeolite SSZ-91 can be subsequently calcined in steam, air or inert gas at temperatures ranging from 200°C to 800°C for periods of time ranging from 1 hour to a number of days, for example 1 to 48 hours. Usually, it is desirable to remove the extra-framework cation (e.g., Na+) by ion exchange and replace it with hydrogen, ammonium, or any desired metal-ion.
[0080] Where the molecular sieve formed 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 by known techniques such as acid leaching.
[0081] Zeolite SSZ-91 made from the process disclosed herein can be formed into a wide variety of physical shapes. Zeolite SSZ-91 can be in the form of a powder, a granule, or a molded product, such as extrudate having a particle size sufficient to pass through a 2-mesh (Tyler) screen and be retained on a 400-mesh (Tyler) screen. In cases where the catalyst is molded, such as by extrusion with an organic binder, the zeolite SSZ-91 can be extruded before drying, or, dried or partially dried and then extruded.
[0082] Zeolite SSZ-91 can be composited with other materials resistant to the temperatures and other conditions employed in organic conversion processes. Such matrix materials include active and inactive materials and synthetic or naturally occurring molecular sieves as well as inorganic materials such as clays, silica, and metal oxides. Examples of such materials and uses are disclosed in U.S. Patent Nos. 4,910,006 and 5,316,753.
[0083] The hydroisomerization, such as a zeolite SSZ-91 catalyst, may be in as-synthesized or calcined form. The catalyst may be formed from zeolite SSZ-91 in calcined form. In some embodiments, the catalyst comprises a molecular sieve selected from zeolite SSZ-91 and a Group 2, 7, 8, 9 or 10 metal (for example, a Group 8-10 metal such as Pt).
[0084] The hydroisomerization catalyst may be formed by compositing molecular sieve zeolite SSZ-91 (in as-synthesized or calcined form) with an oxide binder such as alumina, and / or other support materials as described herein or as known in the art. In some embodiments, compositing molecular sieve zeolite SSZ-91 (in as-synthesized or calcined form) with an oxide binder comprises mixing a molecular sieve selected from zeolite SSZ-91 (in as-synthesized or calcined form) with an oxide binder or support material and extruding the product. The mixture of the molecular sieve and the oxide binder / support may be formed into a particle or extrudate having a wide range of physical shapes and dimensions. In some embodiments, the extrudate or particle may be dried and calcined prior to metal loading. In some embodiments, the extrudate or particle is impregnated with a metal, e.g., a Group 2, 7, 8, 9 or 10 metal (for example, a Group 8-10 metal such as Pt). and then dried and calcined. In some embodiments, the extrudate or particle is dried and calcined prior to metal loading.
[0085] The hydroisomerization catalyst may be prepared by compositing a molecular sieve (such as zeolite SSZ-91) with an oxide binder / support to form an extrudate base; impregnating the extrudateT-11794-W001 base with an impregnation solution containing a metal, e.g., a Group 2, 7, 8, 9 or 10 metal (e.g., a Group 8-10 metal such as Pt), to form a metal-loaded extrudate; drying the metal-loaded extrudate; and calcining the dried metal-loaded extrudate.
[0086] The hydroisomerization catalyst may be formed by impregnating a molecular sieve (such as zeolite SSZ-91) with a solution containing a metal, e.g., a Group 2, 7,8, 9 or 10 metal (for example a Group 8-10 metal such as Pt). In some embodiments, the catalyst may be formed by impregnating the molecular sieve in calcined form with a solution containing a Group 2, 7, 8, 9 or 10 metal (e.g., a Group 8-10 metal such as Pt). In some embodiments, the catalyst is formed by impregnating an extrudate base comprising the molecular sieve and an oxide binder. In some embodiments, the extrudate base is exposed to an impregnation solution (e.g., soaked in an impregnation solution) containing a metal, e.g., a Group 2, 7, 8, 9 or 10 metal (for example, a Group 8-10 metal such as Pt) for 0.1 to 10 hours.
[0087] The extrudate base may be dried (e.g., 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) and calcined (at a temperature in the range of about 390°F (199°C) to about 1200°F (649°C), or about 600°F (316°C) to about 1200°F (649°C) for about 0.1 to about 10 hours) prior to impregnation.
[0088] The extrudate base may be formed by compositing the molecular sieve (such as from zeolite SSZ-91) and an oxide binder / support is dried and calcined prior to impregnation. The dried and calcined extrudate base may be impregnated with an impregnation solution to form a metal-loaded extrudate before being dried and calcined again to form the catalyst.
[0089] The impregnated extrudate base comprising, e.g., zeolite SSZ-91, may 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-loaded extrudate may 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 takes place in air.
[0090] The process of hydroconverting a biofeedstock comprises contacting a biofeedstock with a hydroconversion catalyst under hydroconversion conditions. Hydroconversion takes place in the presence of hydrogen and may include hydroisomerization and / or hydrotreating and hydroisomerization processes. Hydroconversion may include other processes as well, including hydrocracking.
[0091] The hydroconversion may take place in the presence of a hydroconversion catalyst comprising SSZ-91. In some embodiments, the hydroisomerization catalyst comprises SSZ-91. The biofeedstock may contain only renewable biocomponents and / or may exclude, or not purposely include, fossil fuel components. The biofeedstock may also be utilized by itself, i.e., wherein no fossil fuel component or other non-biofeedstock component is added along with the biofeedstock.T-11794-W001
[0092] The process generally makes use of a biofeedstock comprising one or more biocomponents having a Cis+ content of at least about 10 wt.% and the hydroconversion catalyst comprises a hydroisomerization catalyst. In some cases, the biofeedstock may comprise one or more biocomponents having a Cie to C24 content of at least about 10 wt.%. While not limited thereto, the Cie to C24 content of the biocomponent may be at least about 15 wt.%, or 20 wt.%, or 30 wt.%, or 40 wt.%, or 50 wt.%.
[0093] The process may also be a single stage or a two-stage process, e.g., wherein no intermediate and / or final products are removed between stages or catalyst beds. The process may be advantageously carried out within a single reactor in some embodiments. The process may also be carried out in two or more reactors connected in series, e.g., with a first reactor, or catalyst section, comprising a hydrotreating section and a reactor, or catalyst section, and a section or reactor downstream from the first reactor or catalyst section comprising a hydroisomerization section. All of the products from the hydrotreating section are or may be directly passed to the hydroisomerization section, i.e., wherein no intermediate products are removed between the sections. The process may be carried out in two or more reactors, reactor sections, or reactor layers connected in a flow-through sequence, with a first reactor, reactor section, or reactor layer comprising the catalyst system upstream of a second reactor, reactor section, or reactor layer. In some cases, a second reactor, reactor section, or reactor layer comprises a noble metal catalyst. A separate hydrocracking catalyst is not required to be used, or is not used, within the process to produce a renewable product. The skilled artisan will appreciate that various reactor configurations and catalyst loading arrangements are possible according to the invention.
[0094] The hydroconversion (hydroprocessing) conditions may typically comprise a temperature in the range of about 300°F to about 800°F (149°C to 427°C); a pressure in the range of about 15 to about 3000 psig (0.10 to 20.68 MPa gauge); a feed rate of biofeedstock in the range from about 0.1 to about 20 h1LHSV; and hydrogen and biofeedstock feed rates in a ratio from about 1000 or 1500, or 2000 to about 10,000 standard cubic feet H2 per barrel biofeedstock (from about 180 to about 1800 m3Hz / m3feed).
[0095] In some cases, the hydroconversion and / or hydroisomerization conditions may include a temperature in the range of about 300°F to about 800°F (149°C to 427°C), e.g., 400°F (204°C) or 450°F (232°C)to about 730°F (388°C) or 800°F (427°C), or about 550°F to about 700°F (288°C to 371°C). The conditions may include a pressure in the range of about 0, or 15 to about 3000 psig (0 or 0.10 to 20.68 Mpa gauge), for example about 100 to about 2500 psig (0.69 to 17.24 Mpa), or 0 to 2700 psig (0 to 18.62 MPa), or 0 to 2200 psig (0 to 15.17 MPa), or 0 to 1800 psig (0 to 12.41 MPa), or 0 to 1300 psig (0 to 8.96 MPa). The conditions may include a feed rate of the biofeedstock to the reactor containing the hydroisomerization catalyst at a rate in the range from about 0.1 to about 20 h1LHSV, e.g., from about 0.1 to about 5 h1LHSV.T-11794-W001
[0096] In some cases, the hydroconversion and / or hydroisomerization conditions may include hydrogen and biofeedstock fed to the reactor in a ratio from about 1000, or 1500, or 2000 to about 10,000 standard cubic feet H2 per barrel feedstock (from about 180 to about 1800 m3H2 / m3feed, e.g., from about 2500 to about 5000 scf H2 per barrel feedstock (from about 440 to about 890 m3H2 / 1T13feed).
[0097] In some embodiments, hydroconversion and / or hydroisomerization conditions are as follows: 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 (199°C) to about 800°F (427°C), e.g., about 550°F to about 750°F (288°C to 399°C), or 570°F to about 675°F (299°C to 357°C); pressure in the range of about 15 to about 3000 psig (0.10 to 20.68 MPa gauge), e.g., about 100 to about 2500 psig (0.69 to 17.24 MPa); feed rate of feedstock to the reactor containing the hydroisomerization catalyst at a rate in the range from about 0.1 to about 20 h1LHSV, e.g., from about 0.1 to about 5 h1LHSV; and hydrogen and feedstock fed to the reactor in a ratio from about 1000, or 1500, or 2000 to about 10,000 standard cubic feet H2 per barrel feedstock (from about 180 to about 1800 m3Hz / m3feed, e.g., from about 2500 to about 5000 scf H2 per barrel feedstock (from about 440 to about 890 m3H2 / m3feed).
[0098] The process may be generally used to provide a variety of renewable products, including both liquid and gas products. In some cases, renewable products such as base oils, base oil components, lubricating oils, process fluids, or a combination thereof may be produced. Other products may also be produced during the process. While not limited thereto, process fluids that may be produced include drilling fluids, transformer fluids, thermal oils, hydraulic fluids, transmission fluids, metal working fluids, or a combination thereof. Renewable gas products may also be produced including renewable methane and other hydrocarbons.
[0099] Contacting the biofeedstock and the hydroconversion and / or hydroisomerization catalyst according to the process may provide a base oil or a component thereof comprising an increased ratio of isoparaffins to normal paraffins compared to the biofeedstock that has been hydrotreated. In particular, the increased iso to normal paraffin ratio in the product may result when the biofeedstock has been processed over a hydroisomerization catalyst and the comparison is made against a product that has been only hydrotreated. In some embodiments, contacting the biofeedstock and the hydroisomerization catalyst under hydroisomerization conditions according to the process procedure provides a base oil, a fuel product, or a component thereof exhibiting a lower cloud point and / or a lower pour point compared to the cloud point and / or pour point of the same products that have not been subjected to the process procedure.
[0100] In some embodiments, contacting the biofeedstock and the catalyst under suitable conditions provides one or more products, e.g., naphtha, kerosene, jet fuel, and / or diesel fuel.T-11794-W001
[0101] In some embodiments, contacting the biofeedstock and the catalysts according to the procedure provides a base oil, a fuel product, or a component thereof exhibiting a lower cloud point and a lower pour point compared to the cloud point and pour point of the same products before the process is used. In some cases, the base oil, fuel product, or a component thereof exhibits a cloud point at least 2, or 4, or 6, or 8, or 10°C lower than the cloud point and / or a pour point at least 2, or 4, or 6, or 8, or 10°C lower than the pour point of the same products produced without the process run procedure. In some cases, the process run procedure provides a cloud point at least 20°C or at least 30°C lower than the cloud point and / or a pour point at least 20°C or at least 30°C lower than the pour point of the same products produced without the process run procedure.
[0102] In some cases, a base oil product, or a component thereof, may meet Group 111+ base oil specifications, e.g., a base oil having a VI greater than 130. While not limited thereto, 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 less; and / or a viscosity at 100°C of 1.5, or 1.6, or 1.7, or 1.8 cSt or greater; and / or a VI of 105, or 107, or 109, or 113, or 117, or 121, or 125, or 129, or greater; or a combination thereof.
[0103] The biofeedstock may be contacted with a hydrotreating catalyst under hydrotreating conditions prior to contacting the biofeedstock with the hydroisomerization catalyst. In some embodiments, the hydrotreating conditions include a 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), e.g., about 500°F (260°C) or 550°F (288°C) to about 750°F (399°C), 590°F to about 675°F (310°C to 357°C); a pressure in the range of about 15 to about 3000 psig (0.10 to 20.68 MPa gauge), e.g., about 100 to about 2500 psig (0.69 to 17.24 MPa); a feed rate of feedstock to the reactor containing the hydroisomerization catalyst at a rate in the range from about 0.1 to about 20 h1LHSV, e.g., from about 0.1 to about 5 h1LHSV; and hydrogen and feedstock fed to the reactor in a ratio from about 1000, or 1500, or 2000 to about 10,000 standard cubic feet H2per barrel feedstock (from about 180 to about 1800 m3H2 / m3feed), for example, from about 2500 to about 5000 scf H2per barrel feedstock (from about 440 to about 890 m3H2 / m3feed).
[0104] Hydrotreating catalysts may generally comprise a refractory inorganic oxide support and a Group 6 metal modifier, a Group 7 modifier, and / or a Group 8-10 metal modifier. The hydrotreating catalyst may comprise a refractory inorganic oxide support, a Group 6 metal modifier, a Group 7 modifier, and a Group 8-10 metal modifier. The oxide support may also be referred to herein as a binder. The support of the hydrotreating catalyst may be prepared from or comprise alumina, silica, silica / alumina, titania, magnesia, zirconia, and the like, or combinations thereof. The hydrotreating 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, amorphous silica-alumina, and the like.T-11794-W001Example 1
[0105] A representative noble metal catalyst according to the disclosure was used to process a biofeedstock (e.g., soybean oil, canola oil, or an equivalent thereof) into primarily renewable diesel (including middle distillates in general, renewable naphtha, jet fuel, etc.) and to demonstrate the improved product performance and product characteristics resulting from use of the process.
[0106] The catalyst system included noble metal catalyst, arranged so the biofeedstream contacted the noble metal catalyst. Suitable noble metals comprised Pt, Pd, and / or Ru. The system was operated under a pressure of 900 psig, and at a catalyst temperature of 640°F for the noble metal catalyst, The biofeedstock LHSV was 1.125 hr1, and the gas to oil ratio was 12,000 standard cubic feet H2 per barrel (SCFB) feed.
[0107] Table 1 provides cloud point dewaxing results for catalysts comprising the same SSZ-91 zeolite base. As compared with base metal catalysts, the noble metal dewaxing catalysts provided much higher activity under both conditions. The Ru and Pt SSZ-91 catalyst also showed better H2O tolerance than the Pt catalyst for single-stage hydroprocessing. Table 2 shows the actual diesel yield (300°F+) after the dewaxing of the hydrotreated biofeed. In general, the noble metal dewaxing catalysts provided higher diesel selectivity than the base metal dewaxing catalysts to reach the cloud point target.Table 1. Comparison of renewable diesel product cloud point improvement for SSZ-91 zeolite catalystsCatalyst Dewaxing Cloud Point improvement (two- Cloud Point improvement (singleMetals CAT, °F stage hydroprocessing)0, °C stage hydroprocessing)*, °CPt 640 46 25Ru and Pt 640 46 28Re and Pt 640 43 23Ni and W 660 28 13Ni and Mo 660 10 4°The difference between renewable diesel product and hydrotreated biofeeds*The difference between renewable diesel product and hydrotreated biofeeds with 3 wt% H2O presence in the unitsTable 2. Comparison of renewable diesel product yield0for SSZ-91 zeolite catalystsDiesel Yield Diesel Yield, Cloud Point , Cloud PointCatalyst Dewaxing (two-stage (single stage, improvement , ,%improvement , ,Metals CAT F hydroprocessing) hydroprocessing)wt% wt%Pt 640 46 91 25 82Ru and Pt 640 46 91 28 81Re and Pt 640 43 91 23 82T-11794-W001Ni and W 660 28 84 13 78Ni and Mo 660 10 95 4 82“Diesel yield = 300 °F+ product weight / hydrotreated biofeed weight
[0108] Similar or other performance and catalyst run period improvements may be realized using noble metal hydroisomerization catalysts described herein, such as cloud point improvements, or increased catalyst life, and according to the process conditions described in this disclosure, including a temperature in the range of about 300°F to about 800°F (149°C to 427°C); a pressure in the range of about 15 to about 3000 psig (0.10 to 20.68 MPa gauge); a feed rate of biofeedstock in the range from about 0.1 to about 20 h1LHSV; hydrogen and biofeedstock feed rates in a ratio from about 1000 to about 20,000 standard cubic feet H2 per barrel biofeedstock (from about 180 to about 1800 m3Hz / m3feed); or a combination thereof.
[0109] For the avoidance of doubt, the present disclosure is directed to the subject-matter described in the following numbered paragraphs 1 to 24:1. A process for making a renewable product, the process comprising contacting a biofeedstock with a hydroisomerization catalyst under hydroisomerization conditions to produce a renewable product; wherein, the hydroisomerization catalyst comprises an SSZ-91 molecular sieve and the catalytically active metals Pt and Ru or Pt and Re.2. The process of paragraph 1, wherein the catalyst metals content is 0.01-5.0 wt.%, or 0.01-3.0 wt.%, or 0.01-2.0 wt.%, or 0.1-2.0 wt.% (total catalyst weight basis).3. The process of paragraph 1 or 2, wherein the catalyst Pt metal content is 0.01 to 5 wt.%, or 0.01 to 3.0 wt.%, or 0.01 to 2.0 wt.%, or 0.01-1.0 wt.% or 0.010.8 wt.%, or 0.1-1.0 wt.% (total catalyst weight basis).4. The process of paragraphs 1-3, wherein the catalyst Ru or Re metal content is 0.01- to 5 wt.%, or 0.01 to 3.0 wt.%, or 0.01 to 2.0 wt.%, or 0.01-1.5 wt.% or 0.01-1.0 wt.%, or 0.1-1.0 wt.% (total catalyst weight basis).5. The process of paragraphs 1-4, wherein the catalyst Pt metal content is 0.01- to 5 wt.%, or 0.01 to 3.0 wt.%, or 0.01 to 2.0 wt.%, or 0.01-1.0 wt.% or 0.01-0.8 wt.%, or 0.1-1.0 wt.% and the Ru or Re metal content is 0.01- to 5 wt.%, or 0.01 to 3.0 wt.%, or 0.01 to 2.0 wt.%, or 0.01-1.0 wt.% or 0.01-0.8 wt.%, or 0.1-1.0 wt.% (total catalyst weight basis).6. The process of paragraphs 1-5, wherein the molar ratio of Pt to Ru or Pt to Re is in the range of 1000:1 to 1:1000, 500:1 to 1:500, 1:100 to 100:1, 1:20 to 20:1, or 5:1 to 1:20, or 5:1 to 1:10, or 5:1 to 1:5, or 3:1 to 1:3, or 1:1 to 1:2, or 5:1 to 2:1, or 5:1 to 3:1, or 1:1 to 1:3, or 1:1 to 1:4.T-11794-W0017. The process of paragraphs 1-6, wherein the catalyst further comprises a support material selected from alumina, silica, aluminosilicate, titania, zirconia, carbon (e.g., graphite), ceria, magnesia, or a combination thereof.8. The process of paragraphs 1-7, wherein the catalyst comprises 0.01 to 5.0 wt.%, or 0.01 to 3.0 wt.%, or 0.01 to 2.0 wt.%, or 0.01 to 1.0 wt.% of the catalytically active metal, 1 to 99 wt.% of the support material, and 0.1 to 99 wt.% of the SSZ-91 molecular sieve.9. The process of paragraphs 1-8, wherein the catalyst further comprises a metal selected from Groups 6 to 10 and Group 14 of the Periodic Table.10. The process of paragraphs 1-9, wherein the silicon oxide to aluminum oxide mole ratio of the SSZ- 91 molecular sieve is in the range of 40 to 220 or 50 to 220 or 40 to 200.11. The process of paragraphs 1-10, wherein the SSZ-91 molecular sieve comprises ZSM-48 type zeolite material, the molecular sieve having: at least 70% polytype 6 of the total ZSM-48-type material; an EUO-type phase in an amount of between 0 and 3.5 percent by weight; and polycrystalline aggregate morphology comprising crystallites having an average aspect ratio of between 1 and 8.12. The process of paragraphs 1-11, wherein the SSZ-91 molecular sieve comprises one of more of: at least 80%, or 90%, polytype 6 of the total ZSM-48-type material; between 0.1 and 2 wt.% EU-1; crystallites having an average aspect ratio of between 1 and 5, or between 1 and 3; or a combination thereof.13. The process of paragraphs 1-12, wherein the biofeedstock comprises or is a biocomponent feed selected from lipids, vegetable oils and animal fats which comprise triglycerides and free fatty acids, for example wherein the biocomponent feed is selected from canola oil, corn oil, soy oils, castor oil, camelina oil, palm oil and a combination thereof; or wherein the biofeedstock comprises a biofeedstock- derived oxygen containing compound.14. The process of paragraphs 1-13, wherein the biofeedstock comprises or is a biocomponent feed selected from canola oil, corn oil, soy oils, castor oil, camelina oil, palm oil, carinata oil, rapeseed oil, soybean oil, colza oil, tall oil, sunflower oil, hempseed oil, olive oil, linseed oil, coconut oil, castor oil, peanut oil, palm oil, mustard oil, cottonseed oil, tallow, yellow and brown greases, lard, train oil, fats in milk, fish oil, algal oil, sewage sludge, cuphea oil, camelina oil, jatropha oil, curcas oil, babassu oil, palm kernel oil, crambe oil, and the like.15. The process of paragraphs 1-13, wherein the biofeedstock is a biofeedstock containing only renewable biocomponents; or wherein a fossil feedstock is not used as a component of the renewable feedstock.T-11794-W00116. The process of paragraphs 1-13, wherein the biofeedstock comprises a fossil feedstock.17. The process of claim 16, wherein the biofeedstock or fossil feedstock comprises gas oil; vacuum gas oil; long residue; vacuum residue; atmospheric distillate; heavy fuel; oil; wax and paraffin; used oil; used cooking oil; deasphalted residue or crude; charges resulting from thermal or catalytic conversion processes; shale oil; cycle oil; animal and vegetable derived fats, oils and waxes; petroleum and slack wax; Fischer-Tropsch products; or a combination thereof.18. The process of paragraphs 1-17, wherein the process is carried out in a single or dual stage reactor system.19. The process of paragraphs 1-18, wherein the process is carried out in a single stage reactor system, e.g., in a single reactor.20. The process of paragraphs 1-18, wherein the process is carried out in two or more reactors, reactor sections, or reactor layers connected in a flow-through sequence, preferably with the second reactor, reactor section, or reactor layer comprising the SSZ-91 catalyst.21. The process according to paragraphs 1-20, wherein the catalytic conditions comprise: a temperature in the range of about 400°F (204°C), or 450°F (232°C) to about 730°F (388°C), or 800°F (439°C); a pressure in the range of about 0 to about 3000 psig (0 to 20.68 MPa), or 0 to 2700 psig (0 to 18.62 MPa), or 0 to 2200 psig (0 to 15.17 MPa), or 0 to 1800 psig (0 to 12.41 MPa), or 0 to 1300 psig (0 to 8.96 MPa), [other conditions?]22. The process according to paragraphs 1-21, wherein the SSZ-91 catalyst provides improved dewaxing performance compared to SSZ-91 noble metal catalysts comprising Pt and Pd and / or to SSZ-91 base metal catalysts comprising Ni and W and / or Ni and Mo.23. The process according to claim 22, wherein the SSZ-91 catalyst provides an improved diesel product cloud point of greater than O to about 4°C for 2-stage hydroprocessing and / or greater than 0 to about 11°C for 1-stage hydroprocessing.24. The process according to claim 22 or 23, wherein the SSZ-91 catalyst provides an improved diesel product yield of greater than 0 to about 15 wt.%, or 0 to about 10 wt.%, or 0 to about 7 wt.%, or 0 to about 5 wt.%.
[0110] It will be understood that the invention is not limited to the embodiments described above and various modifications and improvements can be made without departing from the concepts described herein. Except where mutually exclusive, any of the features may be employed separately or in combination with any other features and the disclosure extends to and includes all combinations and sub-combinations of one or more features described herein.T-11794-W001
[0111] The foregoing description of one or more embodiments of the invention is primarily for illustrative purposes, it being recognized that variations might be used which would still incorporate the essence of the invention. Reference should be made to the following claims in determining the scope of the invention.
[0112] For the purposes of U.S. patent practice, and in other patent offices where permitted, all patents and publications cited in the foregoing description of the invention are incorporated herein by reference to the extent that any information contained therein is consistent with and / or supplements the foregoing disclosure.
Claims
T-11794-W001WHAT IS CLAIMED IS:
1. A process for making a renewable product, the process comprising contacting a biofeedstock with a hydroisomerization catalyst under hydroisomerization conditions to produce a renewable product; wherein, the hydroisomerization catalyst comprises an SSZ-91 molecular sieve and the catalytically active metals Pt and Ru or Pt and Re.
2. The process of claim 1, wherein the catalyst metals content is 0.01-5.0 wt.%, or 0.01-3.0 wt.%, or 0.01-2.0 wt.%, or 0.1-2.0 wt.% (total catalyst weight basis).
3. The process of claim 1 or 2, wherein the catalyst Pt metal content is 0.01 to 5 wt.%, or 0.01 to 3.0 wt.%, or 0.01 to 2.0 wt.%, or 0.01-1.0 wt.% or 0.01-0.8 wt.%, or 0.1-1.0 wt.% (total catalyst weight basis).
4. The process of claims 1-3, wherein the catalyst Ru or Re metal content is 0.01- to 5 wt.%, or 0.01 to 3.0 wt.%, or 0.01 to 2.0 wt.%, or 0.01-1.5 wt.% or 0.01-1.0 wt.%, or 0.1-1.0 wt.% (total catalyst weight basis).
5. The process of claims 1-4, wherein the catalyst Pt metal content is 0.01- to 5 wt.%, or 0.01 to 3.0 wt.%, or 0.01 to 2.0 wt.%, or 0.01-1.0 wt.% or 0.01-0.8 wt.%, or 0.1-1.0 wt.% and the Ru or Re metal content is 0.01- to 5 wt.%, or 0.01 to 3.0 wt.%, or 0.01 to 2.0 wt.%, or 0.01-1.0 wt.% or 0.01-0.8 wt.%, or 0.1-1.0 wt.% (total catalyst weight basis).
6. The process of claims 1-5, wherein the molar ratio of Pt to Ru or Pt to Re is in the range of 1000:1 to 1:1000, 500:1 to 1:500, 1:100 to 100:1, 1:20 to 20:1, or 5:1 to 1:20, or 5:1 to 1:10, or 5:1 to 1:5, or 3:1 to 1:3, or 1:1 to 1:2, or 5:1 to 2:1, or 5:1 to 3:1, or 1:1 to 1:3, or 1:1 to 1:4.
7. The process of claims 1-6, wherein the catalyst further comprises a support material selected from alumina, silica, aluminosilicate, titania, zirconia, carbon (e.g., graphite), ceria, magnesia, or a combination thereof.
8. The process of claims 1-7, wherein the catalyst comprises 0.01 to 5.0 wt.%, or 0.01 to 3.0 wt.%, or 0.01 to 2.0 wt.%, or 0.01 to 1.0 wt.% of the catalytically active metal, 1 to 99 wt.% of the support material, and 0.1 to 99 wt.% of the SSZ-91 molecular sieve.
9. The process of claims 1-8, wherein the catalyst further comprises a metal selected from Groups 6 to 10 and Group 14 of the Periodic Table.
10. The process of claims 1-9, wherein the silicon oxide to aluminum oxide mole ratio of the SSZ-91 molecular sieve is in the range of 40 to 220 or 50 to 220 or 40 to 200.
11. The process of claims 1-10, wherein the SSZ-91 molecular sieve comprises ZSM-48 type zeolite material, the molecular sieve having:T-11794-W001 at least 70% polytype 6 of the total ZSM-48-type material; an EUO-type phase in an amount of between 0 and 3.5 percent by weight; and polycrystalline aggregate morphology comprising crystallites having an average aspect ratio of between 1 and 8.
12. The process of claims 1-11, wherein the SSZ-91 molecular sieve comprises one of more of: at least 80%, or 90%, polytype 6 of the total ZSM-48-type material; between 0.1 and 2 wt.% EU-1; crystallites having an average aspect ratio of between 1 and 5, or between 1 and 3; or a combination thereof.
13. The process of claims 1-12, wherein the biofeedstock comprises or is a biocomponent feed selected from lipids, vegetable oils and animal fats which comprise triglycerides and free fatty acids, for example wherein the biocomponent feed is selected from canola oil, corn oil, soy oils, castor oil, camelina oil, palm oil and a combination thereof; or wherein the biofeedstock comprises a biofeedstock- derived oxygen containing compound.
14. The process of claims 1-13, wherein the biofeedstock comprises or is a biocomponent feed selected from canola oil, corn oil, soy oils, castor oil, camelina oil, palm oil, carinata oil, rapeseed oil, soybean oil, colza oil, tall oil, sunflower oil, hempseed oil, olive oil, linseed oil, coconut oil, castor oil, peanut oil, palm oil, mustard oil, cottonseed oil, tallow, yellow and brown greases, lard, train oil, fats in milk, fish oil, algal oil, sewage sludge, cuphea oil, camelina oil, jatropha oil, curcas oil, babassu oil, palm kernel oil, crambe oil, and the like.
15. The process of claims 1-13, wherein the biofeedstock is a biofeedstock containing only renewable biocomponents; or wherein a fossil feedstock is not used as a component of the renewable feedstock.
16. The process of claims 1-13, wherein the biofeedstock comprises a fossil feedstock.
17. The process of claim 16, wherein the biofeedstock or fossil feedstock comprises gas oil; vacuum gas oil; long residue; vacuum residue; atmospheric distillate; heavy fuel; oil; wax and paraffin; used oik- used cooking oil; deasphalted residue or crude; charges resulting from thermal or catalytic conversion processes; shale oil; cycle oil; animal and vegetable derived fats, oils and waxes; petroleum and slack wax; Fischer-Tropsch products; or a combination thereof.
18. The process of claims 1-17, wherein the process is carried out in a single or dual stage reactor system.
19. The process of claims 1-18, wherein the process is carried out in a single stage reactor system, e.g., in a single reactor.T-11794-W00120. The process of claims 1-18, wherein the process is carried out in two or more reactors, reactor sections, or reactor layers connected in a flow-through sequence, preferably with the second reactor, reactor section, or reactor layer comprising the SSZ-91 catalyst.
21. The process according to claims 1-20, wherein the catalytic conditions comprise: a temperature in the range of about 400°F (204°C), or 450°F (232°C) to about 730°F (388°C), or 800°F (439°C); a pressure in the range of about 0 to about 3000 psig (0 to 20.68 MPa), or 0 to 2700 psig (0 to 18.62 MPa), or 0 to 2200 psig (0 to 15.17 MPa), or 0 to 1800 psig (0 to 12.41 MPa), or 0 to 1300 psig (0 to 8.96 MPa), [other conditions?]22. The process according to claims 1-21, wherein the SSZ-91 catalyst provides improved dewaxing performance compared to SSZ-91 noble metal catalysts comprising Pt and Pd and / or to SSZ-91 base metal catalysts comprising Ni and W and / or Ni and Mo.
23. The process according to claim 22, wherein the SSZ-91 catalyst provides an improved diesel product cloud point of greater than 0 to about 4°C for 2-stage hydroprocessing and / or greater than 0 to about 11°C for 1-stage hydroprocessing.
24. The process according to claim 22 or 23, wherein the SSZ-91 catalyst provides an improved diesel product yield of greater than 0 to about 15 wt.%, or 0 to about 10 wt.%, or 0 to about 7 wt.%, or 0 to about 5 wt.%.
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