Process for hydroisomerising a hydrocarbon feed

Abstract

This article describes a process for hydroisomerizing a hydrocarbon feed. The process may include: combining the hydrocarbon feed and a hydroisomerizing additive to provide a combined feed; and contacting the combined feed with a hydroisomerizing catalyst comprising zeolite SSZ-91, wherein the hydroisomerizing additive is a substituted or unsubstituted nitrogen heterocycle.

Description

Technical Field

[0001] This article describes a new process for hydroisomerizing hydrocarbon feedstocks using hydroisomerization additives. Prior Technology

[0002] Hydroisomerization is a process that increases the ratio of isoalkanes to n-alkanes during the hydroisomerization of hydrocarbon feedstock. Therefore, hydroisomerization is used to upgrade hydrocarbon feedstocks, providing base oils with improved properties compared to the hydrocarbon feedstock from which the base oil is derived, such as a lower pour point. Hydroisomerization catalysts contain molecular sieves, the pore size of which determines the size and shape of molecules that can enter the molecular sieve.

[0003] There is a continuous need to develop new and improved hydroisomerization processes. Summary of the Invention

[0004] []

[0005] This invention relates to a process for increasing the yield of base oils produced by hydroisomerization of hydrocarbon feedstocks. The invention is based on the inventors' remarkable discovery that adding nitrogen-containing heterocyclic compounds to hydrocarbon feedstocks as hydroisomerization additives increases the yield of base oils produced by contacting hydrocarbon feedstocks with a hydroisomerization catalyst containing zeolite SSZ-91.

[0006] Based on the first state sample, a process for hydroisomerizing a hydrocarbon feedstock is provided, the process comprising: Combined hydrocarbon feedstock and hydroisomerization additives to provide combined feedstock; and This allows the combined feedstock to contact the hydroisomerization catalyst. The hydroisomerization additive is a substituted or unsubstituted nitrogen heterocycle, and the hydroisomerization catalyst contains zeolite SSZ-91.

[0007] According to the second sample, a process is provided for increasing the yield of base oil produced by hydroisomerization of hydrocarbon feedstock, the process comprising: Combined hydrocarbon feedstock and hydroisomerization additives to provide combined feedstock; and The combined feedstock is contacted with a hydroisomerization catalyst containing zeolite SSZ-91 to form a base oil product. The hydrogenated isomerizing additive is a substituted or unsubstituted nitrogen heterocycle, and Compared to the process performed in the absence of the hydroisomerizing additive, the yield of the base oil product is increased by at least 1.0 wt%.

[0008] According to the third sample, the use of the hydroisomerization additive in improving the yield of base oil produced by the following processes is provided: contacting a hydrocarbon feedstock and a hydroisomerization catalyst; combining the hydrocarbon feedstock and the hydroisomerization additive to form a combined feedstock, and then contacting the combined feedstock and the hydroisomerization catalyst. The hydroisomerization additive is a substituted or unsubstituted nitrogen heterocycle, and the hydroisomerization catalyst contains zeolite SSZ-91.

[0009] Those skilled in this art will understand that, except in cases of mutual exclusion, the features described for any of the above-described states can be applied by analogy to any other state. Furthermore, except in cases of mutual exclusion, any feature described herein can be applied to any state and / or combined with any other feature described herein. Simple Explanation of the Diagram

[0010] []

[0011] Figure 1 schematically illustrates a process for hydroisomerizing a hydrocarbon feedstock according to one embodiment of the present invention. Implementation

[0012] [] Cross-reference to related applications

[0013] This application claims the benefit of priority to U.S. Patent Application No. 17 / 138,223, filed on December 30, 2020, the entire disclosure of which is incorporated herein by reference. Introduction

[0014] As used herein, the term "nitrogen heterocycle" refers to a heterocyclic compound containing at least one nitrogen heteroatom occupying a ring position. In embodiments, the heteroatom contained in the nitrogen heterocycle is composed of nitrogen. In embodiments, the nitrogen heterocycle contains only a single heteroatom, which is nitrogen.

[0015] As used herein, the term "double bond equivalent" or "DBE" refers to the number of molecules that must be added to a given molecule (e.g., to an nitrogen heterocycle as described herein) to convert all pi bonds to single bonds and all rings to acyclic H₂ structures. The DBE (double bond equivalent) number can be determined from the molecular formula using the following equation: DBE = C – (H / 2) + (N / 2) + 1 Where C represents the number of carbon atoms, H represents the number of hydrogen atoms, and N represents the number of nitrogen atoms in the molecule. For example, a DBE number of 1 corresponds to one ring or one double bond, and a DBE number of 2 corresponds to two rings, two double bonds, one triple bond, or one ring plus one double bond. For example, carbazole has a DBE number of 9 (one of each of the three rings and one of each of the three double bonds), and ethylcarbazole also has a DBE number of 9 (one of each of the three rings and one of each of the three double bonds).

[0016] As used herein, the term "pour point" refers to the temperature at which an oil of hydrocarbon feed, such as that described herein, begins to flow under controlled conditions. Pour point can be determined according to ASTM D5950.

[0017] Unless otherwise specified, the “feed rate” of hydrocarbon feed to the catalytic reaction zone is expressed herein as the feed volume per hour per volume of catalyst, which may be referred to as the liquid space time (LHSV) in reciprocal hours (h⁻¹).

[0018] The terms "MRE-type molecular sieve" and "EUO-type molecular sieve" include all molecular sieves and their isotypes that have been assigned to the International Zeolite Association framework, as described in the Zeolite Framework Type Atlas edited by Baerlocher, LB McCusker and DH Olson, Elsevier, 6th revision, 2007, and in the Zeolite Structure Database on the International Zeolite Association website (http: / / www.iza-online.org).

[0019] "Group 2, Group 8, Group 9 and Group 10 metals" refers to metals selected from Group 2, Group 8, Group 9 and Group 10 of the periodic table and / or metal compounds containing these metals.

[0020] The term "periodic table" refers to the IUPAC version of the periodic table of elements dated December 1, 2018.

[0021] For the purposes of this specification and the appended claims, unless otherwise indicated, all figures representing quantities, percentages or proportions and other numerical values ​​used in the specification and claims should be understood to be modified by the term "about" in all cases. Therefore, unless indicated to the contrary, the numerical parameters set forth in the following specification and the appended claims are approximate values, which may vary depending on the desired nature sought to be obtained. Note that, as used in this specification and the appended claims, the singular forms "a" and "the" include plural references unless explicitly and unambiguously limited to a single reference. As used herein, the term "comprising" and its grammatical variations are intended to be non-limiting, such that the listing of items does not exclude other similar items that may be substituted for or added to the listed items. As used herein, the term "comprising" means including the element or step identified after the term, but any such element or step is not exhaustive, and embodiments may include other elements or steps.

[0022] Unless otherwise specified, descriptions of the types of elements, materials, or other components from which a single component or mixture of components may be selected are intended to include all possible subgenus combinations of the listed components and mixtures thereof. Furthermore, all numerical ranges presented herein include both upper and lower limits of such ranges.

[0023] If a standard test is mentioned herein, unless otherwise stated, the version of the test mentioned is the latest version at the time of filing this patent application.

[0024] The scope of a patent may be defined by the scope of the patent application and may include other instances that would occur to a person skilled in the art. Such other instances are intended to be within the scope of the patent application if they have structural elements that are indistinguishable from the literal language of the scope of the patent application, or if such other instances include equivalent structural elements that are not substantially different from the literal language of the scope of the patent application. All citations used herein, without contradiction, are incorporated herein by reference. [Hydroisomerization additive] []

[0025] This article describes a hydroisomerization additive that can be introduced into the hydrocarbon feed prior to hydroisomerization using a hydroisomerization catalyst. Surprisingly, it was found that adding the hydroisomerization additive to the hydrocarbon feed increased the yield of hydroisomerized base oil products produced by the hydroisomerization process described herein.

[0026] The hydroisomerizing additive is a substituted or unsubstituted nitrogen heterocycle. In the examples, the substituted or unsubstituted nitrogen heterocycle is a substituted or unsubstituted aromatic nitrogen heterocycle.

[0027] In an embodiment, the hydroisomerizing additive has a double bond equivalent (DBE) number in the range of 3 to 10 (e.g., 4 to 10, 6 to 10, 7 to 10, 8 to 10, or 7 to 9). In an embodiment, the double bond equivalent (DBE) number of the hydroisomerizing additive is 9.

[0028] In the embodiments, the molecular weight of the hydroisomerizing additive is less than about 600, for example less than about 500, less than about 250, or less than about 200. In the embodiments, the molecular weight of the hydroisomerizing additive is in the range of about 60 to about 600 (e.g., about 60 to about 250).

[0029] In the embodiments, the hydroisomerizing additive is selected from: substituted or unsubstituted tricyclic fused-ring aromatic nitrogen heterocycles (e.g., substituted or unsubstituted 11- to 14-membered tricyclic fused-ring aromatic nitrogen heterocycles); substituted or unsubstituted bicyclic fused-ring aromatic nitrogen heterocycles (e.g., substituted or unsubstituted 8- to 10-membered bicyclic fused-ring aromatic nitrogen heterocycles); and monocyclic aromatic nitrogen heterocycles (e.g., substituted or unsubstituted 5- or 6-membered bicyclic fused-ring aromatic nitrogen heterocycles). In the embodiments, the hydroisomerizing additive is selected from substituted or unsubstituted carbazole, substituted or unsubstituted pyrrole, substituted or unsubstituted pyridine, substituted or unsubstituted indole, substituted or unsubstituted quinoline, and substituted or unsubstituted acridine. In the embodiments, the hydroisomerizing additive is a substituted or unsubstituted carbazole. In the embodiments, the hydroisomerizing additive is a substituted carbazole. In the embodiments, the hydroisomerizing additive is N-ethylcarbazole.

[0030] In the embodiments, the hydroisomerizing additive is a substituted nitrogen heterocycle (e.g., a substituted aromatic nitrogen heterocycle) that is independently substituted with one or more substituents selected from the following: alkyl; hydroxyl; alkoxy; carboxyl; and -NR'R”, wherein R' and R” are independently H or alkyl. In the embodiments, the hydroisomerizing additive is a substituted nitrogen heterocycle (e.g., a substituted aromatic nitrogen heterocycle) that is independently substituted with one or more substituents selected from the following: C1-10 alkyl; hydroxyl; C1-10 alkoxy; C1-10 carboxyl; and -NR'R”, wherein R' and R” are independently H or C1-10 alkyl. In the embodiments, the hydroisomerizing additive is a substituted nitrogen heterocycle (e.g., a substituted aromatic nitrogen heterocycle) that is independently substituted with one or more substituents selected from the following: C1-6 alkyl, hydroxyl, C1-6 alkoxy, C1-6 carboxyl, and -NR'R"", wherein R' and R" are independently H or C1-6 alkyl. In the embodiments, the hydroisomerizing additive is a substituted nitrogen heterocycle (e.g., a substituted aromatic nitrogen heterocycle) that is independently substituted with one or more substituents selected from the following: C1-4 alkyl, hydroxyl, C1-4 alkoxy, C1-4 carboxyl, and -NR'R"", wherein R' and R" are independently H or C1-4 alkyl. In the embodiments, the hydroisomerizing additive is a substituted nitrogen heterocycle (e.g., a substituted aromatic nitrogen heterocycle) that is independently substituted with one or more substituents selected from C1-10 alkyl. In the examples, the hydroisomerizing additive is a substituted nitrogen heterocycle (e.g., a substituted aromatic nitrogen heterocycle) that is independently substituted with one or more substituents selected from C1-6 alkyl groups. In the examples, the hydroisomerizing additive is a substituted nitrogen heterocycle (e.g., a substituted aromatic nitrogen heterocycle) that is independently substituted with one or more substituents selected from C1-4 alkyl groups.

[0031] In the examples, the hydroisomerizing additive is an unsubstituted nitrogen heterocycle (e.g., an unsubstituted aromatic nitrogen heterocycle).

[0032] In the embodiments, the hydroisomerizing additive is a substituted or unsubstituted aromatic nitrogen heterocycle according to Formula I: (I) in R1 is selected from hydrogen, C1-10 alkyl, hydroxyl, C1-10 alkoxy, and C1-10 carboxyl; and R2 and R3 are independently selected from hydrogen, C1-10 alkyl, hydroxyl, C1-10 alkoxy, C1-10 carboxyl and -NR'R”, wherein R' and R” are independently H or C1-10 alkyl.

[0033] In the examples, R1 is selected from hydrogen, C1-10 alkyl, hydroxyl, C1-10 alkoxy, and C1-10 carboxyl. In the examples, R1 is selected from hydrogen, C1-6 alkyl, hydroxyl, C1-6 alkoxy, and C1-6 carboxyl. In the examples, R1 is selected from hydrogen, C1-4 alkyl, hydroxyl, C1-4 alkoxy, and C1-4 carboxyl. In the examples, R1 is selected from hydrogen and C1-10 alkyl. In the examples, R1 is selected from hydrogen and C1-6 alkyl. In the examples, R1 is selected from hydrogen and C1-4 alkyl. In the examples, R1 is a C1-10 alkyl. In the examples, R1 is a C1-6 alkyl. In the examples, R1 is a C1-4 alkyl.

[0034] In the embodiments, R2 and R3 are independently selected from hydrogen, C1-10 alkyl, hydroxyl, C1-10 alkoxy, C1-10 carboxyl, and -NR'R"", wherein R' and R" are independently H or C1-10 alkyl. In the embodiments, R2 and R3 are independently selected from hydrogen, C1-6 alkyl, hydroxyl, C1-6 alkoxy, C1-6 carboxyl, and -NR'R"", wherein R' and R" are independently H or C1-6 alkyl. In the embodiments, R2 and R3 are independently selected from hydrogen, C1-4 alkyl, hydroxyl, C1-4 alkoxy, C1-4 carboxyl, and -NR'R"", wherein R' and R" are independently H or C1-4 alkyl. In the embodiments, R2 and R3 are independently selected from hydrogen and C1-10 alkyl. In the embodiments, R2 and R3 are independently selected from hydrogen and C1-6 alkyl. In the embodiments, R2 and R3 are independently selected from hydrogen and C1-4 alkyl groups. In the embodiments, R2 and R3 are hydrogen.

[0035] In the examples, R1 is selected from hydrogen, C1-6 alkyl, hydroxyl, C1-6 alkoxy, and C1-6 carboxyl; and R2 and R3 are independently selected from hydrogen, C1-6 alkyl, hydroxyl, C1-6 alkoxy, C1-6 carboxyl, and -NR'R"", wherein R' and R" are independently H or C1-6 alkyl. In the examples, R1 is selected from hydrogen, C1-4 alkyl, hydroxyl, C1-4 alkoxy, and C1-4 carboxyl; and R2 and R3 are independently selected from hydrogen, C1-4 alkyl, hydroxyl, C1-4 alkoxy, C1-4 carboxyl, and -NR'R"", wherein R' and R" are independently H or C1-4 alkyl. In the examples, R1 is selected from hydrogen and C1-10 alkyl; and R2 and R3 are independently selected from hydrogen and C1-10 alkyl. In the embodiments, R1 is selected from hydrogen and C1-6 alkyl; and R2 and R3 are independently selected from hydrogen and C1-6 alkyl. In the embodiments, R1 is selected from hydrogen and C1-4 alkyl; and R2 and R3 are independently selected from hydrogen and C1-4 alkyl. In the embodiments, R1 is C1-10 alkyl; and R2 and R3 are hydrogen. In the embodiments, R1 is C1-6 alkyl; and R2 and R3 are hydrogen. In the embodiments, R1 is C1-4 alkyl; and R2 and R3 are hydrogen. In the embodiments, R1 is C1-3 alkyl; and R2 and R3 are hydrogen. In the embodiments, R1 is C1-2 alkyl; and R2 and R3 are hydrogen. In the embodiments, R1 is C2 alkyl; and R2 and R3 are hydrogen.

[0036] In the examples, R1 is selected from hydrogen, C1-10 alkyl, hydroxyl, C1-10 alkoxy, and C1-10 carboxyl; and R2 and R3 are independently selected from hydrogen, C1-6 alkyl, hydroxyl, C1-6 alkoxy, C1-6 carboxyl, and -NR'R"", wherein R' and R" are independently H or C1-6 alkyl. In the examples, R1 is selected from hydrogen, C1-10 alkyl, hydroxyl, C1-10 alkoxy, and C1-10 carboxyl; and R2 and R3 are independently selected from hydrogen, C1-4 alkyl, hydroxyl, C1-4 alkoxy, C1-4 carboxyl, and -NR'R"", wherein R' and R" are independently H or C1-4 alkyl. In the examples, R1 is selected from hydrogen, C1-10 alkyl, hydroxyl, C1-10 alkoxy, and C1-10 carboxyl; and R2 and R3 are independently selected from hydrogen and C1-10 alkyl. In the examples, R1 is selected from hydrogen, C1-10 alkyl, hydroxyl, C1-10 alkoxy, and C1-10 carboxyl; and R2 and R3 are independently selected from hydrogen and C1-6 alkyl. In the examples, R1 is selected from hydrogen, C1-10 alkyl, hydroxyl, C1-10 alkoxy, and C1-10 carboxyl; and R2 and R3 are independently selected from hydrogen and C1-4 alkyl. In the examples, R1 is selected from hydrogen, C1-10 alkyl, hydroxyl, C1-10 alkoxy, and C1-10 carboxyl; and R2 and R3 are hydrogen.

[0037] In the examples, R1 is selected from hydrogen, C1-6 alkyl, hydroxyl, C1-6 alkoxy, and C1-6 carboxyl; and R2 and R3 are independently selected from hydrogen, C1-10 alkyl, hydroxyl, C1-10 alkoxy, C1-10 carboxyl, and -NR'R"", wherein R' and R" are independently H or C1-10 alkyl. In the examples, R1 is selected from hydrogen, C1-4 alkyl, hydroxyl, C1-4 alkoxy, and C1-4 carboxyl; and R2 and R3 are independently selected from hydrogen, C1-10 alkyl, hydroxyl, C1-10 alkoxy, C1-10 carboxyl, and -NR'R"", wherein R' and R" are independently H or C1-10 alkyl. In the examples, R1 is selected from hydrogen and C1-10 alkyl; and R2 and R3 are independently selected from hydrogen, C1-10 alkyl, hydroxyl, C1-10 alkoxy, C1-10 carboxyl and -NR'R"", wherein R' and R" are independently H or C1-10 alkyl. In the examples, R1 is selected from hydrogen and C1-6 alkyl. In the examples, R1 is selected from hydrogen and C1-4 alkyl; and R2 and R3 are independently selected from hydrogen, C1-10 alkyl, hydroxyl, C1-10 alkoxy, C1-10 carboxyl and -NR'R"", wherein R' and R" are independently H or C1-10 alkyl. In the examples, R1 is a C1-10 alkyl group; and R2 and R3 are independently selected from hydrogen, C1-10 alkyl, hydroxyl, C1-10 alkoxy, C1-10 carboxyl, and -NR'R"", wherein R' and R" are independently H or C1-10 alkyl. In the examples, R1 is a C1-6 alkyl group; and R2 and R3 are independently selected from hydrogen, C1-10 alkyl, hydroxyl, C1-10 alkoxy, C1-10 carboxyl, and -NR'R"", wherein R' and R" are independently H or C1-10 alkyl. In the examples, R1 is a C1-4 alkyl group; and R2 and R3 are independently selected from hydrogen, C1-10 alkyl, hydroxyl, C1-10 alkoxy, C1-10 carboxyl, and -NR'R"", wherein R' and R" are independently H or C1-10 alkyl. [Hydroisomerization catalyst] []

[0038] In the examples, the hydroisomerization catalyst comprises zeolite SSZ-91.

[0039] In the embodiments, the hydroisomerization catalyst comprises about 5 to about 95% by weight of zeolite SSZ-91 based on the total weight of the hydroisomerization catalyst, such as about 10 to about 95% by weight of zeolite SSZ-91, about 20 to about 90% by weight of zeolite SSZ-91, about 25 to about 85% by weight of zeolite SSZ-91, about 30 to about 80% by weight of zeolite SSZ-91, about 35 to about 75% by weight of zeolite SSZ-91, about 35 to about 55% by weight of zeolite SSZ-91, about 45 to about 75% by weight of zeolite SSZ-91, or about 55 to about 75% by weight of zeolite SSZ-91 based on the total weight of the hydroisomerization catalyst.

[0040] The hydroisomerization catalyst further comprises a metal modifier, such as a metal modifier selected from Group 2, Group 8, Group 9, and Group 10 metals or combinations thereof. In embodiments, the metal modifier is selected from Group 8, Group 9, or Group 10 metals or combinations thereof; for example, the metal modifier may be selected from Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, or combinations thereof. In embodiments, the metal modifier is selected from Group 10 metals or combinations thereof. In embodiments, the hydroisomerization catalyst comprises platinum.

[0041] In the embodiments, the hydroisomerization catalyst comprises about 0.05 to about 2.0% by weight of a metal modifier (e.g., a Group 8, Group 9, or Group 10 metal, such as a Group 10 metal, like platinum) based on the total weight of the hydroisomerization catalyst, for example, about 0.1 to about 1.5% by weight, or about 0.2 to about 1.5% by weight, or about 0.1 to about 1% by weight based on the total weight of the hydroisomerization catalyst.

[0042] In embodiments, the hydroisomerization catalyst comprises an oxide binder. In embodiments, the oxide binder is an inorganic oxide. In embodiments, the hydroisomerization catalyst comprises an oxide binder selected from alumina, silica, cerium oxide, titanium dioxide, tungsten oxide, zirconium oxide, and combinations thereof. In embodiments, the hydroisomerization catalyst comprises an oxide binder comprising alumina. Suitable alumina is commercially available, including, for example, Catapal® alumina and Pural® alumina from Sasol® or Versal® alumina from UOP®. Generally, alumina can be any alumina known to be used as a matrix material in a catalyst matrix. For example, alumina can be boehmite, gibbsite, γ-alumina, η-alumina, θ-alumina, δ-alumina, χ-alumina, or mixtures thereof. In the embodiments, the hydroisomerization catalyst comprises about 5 to 95% by weight of an oxide binder based on the total weight of the hydroisomerization catalyst, such as about 5 to 80% by weight of an oxide binder, about 10 to 70% by weight of oxide binder a, and about 20 to 70% by weight of an oxide binder, such as about 25 to 65% by weight of an oxide binder.

[0043] In the embodiments, the hydroisomerization catalyst comprises: Approximately 5% to approximately 95% by weight of zeolite SSZ-91; About 0.05 to about 2.0% by weight of Group 8 to Group 10 metals; and The oxide binder comprises approximately 5 to approximately 95% by weight of the total weight of the hydroisomerization catalyst.

[0044] In the embodiments, the hydroisomerization catalyst comprises: Approximately 30 to approximately 80% by weight of zeolite SSZ-91; About 0.1 to about 1.5% by weight of Group 8 to Group 10 metals; and Oxide binder comprising approximately 20 to approximately 70% by weight of the total weight of the hydroisomerization catalyst. [, zeolite , ] [, SSZ-91 , ]

[0045] Zeolite SSZ-91 and the method for manufacturing zeolite SSZ-91 are described in US-A-9920260. Zeolite SSZ-91 can also be referred to as SSZ-91 molecular sieve.

[0046] Zeolite SSZ-91 has a SiO2 / Al2O3 molar ratio (SAR) of 40:220. In embodiments, zeolite SSZ-91 has the following SiO2 / Al2O3 molar ratio (SAR): 40:200, for example 70:200, 80:200, 70:180, 80:180, 70:160, 80:160, 70:140, 80:140, 100:160, 100:140, or 120:140. SAR is determined by inductively coupled plasma (ICP) elemental analysis.

[0047] Zeolite SSZ-91 comprises at least 70% polymorph 6 of all ZSM-48 type materials present in the product. The proportion of polymorph 6 of all ZSM-48 type materials 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 disorder is tuned by three different failure probabilities. It should be noted that the phrase "at least X%" includes the absence of other ZSM-48 polymorphs in the structure, i.e., the material is 100% polymorph 6. The structure of polymorph 6 is described by Lobo and Koningsveld (see J. Am. Chem. Soc. 2002, 124, 13222-13230). In an embodiment, the SSZ-91 material comprises at least 80% polymorph 6 of all ZSM-48 type materials present in the product. In this embodiment, the SSZ-91 material comprises at least 90% polytype 6 of all ZSM-48 type materials present in the product. The polytype 6 structure has been given a framework code *MRE by the Structure Committee of the International Zeolite Association.

[0048] The morphological characteristics of zeolite SSZ-91 are that it comprises polycrystalline aggregates of microcrystals having an average aspect ratio in the range of 1 to 8. In an embodiment, zeolite SSZ-91 is characterized by comprising polycrystalline aggregates of microcrystals having an average aspect ratio in the range of 1 to 6 (e.g., 1 to 5, 1 to 4, or 1 to 3).

[0049] In this embodiment, the morphology of zeolite SSZ-91 is characterized by polycrystalline aggregates with diameters between about 100 nm and 1.5 μm, each aggregate comprising a collection of microcrystals having an average aspect ratio in the range of 1 to 8. In this embodiment, the morphology of zeolite SSZ-91 is characterized by polycrystalline aggregates with diameters between about 100 nm and 1.5 μm, each aggregate comprising a collection of microcrystals having an average aspect ratio in the range of 1 to 6 (e.g., 1 to 5, 1 to 4, or 1 to 3). As used herein, the term diameter refers to the shortest length at the short end of each microcrystal examined.

[0050] Zeolite SSZ-91 is a substantially phase-pure material. As used herein, the term "substantially phase-pure material" means that the material contains no zeolite phases other than those belonging to the ZSM-48 series of zeolites, or that the amount of zeolite present has a minimal measurable effect on the material's selectivity or imparts fewer material disadvantages to the material. Two common phases that co-crystallize with SSZ-91 are EUO-type molecular sieves such as EU-1, and natural sodium silicate and naphthalene silicate. These additional phases can exist as separate phases or can interact with SSZ-91.

[0051] In one embodiment, zeolite SSZ-91 comprises an EUO-type molecular sieve phase in the range of 0 to 7 wt% based on the total weight of the zeolite SSZ-91 product. In another embodiment, zeolite SSZ-91 comprises an EUO-type molecular sieve phase in the range of 0 to 5.0 wt% (e.g., 0 to 4.0 wt%, or 0 to 3.5 wt%). In yet another embodiment, zeolite SSZ-91 comprises an EUO-type molecular sieve phase in the range of 0.1 to 7.0 wt% (e.g., 0.1 to 5.0 wt%, or 0.1 to 4.0 wt%, or 0.1 to 3.5 wt%). In the embodiments, zeolite SSZ-91 contains 0 to 7% by weight of EU-1, such as 0 to 5.0% by weight of EU-1, 0 to 4.0% by weight of EU-1, 0 to 3.5% by weight of EU-1, 0.1 to 7.0% by weight of EU-1, 0.1 to 5.0% by weight of EU-1, 0.1 to 4.0% by weight of EU-1, 0.1 to 3.5% by weight of EU-1, 0.1 to 2% by weight of EU-1, or 0.1 to 1% by weight of EU-1.

[0052] As is well known, the ratio of peak intensities in powder XRD varies linearly as a function of the weight fraction of any two phases in a mixture: (Iα / Iβ) = (RIRα / RIRβ)*(xα / xβ), where the RIR (reference intensity ratio) parameter can be found in the Powder Diffraction Archive (PDF) database of the International Center for Diffraction Data (http: / / www.icdd.com / products / ). Therefore, the weight percentage of the EUO phase in zeolite SSZ-91 can be calculated by measuring the ratio between the peak intensities of the EUO phase and the peak intensities of the SSZ-91 phase.

[0053] In this embodiment, zeolite SSZ-91 comprises: The molar ratio (SAR) of silicon oxide (SiO₂) to aluminum oxide (Al₂O₃) is 40 to 220. At least 70% of all ZSM-48 materials are multi-type 6; 0 to 7.0% by weight of EUO type molecular sieve phase; The morphological characteristics of zeolite SSZ-91 are that it contains polycrystalline aggregates of microcrystals with an average aspect ratio between 1 and 8.

[0054] In this embodiment, zeolite SSZ-91 comprises: The molar ratio (SAR) of silicon oxide (SiO₂) to aluminum oxide (Al₂O₃) is 40 to 220. At least 70% of all ZSM-48 materials are multi-type 6; 0 to 4.0% by weight of EUO type molecular sieve phase; The morphological characteristics of zeolite SSZ-91 are that it contains polycrystalline aggregates of microcrystals with an average aspect ratio between 1 and 8.

[0055] In this embodiment, zeolite SSZ-91 comprises: The molar ratio (SAR) of silicon oxide (SiO₂) to aluminum oxide (Al₂O₃) is 40 to 220. At least 70% of all ZSM-48 materials are multi-type 6; 0 to 3.5% by weight of EUO type molecular sieve phase; The morphological characteristics of zeolite SSZ-91 are that it contains polycrystalline aggregates of microcrystals with an average aspect ratio between 1 and 8.

[0056] In this embodiment, zeolite SSZ-91 comprises: The molar ratio (SAR) of silicon oxide (SiO₂) to aluminum oxide (Al₂O₃) is 40 to 200. At least 70% of all ZSM-48 materials are multi-type 6; 0 to 4.0% by weight of EUO type molecular sieve phase; The morphological characteristics of zeolite SSZ-91 are that it contains polycrystalline aggregates of microcrystals with an average aspect ratio between 1 and 8.

[0057] In this embodiment, zeolite SSZ-91 comprises: The molar ratio (SAR) of silicon oxide (SiO₂) to aluminum oxide (Al₂O₃) is 70 to 200. At least 70% of all ZSM-48 materials are multi-type 6; 0 to 4.0% by weight of EUO type molecular sieve phase; The morphological characteristics of zeolite SSZ-91 are that it contains polycrystalline aggregates of microcrystals with an average aspect ratio between 1 and 6.

[0058] In this embodiment, zeolite SSZ-91 comprises: The molar ratio (SAR) of silicon oxide (SiO₂) to aluminum oxide (Al₂O₃) is 80 to 200. At least 70% of all ZSM-48 materials are multi-type 6; 0.1 to 7.0 wt% EUO type molecular sieve phase; The morphological characteristics of zeolite SSZ-91 are that it contains polycrystalline aggregates of microcrystals with an average aspect ratio between 1 and 6.

[0059] In this embodiment, zeolite SSZ-91 comprises: The molar ratio (SAR) of silicon oxide (SiO₂) to aluminum oxide (Al₂O₃) is 80 to 200. At least 70% of all ZSM-48 materials are multi-type 6; 0.1 to 4.0 wt% EUO type molecular sieve phase; The morphological characteristic of zeolite SSZ-91 is that it consists of polycrystalline aggregates, which contain microcrystals with an average aspect ratio between 1 and 6.

[0060] In this embodiment, zeolite SSZ-91 comprises: The molar ratio (SAR) of silicon oxide (SiO₂) to aluminum oxide (Al₂O₃) is 80 to 200. At least 70% of all ZSM-48 materials are multi-type 6; 0.1 to 4.0 wt% EU-1; The morphological characteristics of zeolite SSZ-91 are that it contains polycrystalline aggregates of microcrystals with an average aspect ratio between 1 and 6.

[0061] In this embodiment, zeolite SSZ-91 comprises: The molar ratio (SAR) of silicon oxide (SiO₂) to aluminum oxide (Al₂O₃) is 80 to 200. At least 70% of all ZSM-48 materials are multi-type 6; 0.1 to 4.0 wt% EUO type molecular sieve phase; The morphological characteristics of zeolite SSZ-91 are that it contains polycrystalline aggregates of microcrystals with an average aspect ratio between 1 and 6.

[0062] In this embodiment, zeolite SSZ-91 comprises: The molar ratio (SAR) of silicon oxide (SiO₂) to aluminum oxide (Al₂O₃) is 80 to 160. At least 70% of all ZSM-48 materials are multi-type 6; 0.1 to 4.0 wt% EUO type molecular sieve phase; The morphological characteristics of zeolite SSZ-91 are that it contains polycrystalline aggregates of microcrystals with an average aspect ratio between 1 and 6.

[0063] In this embodiment, zeolite SSZ-91 comprises: The molar ratio (SAR) of silicon oxide (SiO₂) to aluminum oxide (Al₂O₃) is 70 to 160. At least 70% of all ZSM-48 materials are multi-type 6; 0.1 to 4.0 wt% EUO type molecular sieve phase; The morphological characteristics of zeolite SSZ-91 are that it contains polycrystalline aggregates of microcrystals with an average aspect ratio between 1 and 6.

[0064] In this embodiment, zeolite SSZ-91 comprises: The molar ratio (SAR) of silicon oxide (SiO₂) to aluminum oxide (Al₂O₃) is 70 to 200. At least 80% of all ZSM-48 materials are multi-body 6; 0.1 to 4.0 wt% EUO type molecular sieve phase; The morphological characteristics of zeolite SSZ-91 are that it contains polycrystalline aggregates of microcrystals with an average aspect ratio between 1 and 6.

[0065] In this embodiment, zeolite SSZ-91 comprises: The molar ratio (SAR) of silicon oxide (SiO₂) to aluminum oxide (Al₂O₃) is 80 to 200. At least 80% of all ZSM-48 materials are multi-body 6; 0.1 to 4.0 wt% EUO type molecular sieve phase; The morphological characteristics of zeolite SSZ-91 are that it contains polycrystalline aggregates of microcrystals with an average aspect ratio between 1 and 6.

[0066] In this embodiment, zeolite SSZ-91 comprises: The molar ratio (SAR) of silicon oxide (SiO₂) to aluminum oxide (Al₂O₃) is 80 to 200. At least 80% of all ZSM-48 materials are multi-body 6; 0.1 to 7.0 wt% EUO type molecular sieve phase; The morphological characteristics of zeolite SSZ-91 are that it contains polycrystalline aggregates of microcrystals with an average aspect ratio between 1 and 4.

[0067] In this embodiment, zeolite SSZ-91 comprises: The molar ratio (SAR) of silicon oxide (SiO₂) to aluminum oxide (Al₂O₃) is 80 to 200. At least 80% of all ZSM-48 materials are multi-body 6; 0.1 to 4.0 wt% EUO type molecular sieve phase; The morphological characteristics of zeolite SSZ-91 are that it contains polycrystalline aggregates of microcrystals with an average aspect ratio between 1 and 4.

[0068] In this embodiment, zeolite SSZ-91 comprises: The molar ratio (SAR) of silicon oxide (SiO₂) to aluminum oxide (Al₂O₃) is 80 to 160. At least 80% of all ZSM-48 materials are multi-body 6; 0.1 to 4.0 wt% EUO type molecular sieve phase; The morphological characteristics of zeolite SSZ-91 are that it contains polycrystalline aggregates of microcrystals with an average aspect ratio between 1 and 4.

[0069] In this embodiment, zeolite SSZ-91 comprises: The molar ratio (SAR) of silicon oxide (SiO₂) to aluminum oxide (Al₂O₃) is 100 to 140. At least 80% of all ZSM-48 materials are multi-body 6; 0.1 to 4.0 wt% EUO type molecular sieve phase; The morphological characteristics of zeolite SSZ-91 are that it contains polycrystalline aggregates of microcrystals with an average aspect ratio between 1 and 4.

[0070] In this embodiment, zeolite SSZ-91 comprises: The molar ratio (SAR) of silicon oxide (SiO₂) to aluminum oxide (Al₂O₃) is 100 to 140. At least 80% of all ZSM-48 materials are multi-body 6; 0.1 to 4.0 wt% EU-1; The morphological characteristics of zeolite SSZ-91 are that it contains polycrystalline aggregates of microcrystals with an average aspect ratio between 1 and 4.

[0071] The synthesized zeolite SSZ-91 described herein can be characterized by its XRD pattern. The powder XRD lines in Table 1 represent the initially synthesized zeolite SSZ-91. Minor variations in the diffraction pattern can be caused by changes in the molar ratio of the framework species in a specific sample due to variations in the lattice constant. Additionally, sufficiently small crystals can affect the shape and intensity of peaks, resulting in significant peak broadening. Minor variations in the diffraction pattern can also be caused by variations in the organic compounds used in the preparation and by variations in the Si / Al molar ratio between samples. Calcination can also lead to minor variations in the XRD pattern. Despite these minor perturbations, the basic crystal structure remains unchanged. Table 1 Characteristic peaks of the initially synthesized SSZ-91 2-θ (a) d-Spacing (nm) Relative intensity (b) 7.55 1.170 W 8.71 1.015 W 12.49 0.708 W 15.12 0.586 W 21.18 0.419 VS 22.82 0.390 VS 24.62 0.361 W 26.39 0.337 W 29.03 0.307 W 31.33 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 = moderate (>20 to ≤40); S = strong (>40 to ≤60); VS = very strong (>60 to ≤100).

[0072] The X-ray diffraction patterns in Table 2 represent calcined SSZ-91. Table 2 Characteristic peaks of calcined SSZ-91 2-θ (a) d-Spacing (nm) Relative intensity (b) 7.67 1.152 M 8.81 1.003 W 12.61 0.701 W 15.30 0.579 W 21.25 0.418 VS 23.02 0.386 VS 24.91 0.357 W 26.63 0.334 W 29.20 0.306 W 31.51 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 = moderate (>20 to ≤40); S = strong (>40 to ≤60); VS = very strong (>60 to ≤100).

[0073] The powder X-ray diffraction patterns presented in this paper were collected using standard techniques. The radiation is Cuk α radiation. The peak height and position were read as a function of 2θ from the relative intensity of the peaks (adjusted for background), where θ is the Bragg angle, and the interplanar spacing d corresponding to the recorded lines can be calculated. [, zeolite , ] [, SSZ-91 , ] [, Preparation , ] [] reaction mixture and crystals

[0074] In the preparation of zeolite SSZ-91, at least one organic compound selectively synthesized from ZSM-48 series zeolites is used as a structure directing agent ("SDA"), also known as a crystallization template. The SDA used to manufacture zeolite SSZ-91 is represented by the following structure (1): (1) N,N,N,N',N',N'-Hexamethylhexamethylenediammonium or hexahydroxyquaternary ammonium cation

[0075] SDA cations typically associate with anions, which can be any anion that is harmless to the formation of the molecular sieve. Representative examples of anions include hydroxide, acetate, sulfate, carboxyl, and halogens, such as fluoride, chloride, bromide, and iodide ions. In one embodiment, the anion is a bromide ion.

[0076] Generally, zeolite SSZ-91 is prepared by the following operation: (a) Preparation of a reaction mixture containing: (1) at least one silicon oxide source; (2) at least one aluminum oxide source; (3) at least one source selected from elements of Groups 1 and 2 of the periodic table; (4) hydroxide ions; (5) hexahydroxyquaternary ammonium cations; (6) water; and (b) Keep the reaction mixture under crystallization conditions sufficient to form molecular sieve crystals.

[0077] The composition of the reaction mixture used to form zeolite SSZ-91, in terms of molar ratio, is determined as follows: Components Mörby SiO₂ / Al₂O₃ 50 – 220 M / SiO 2 0.05 – 1.0 Q / SiO 2 0.01 – 0.2 OH / SiO 2 0.05 – 0.4 H₂O / SiO₂ 3 – 100 in, (1) M is a group composed of elements from Groups 1 and 2 of the periodic table; and (2) Q is the structure-directing agent represented by structure 1 above.

[0078] In the embodiments, the composition of the reaction mixture used to form zeolite SSZ-91 was determined in terms of molar ratio as follows: Components Mörby SiO₂ / Al₂O₃ 85 – 180 M / SiO 2 0.1 – 0.8 Q / SiO 2 0.02 – 0.1 OH / SiO 2 0.10 – 0.3 H₂O / SiO₂ 10 – 50 in, (1) M is a group composed of elements from Groups 1 and 2 of the periodic table; and (2) Q is the structure-directing agent represented by structure 1 above.

[0079] In the embodiments, the composition of the reaction mixture used to form zeolite SSZ-91 was determined in terms of molar ratio as follows: Components Mörby SiO₂ / Al₂O₃ 50 – 220 M / SiO 2 0.05 – 1.0 Q / SiO 2 0.01 – 0.2 OH / SiO 2 0.05 – 0.4 H₂O / SiO₂ 3-100 in, (1) M is a group composed of elements from Groups 1 and 2 of the periodic table; and (2) Q is the structure-directing agent represented by structure 1 above.

[0080] In the embodiments, the composition of the reaction mixture used to form zeolite SSZ-91 was determined in terms of molar ratio as follows: Components Mörby SiO₂ / Al₂O₃ 50 – 220 M / SiO 2 0.05 – 1.0 Q / SiO 2 0.02 – 0.1 OH / SiO 2 0.05 – 0.4 H₂O / SiO₂ 3 – 100 in, (1) M is a group composed of elements from Groups 1 and 2 of the periodic table; and (2) Q is the structure-directing agent represented by structure 1 above.

[0081] In the embodiments, the composition of the reaction mixture used to form zeolite SSZ-91 was determined in terms of molar ratio as follows: Components Mörby SiO₂ / Al₂O₃ 80 – 180 M / SiO 2 0.05 – 1.0 Q / SiO 2 0.02 – 0.1 OH / SiO 2 0.05 – 0.4 H₂O / SiO₂ 3 – 100 in, (1) M is a group composed of elements from Groups 1 and 2 of the periodic table; and (2) Q is the structure-directing agent represented by structure 1 above.

[0082] In the embodiments, the composition of the reaction mixture used to form zeolite SSZ-91 was determined in terms of molar ratio as follows: Components Mörby SiO₂ / Al₂O₃ 80 – 160 M / SiO 2 0.05 – 1.0 Q / SiO 2 0.02 – 0.1 OH / SiO 2 0.1 – 0.4 H₂O / SiO₂ 3 – 100 in, (1) M is a group composed of elements from Groups 1 and 2 of the periodic table; and (2) Q is the structure-directing agent represented by structure 1 above.

[0083] Sources of silica that can be used in this article include fumed silica, precipitated silica, silica hydrogels, silicic acid, colloidal silica, tetraalkyl orthosilicate (e.g., tetraethyl orthosilicate), and silica hydroxides.

[0084] The reaction mixture can be formed containing at least one source (referred to herein as M) of an element selected from Group 1 and Group 2 of the periodic table. In examples, the reaction mixture is formed using a source of an element from Group 1 of the periodic table. In examples, the reaction mixture is formed using a sodium (Na) source. Any M-containing compound that is harmless to the crystallization process is suitable. Such sources of Group 1 and Group 2 elements include oxides, hydroxides, nitrates, sulfates, halides, oxalates, citrates, and acetates of these elements.

[0085] For each embodiment described herein, the molecular sieve reaction mixture may be provided from more than one source. Furthermore, two or more reaction components may be provided from a single source.

[0086] The reaction mixture can be maintained at an elevated temperature until crystals of the molecular sieve (zeolite SSZ-91) form. Zeolite hydrothermal crystallization is typically carried out under pressure, usually in an autoclave, subjecting the reaction mixture to autogenous pressure and optionally stirring at a temperature ranging from about 125°C to about 200°C for a suitable period, for example, from about one hour to several days, such as from about one hour to about 10 days, from about one hour to about 9 days, from about one hour to about 8 days, from about one hour to about 7 days, or from about one hour to about 6 days, or from about one hour to about 5 days, or from about one hour to about 4 days, or from about one hour to about 3 days, or from about one hour to about 48 hours, or from about one hour to about 36 hours, or from about one hour to about 24 hours, or from about one hour to about 18 hours.

[0087] In an embodiment, zeolite SSZ-91 is prepared by a method comprising the following operations: preparing a reaction mixture containing at least one silicon source, at least one aluminum source, at least one source selected from elements of Groups 1 and 2 of the periodic table, hydroxide ions, hexahydroxyquaternary ammonium cations, and water; and subjecting the reaction mixture to crystallization conditions; wherein the reaction mixture comprises: Components Mörby SiO₂ / Al₂O₃ 50 – 220 M / SiO 2 0.05 – 1.0 Q / SiO 2 0.01 – 0.2 OH / SiO 2 0.05 – 0.4 H₂O / SiO₂ 3 – 100 M is selected from the group consisting of elements in Groups 1 and 2 of the periodic table; Q is a hexahydroxyquaternary ammonium cation; and the crystallization conditions include maintaining the reaction mixture at an elevated temperature in the range of about 125°C to about 200°C.

[0088] In an embodiment, zeolite SSZ-91 is prepared by a method comprising the following operations: preparing a reaction mixture containing at least one silicon source, at least one aluminum source, at least one source selected from elements of Groups 1 and 2 of the periodic table, hydroxide ions, hexahydroxyquaternary ammonium cations, and water; and subjecting the reaction mixture to crystallization conditions; wherein the reaction mixture comprises: Components Mörby SiO₂ / Al₂O₃ 50 – 220 M / SiO 2 0.05 – 1.0 Q / SiO 2 0.02 – 0.1 OH / SiO 2 0.05 – 0.4 H₂O / SiO₂ 3 – 100 M is selected from the group consisting of elements in Groups 1 and 2 of the periodic table; Q is a hexahydroxyquaternary ammonium cation; and the crystallization conditions include maintaining the reaction mixture at an elevated temperature in the range of about 125°C to about 200°C (e.g., about 125°C to about 180°C, or about 125°C to about 160°C).

[0089] In an embodiment, zeolite SSZ-91 is prepared by a method comprising the following operations: preparing a reaction mixture containing at least one silicon source, at least one aluminum source, at least one source selected from elements of Groups 1 and 2 of the periodic table, hydroxide ions, hexahydroxyquaternary ammonium cations, and water; and subjecting the reaction mixture to crystallization conditions; wherein the reaction mixture comprises: Components Mörby SiO₂ / Al₂O₃ 80 – 180 M / SiO 2 0.05 – 1.0 Q / SiO 2 0.05 – 0.2 OH / SiO 2 0.05 – 0.4 H₂O / SiO₂ 3 – 100 M is selected from the group consisting of elements in Groups 1 and 2 of the periodic table; Q is a hexahydroxyquaternary ammonium cation; and the crystallization conditions include maintaining the reaction mixture at an elevated temperature in the range of about 125°C to about 200°C (e.g., about 125°C to about 180°C, or about 125°C to about 160°C).

[0090] In an embodiment, zeolite SSZ-91 is prepared by a method comprising the following operations: preparing a reaction mixture containing at least one silicon source, at least one aluminum source, at least one source selected from elements of Groups 1 and 2 of the periodic table, hydroxide ions, hexahydroxyquaternary ammonium cations, and water; and subjecting the reaction mixture to crystallization conditions; wherein the reaction mixture comprises: Components Mörby SiO₂ / Al₂O₃ 80 – 160 M / SiO 2 0.05 – 1.0 Q / SiO 2 0.02 – 0.1 OH / SiO 2 0.1 – 0.4 H₂O / SiO₂ 3 – 100 M is selected from the group consisting of elements in Groups 1 and 2 of the periodic table; Q is a hexahydroxyquaternary ammonium cation; and the crystallization conditions include maintaining the reaction mixture at an elevated temperature in the range of about 125°C to about 200°C (e.g., about 125°C to about 180°C, or about 125°C to about 160°C).

[0091] In embodiments, the crystallization conditions include maintaining the reaction mixture at elevated temperatures ranging from about 125°C to about 200°C (e.g., about 125°C to about 180°C, about 125°C to about 180°C, about 125°C to about 170°C, about 125°C to about 160°C).

[0092] By selecting the optimal hydrogel composition, temperature, and crystallization time, the formation of a large amount of EUO phase can be suppressed, thereby minimizing EUO phase formation and maximizing the yield of SSZ-91 products. The examples provided in US-A-9920260 offer guidance on how variations in these process variables can minimize EU-1 formation. Zeolite manufacturers with common expertise in the art will be able to easily select the process variables required to minimize EU-1 formation, as these variables will depend on the scale of the production operation, the capacity of available equipment, the desired target yield, and the acceptable content of EU-1 material in the product.

[0093] During the hydrothermal crystallization step, molecular sieve crystals can be allowed to spontaneously nucleate from the reaction mixture. Using molecular sieve crystals as seed materials can help reduce the time required for complete crystallization. Furthermore, seeding can lead to increased purity of the product obtained by promoting nucleation and / or the formation of molecular sieves on any unwanted phases. However, it has been found that if seeding is used, the seed crystals must be very pure SSZ-91 to avoid the formation of a large amount of EUO phase. When used as seed crystals, the amount added is between 0.5% and 5% by weight of the silicon source used in the reaction mixture.

[0094] Natural sodium silicate and naphthoic silicate are formed by optimizing the hexahydroxyquaternary ammonium bromide / SiO₂ ratio, controlling the hydroxide concentration, and minimizing the sodium concentration, since natural sodium silicate and naphthoic silicate are layered sodium silicate compositions. The examples provided in US-A-9920260 offer guidance on how variations in gel conditions can minimize EU-1 formation.

[0095] Once the molecular sieve crystals have formed, the solid product is separated from the reaction mixture using standard mechanical separation techniques such as filtration. The crystals are washed with water and then dried to obtain the initially synthesized molecular sieve crystals. The drying step can be performed at atmospheric pressure or under vacuum. Post-crystallization treatment

[0096] SSZ-91 zeolite can be used immediately after initial synthesis, but it typically undergoes heat treatment (calcination). The term "initial synthesis" refers to SSZ-91 zeolite in its crystallized form before the removal of SDA cations. SDA can be removed by heat treatment (e.g., calcination), for example in an oxidizing atmosphere (e.g., air, a gas with an oxygen partial pressure greater than 0 kPa), at a temperature readily determined by those skilled in the art to be sufficient to remove SDA from the molecular sieve. SDA can also be removed by ozonolysis and photolysis techniques (e.g., exposing the SDA-containing molecular sieve product to light or electromagnetic radiation with wavelengths shorter than visible light under conditions sufficient to selectively remove organic compounds from the molecular sieve), as described in U.S. Patent No. 6,960,327.

[0097] The SSZ-91 zeolite can then be calcined in steam, air, or an inert gas at a temperature ranging from 200°C to 800°C for 1 to 48 hours or longer. Typically, it is necessary to remove the extra-framework cations (e.g., Na+) by ion exchange and replace them with hydrogen, ammonium, or any desired metal ion.

[0098] When 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. The target molecular sieve (e.g., zeolite SSZ-91) can also be achieved by removing heteroatoms from the lattice using known techniques such as acid leaching.

[0099] Zeolite SSZ-91 manufactured using the process disclosed herein can be formed into various physical shapes. Zeolite SSZ-91 can be in the form of powder, granules, or molded products, such as extrudates with particle sizes large enough to pass through a 2-mesh (Tyler) sieve and remain on a 400-mesh (Tyler) sieve. In cases where the catalyst is molded, zeolite SSZ-91 can be extruded before drying, such as by extrusion with an organic binder, or after drying or partial drying, followed by extrusion.

[0100] Zeolite SSZ-91 can be combined with other materials that resist the temperatures and other conditions used 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 clay, silica, and metal oxides. Examples of such materials and their uses are disclosed in U.S. Patents 4,910,006 and 5,316,753. Preparation of hydroisomerization catalysts

[0101] The hydroisomerization catalyst comprises zeolite SSZ-91. SSZ-91 can be in its initial synthetic or calcined form. In the examples, the hydroisomerization catalyst is formed from calcined SSZ-91 zeolite.

[0102] In embodiments, the hydroisomerization catalyst is formed by compounding zeolite SSZ-91 (in its initial synthetic or calcined form) with an oxide binder such as alumina. In embodiments, compounding zeolite SSZ-91 with the oxide binder involves mixing zeolite SSZ-91 with the oxide binder (e.g., alumina) and extruding the product. The mixture of molecular sieve (zeolite SSZ-91) and oxide binder can be formed into particles or extrudates having various solid shapes and sizes. In embodiments, the extrudates or particles are dried and calcined before metal loading. In embodiments, the extrudates or particles are impregnated with metals, such as Group 2, Group 8, Group 9, and / or Group 10 metals (e.g., Group 8 to Group 10 metals, such as Pt), and then dried and calcined. In embodiments, the extrudates or particles are dried and calcined before metal loading.

[0103] In the examples, the hydroisomerization catalyst was prepared by the following operation: Zeolite SSZ-91 was combined with an oxide binder to form an extrudate matrix; The extrudate matrix is ​​impregnated with an impregnation solution containing, for example, metals from Group 8 to Group 10 to form a metal-loaded extrudate; The extrusion of the loaded metal is dried; and The extrusion of the dried loaded metal is calcined.

[0104] In some embodiments, the hydroisomerization catalyst is formed by impregnating zeolite SSZ-91 with a solution containing a metal, such as a Group 2, Group 8, Group 9, and / or Group 10 metal (e.g., Group 8 to 10 metals, such as Pt). In some embodiments, the hydroisomerization catalyst is formed by impregnating calcined zeolite SSZ-91 with a solution containing a Group 2, Group 8, Group 9, and / or Group 10 metal (e.g., Group 8 to 10 metals, such as Pt). In some embodiments, the hydroisomerization catalyst is formed by impregnating an extrusion matrix comprising zeolite SSZ-91 and an oxide binder.

[0105] In an embodiment, the extrudate matrix is ​​exposed to an impregnation solution containing metals (Group 2, Group 8, Group 9 and / or Group 10 metals; for example, Group 8 to Group 10 metals, such as Pt) for 0.1 to 10 hours.

[0106] In the embodiments, the extrudate matrix is ​​dried (e.g., for about 0.1 to about 10 hours at a temperature in the range of about 100℉ (38°C) to about 300℉ (149°C)) and calcined (for about 0.1 to about 10 hours at a temperature in the range of about 600℉ (316°C) to about 1200℉ (649°C)) before impregnation.

[0107] In one embodiment, the extrudate matrix formed by combining zeolite SSZ-91 with an oxide binder is dried and calcined before impregnation. In another embodiment, the dried and calcined extrudate matrix is ​​impregnated with an impregnation solution to form a metal-loaded extrudate, and then dried and calcined again to form a hydroisomerization catalyst.

[0108] In an embodiment, the impregnated zeolite SSZ-91 (e.g., an impregnated extrudate matrix containing zeolite SSZ-91) is dried for about 0.1 to about 10 hours at a temperature ranging from about 100℉ (38°C) to about 300℉ (149°C).

[0109] In an embodiment, the dried impregnated zeolite SSZ-91 (e.g., a dried extrusion of a loaded metal) was calcined for about 0.1 to about 10 hours at a temperature ranging from about 600℉ (316°C) to about 1200℉ (649°C). In an embodiment, the calcination was carried out in air. [Hydrocarbon feed] []

[0110] In the embodiments, the hydrocarbon feedstock is selected from whole crude oil, distillate residue crude oil, vacuum tower residue oil, circulating oil, synthetic crude oil, gas-generating oil, vacuum gas-generating oil, foot oil, Fischer-Tropsch derivative wax, middle distillate feedstock (including gas-generating oil, kerosene, jet fuel, lubricating oil feedstock, heating oil), heavy neutral feedstock, hydrotreated gas-generating oil, hydrocracking gas-generating oil, hydrotreated lubricating oil residue, bright oil, lubricating oil feedstock, synthetic oil, Fischer-Tropsch synthetic oil, high pour point polyolefins (e.g., polyolefins with a pour point of about 0°C or higher); common α-olefin wax, pine wax, deoiled wax, microcrystalline wax, residual fraction from atmospheric distillation processes, solvent-deasphalted petroleum residue, shale oil, circulating oil, animal-derived fats, animal-derived oils, animal-derived waxes, plant-derived fats, plant-derived oils, plant-derived waxes, petroleum wax, pine wax, and waxes produced in chemical plant processes.

[0111] In the embodiments, the hydrocarbon feedstock is selected from whole crude oil, distillation residue crude oil, vacuum tower residue oil, circulating oil, synthetic crude oil, gas-generating oil, vacuum gas-generating oil, foot oil, and Fischer-Tropsch derivative wax.

[0112] In the embodiments, the hydrocarbon feedstock is selected from: hydrotreated or hydrocracking gas oil; hydrotreated base oil raffinate; bright oil; lubricating oil stock; synthetic oil; scrap oil; Fischer-Tropsch synthetic oil; high pour point polyolefins (e.g., polyolefins with a pour point of about 0°C or higher); common alpha-olefin wax; pine wax; deoiled wax; microcrystalline wax; gas oil and vacuum gas oil; residual fractions from atmospheric distillation processes; solvent-deasphalted petroleum residues; shale oil, circulating oil; animal and plant-derived fats, oils and waxes; petroleum and waxes; and waxes produced in chemical plant processes. In the embodiments, the hydrocarbon feedstock is selected from hydrotreated or hydrocracking gas oil, hydrotreated base oil raffinate, bright oil, lubricating oil stock, synthetic oil, scrap oil, Fischer-Tropsch synthetic oil, high pour point polyolefins (e.g., polyolefins with a pour point of about 0°C or higher), common alpha-olefin wax, pine wax, deoiled wax, and microcrystalline wax.

[0113] In the embodiments, the hydrocarbon feed is or contains heavy feed, such as heavy neutral (600N) and bright oil.

[0114] In the embodiments, the hydrocarbon feed is a wax-containing feed, that is, a hydrocarbon feed with a pour point of about 0°C or higher, for example, a pour point of about 10°C or higher, or a pour point of about 20°C or higher.

[0115] In the embodiments, the hydrocarbon feed has a kinematic viscosity at 100°C in the range of about 3 to about 30 cSt, for example about 3.5 to about 15 cSt.

[0116] In one embodiment, the hydrocarbon feed has a distillation temperature range of about 400℉ (204°C) to about 1300℉ (704°C), for example, about 500℉ (260°C) to about 1100℉ (593°C), or about 600℉ (316°C) to about 1050℉ (566°C). In another embodiment, the hydrocarbon feed has a distillation temperature range of about 400℉ (204°C) to about 1300℉ (704°C) and a kinematic viscosity at 100°C in the range of about 3 to about 30 cSt. In yet another embodiment, the hydrocarbon feed has a distillation temperature range of about 500℉ (260°C) to about 1100℉ (593°C) and a kinematic viscosity at 100°C in the range of about 3.5 to about 15 cSt.

[0117] In the embodiments, the hydrocarbon feed has a 5% distillation temperature of at least about 700℉ (371°C), for example at least about 750℉ (339°C), or at least about 800℉ (426°C). In the embodiments, the hydrocarbon feed has a 10% distillation temperature of at least about 750℉ (399°C), for example at least about 800℉ (426°C), or at least about 840℉ (449°C). In the embodiments, the hydrocarbon feed has a 30% distillation temperature of at least about 850℉ (399°C), for example at least about 900℉ (482°C). The distillation temperature of the hydrocarbon feed can be determined according to ASTM D 2887.

[0118] In the examples, the hydrocarbon feed has a pour point of about 20°C or higher and a 10% distillation temperature of at least about 750°F (399°C).

[0119] In the embodiments, the hydrocarbon feed contains more than about 5%, more than about 10%, or more than about 15% wax. In the embodiments, the hydrocarbon feed contains about 5% to about 30% wax. As used herein, the term "waxy hydrocarbon feed" may include plant waxes other than petroleum-derived waxes and animal-derived waxes. As used herein, the term "wax" refers to a hydrocarbon component with a pour point above 0°C, for example, above 20°C. [Used in processes that hydroisomerize hydrocarbon feedstocks]

[0120] This article describes a process for hydroisomerizing hydrocarbon feedstocks. The process includes: Combined hydrocarbon feedstock and hydroisomerization additives to provide combined feedstock; and This allows the combined feedstock to contact the hydroisomerization catalyst. The hydroisomerization additive is a substituted or unsubstituted nitrogen heterocycle, and the hydroisomerization catalyst contains zeolite SSZ-91.

[0121] In one embodiment, the combined hydrocarbon feed and hydroisomerizing additive comprises adding at least about 10 ppm of the hydroisomerizing additive to the hydrocarbon feed based on the weight of the hydrocarbon feed, for example, adding at least about 20 ppm, at least about 30 ppm, or at least about 50 ppm of the hydroisomerizing additive to the hydrocarbon feed based on the weight of the hydrocarbon feed. In another embodiment, the combined hydrocarbon feed and hydroisomerizing additive comprises adding up to about 500 ppm of the hydroisomerizing additive to the hydrocarbon feed based on the weight of the hydrocarbon feed, for example, adding up to about 300 ppm, up to about 250 ppm, up to about 200 ppm, or up to about 150 ppm of the hydroisomerizing additive to the hydrocarbon feed based on the weight of the hydrocarbon feed. In an embodiment, the combined hydrocarbon feed and hydroisomerizing additive comprises adding about 10 to about 500 ppm of the hydroisomerizing additive to the hydrocarbon feed based on the weight of the hydrocarbon feed, for example, adding about 10 to about 250 ppm, about 20 to about 250 ppm, about 20 to about 200 ppm, about 50 to about 250 ppm, about 50 to 200 ppm, about 50 to 150 ppm, or about 100 to 150 ppm or about 50 to 100 ppm of the hydroisomerizing additive to the hydrocarbon feed based on the weight of the hydrocarbon feed.

[0122] In one embodiment, the combined hydrocarbon feed and hydroisomerizing additive comprises adding a hydroisomerizing additive providing nitrogen in an amount of at least about 0.1 ppm (e.g., at least about 0.5 ppm or at least about 1 ppm) based on the weight of the hydrocarbon feed. In another embodiment, the combined hydrocarbon feed and hydroisomerizing additive comprises adding a hydroisomerizing additive providing nitrogen in an amount of up to about 50 ppm (e.g., up to about 30 ppm, up to about 25 ppm, up to about 20 ppm, or up to about 15 ppm) based on the weight of the hydrocarbon feed. In yet another embodiment, the combined hydrocarbon feed and hydroisomerizing additive comprises adding a hydroisomerizing additive providing nitrogen in an amount ranging from about 0.1 to about 50 ppm (about 0.5 to about 25 ppm or about 1 to about 20 ppm) based on the weight of the hydrocarbon feed.

[0123] In the embodiment, a combined feed consisting of a combined hydrocarbon feed and a hydroisomerizing additive is fed into the hydroisomerizing reactor.

[0124] In the embodiments, the hydrocarbon feed and the hydroisomerization additive are fed independently into the hydroisomerization reactor to form a combined feed in the hydroisomerization reactor.

[0125] Hydroisomerization of the hydrocarbon feedstock occurs in the presence of hydrogen. In the embodiment shown in Figure 1, the hydrocarbon feedstock 10 can be combined with a hydroisomerization additive 11 to form a combined feedstock 13. The combined feedstock 13 can be fed together with hydrogen 12 into a hydroisomerization reactor 14, which contains a hydroisomerization catalyst 16. Within the reactor 14, the combined feedstock 13 can be contacted with the hydroisomerization catalyst 16 under hydroisomerization conditions in the presence of hydrogen to provide a hydroisomerized feedstock 18.

[0126] In an embodiment, the hydroisomerization catalyst 16 is activated before the hydrocarbon feed 10 (e.g., combined feed 13) is introduced into the hydroisomerization reactor 14. In an embodiment, the activation of the catalyst involves reduction at a temperature of 450 to 650℉ (232 to 343°C) for 1 to 10 hours.

[0127] In the embodiments, the hydroisomerization conditions (e.g., the hydroisomerization conditions in reactor 14) include temperatures in the range of about 390℉ to about 800℉ (199°C to 427°C), for example, about 550℉ to about 700℉ (288°C to 371°C).

[0128] In the embodiments, the hydroisomerization conditions (e.g., the hydroisomerization conditions in reactor 14) include pressures in the range of about 15 to about 3000 psig (0.10 to 20.68 MPa gauge), for example about 100 to about 2500 psig (0.69 to 17.24 MPa).

[0129] In an embodiment, the hydroisomerization conditions (e.g., the hydroisomerization conditions in reactor 14) include the combined feed rate to the reactor containing the hydroisomerization catalyst, which is in the range of about 0.1 to about 20 h⁻¹ LHSV, for example, about 0.1 to about 5 h⁻¹ LHSV.

[0130] In the embodiments, the hydroisomerization conditions (e.g., the hydroisomerization conditions in reactor 14) include a feed rate of hydrogen to the reactor containing the hydroisomerization catalyst, which is in the range of about 0.1 to about 20 h⁻¹ LHSV, for example, about 0.1 to about 5 h⁻¹ LHSV.

[0131] In an embodiment, the hydroisomerization conditions (e.g., the hydroisomerization conditions in reactor 14) include hydrogen and combined feed fed to the reactor at a rate of approximately 2,000 to approximately 10,000 standard cubic feet of H2 per barrel of combined feed (approximately 360 to approximately 1,800 m3H2 / m3 feed), for example, approximately 2,500 to approximately 5,000 scf H2 per barrel of combined feed (approximately 440 to approximately 890 m3H2 / m3 feed).

[0132] In an embodiment, hydroisomerization conditions (e.g., hydroisomerization conditions in reactor 14) include hydrogen and hydrocarbon feeds to the reactor at a ratio of approximately 2,000 to approximately 10,000 standard cubic feet of H2 per barrel combined feed (approximately 360 to approximately 1,800 m3H2 / m3 feed), for example, approximately 2,500 to approximately 5,000 scf H2 per barrel hydrocarbon feed (approximately 440 to approximately 890 m3H2 / m3 feed).

[0133] In the embodiments, the hydroisomerization conditions (e.g., the hydroisomerization conditions in reactor 14) include: Temperatures within the following ranges: approximately 390℉ to approximately 800℉ (199°C to 427°C), for example, approximately 550℉ to approximately 750℉ (288°C to 399°C), or 570℉ to approximately 675℉ (299°C to 357°C); Pressure within the following ranges: approximately 15 to approximately 3000 psig (0.10 to 20.68 MPa gauges), for example, approximately 100 to approximately 2500 psig (0.69 to 17.24 MPa); The feed rate of the combined feed to the reactor containing the hydroisomerization catalyst is in the range of about 0.1 to about 20 h⁻¹ LHSV, for example, about 0.1 to about 5 h⁻¹ LHSV; and Hydrogen and combined feed are fed to the reactor at a ratio of approximately 2,000 to approximately 10,000 standard cubic feet of H2 per barrel (approximately 360 to approximately 1,800 m3H2 / m3 feed), for example, approximately 2,500 to approximately 5,000 scf H2 per barrel (approximately 440 to approximately 890 m3H2 / m3 feed).

[0134] In an embodiment, the hydroisomerized stream (e.g., hydroisomerized stream 18) produced after contacting the combined feed and hydroisomerized catalyst may undergo a hydrorefining step. In another embodiment, the hydroisomerized stream produced after contacting the combined feed and hydroisomerized catalyst may be fed into a hydrorefining unit to contact with a hydrorefining catalyst to form a hydrorefined hydroisomerized stream. The hydrorefining step can remove trace amounts of any aromatics, olefins, chromophores, etc., from the base oil product. In another embodiment, the hydrorefining catalyst comprises an alumina support and a noble metal, such as palladium, or platinum combined with palladium.

[0135] In an embodiment, the hydroisomerized feed stream produced after contacting the combined feed and hydroisomerization catalyst, or the hydrorefined hydroisomerized feed stream, can be fed to the distillation unit. In an embodiment, the hydroisomerized feed stream is fed to the distillation unit to provide base oil with a pour point of -5°C or lower.

[0136] In the embodiments, the process for hydroisomerizing hydrocarbon feedstocks provides base oils with a pour point of -5°C or lower. In the embodiments, the process for hydroisomerizing hydrocarbon feedstocks provides base oils with a kinematic viscosity at 100°C in the following ranges: about 3 to about 12 cSt, for example, about 4 to about 12 cSt, about 6 to about 12 cSt, about 8 to about 12 cSt, about 10 to about 12 cSt, about 4 to about 10 cSt, about 6 to about 10 cSt, about 8 to about 10 cSt, or about 10 cSt. The kinematic viscosity of the base oil at 100°C can be determined according to ASTM D 445.

[0137] In the embodiments, the yield of base oil produced by the process described herein is increased by at least 1.0% by weight compared to the process performed in the absence of hydroisomerizing additives. In the embodiments, the yield of base oil produced by the process described herein is increased by at least 2.0% by weight compared to the process performed in the absence of hydroisomerizing additives.

[0138] In the embodiments, the process described herein provides a base oil yield of at least about 85%. [Example] []

[0139] The following illustrative examples are intended to be non-restrictive. [Example Overview] []

[0140] The following examples demonstrate that the processes and methods described herein effectively provide a hydroisomerization process that unexpectedly delivers improved yields of base oil products produced from hydrocarbon feedstocks. [] [, Hydroisomerization catalyst , ] [, , ] [Example] [1]

[0141] Zeolite SSZ-91 is prepared according to US-A-9920260 (incorporated herein by reference) and the preceding paragraph

[0067] .

[0142] The SSZ-91 zeolite product was then compounded with alumina to provide a mixture containing 65 wt% SSZ-91 zeolite. The mixture was extruded, dried, and calcined to form an extrudate matrix. The extrudate matrix was impregnated with a platinum-containing solution. The impregnated catalyst was then dried in air and calcined to provide a hydroisomerization catalyst. The total platinum loading of the hydroisomerization catalyst product was 0.6 wt%. [, Hydroisomerization of hydrocarbon feedstock , ] [, , ]

[0143] The hydroisomerization catalyst produced according to Example 1 is used in the hydroisomerization processes of Reference Examples 2, 3, and 4 to hydroisomerize hydrocarbon feedstocks. The hydrocarbon feedstocks used in the hydroisomerization processes of Reference Examples 2, 3, and 4 are heavy neutral feedstocks, the properties of which are described in Table 3 below: Table 3 API Gravity 29.6 Nitrogen, ppm 1 Sulfur, ppm 32 SIMDIST TBP (wt%),℉ TBP @0.5 716 TBP @5 808 TBP @10 842 TBP @30 909 TBP @50 950 TBP @70 990 TBP @90 1043 TBP @95 1065 TBP @99.5 1110

[0144] Each of the hydroisomerization processes described below in Reference Examples 2, 3, and 4 is carried out in a micro-unit comprising a downflow fixed-bed hydroisomerization reactor, a hydrorefining reactor, and a distillation unit. The hydroisomerization reactor is loaded with the hydroisomerization catalyst of Example 1 in a fixed bed. The hydrorefining reactor is loaded with a Pd / Pt hydrorefining catalyst in a fixed bed.

[0145] Before introducing hydrocarbon or combined feedstock into the hydroisomerization reactor in each of the processes in Reference Examples 2, 3 and 4, the hydroisomerization catalyst is activated by a standard reduction procedure as described herein.

[0146] Before introducing the hydroisomerization feed into the hydrorefining reactor in each of the processes in Reference Examples 2, 3, and 4, the hydrorefining catalyst is activated by a standard reduction procedure as described herein.

[0147] For each of the processes in Reference Examples 2, 3, and 4: the hydroisomerization reactor operates at a temperature of 600 to 650℉ (316 to 343°C) and a pressure of 2100 psig; and the hydrorefining reactor operates at a temperature of 450℉ (232°C) and a pressure of 2100 psig.

[0148] For each of the processes in Reference Examples 2, 3, and 4, the hydrorefined product produced by the hydrorefining reactor is transferred to the distillation unit to provide base oils with a boiling point of 750℉ and above and a pour point of -15℃. [Reference Example] [2]

[0149] The hydroisomerization catalyst of Example 1 was placed in a hydroisomerization reactor and activated using the standard reduction procedure described above. The hydrocarbon feed was introduced into the hydroisomerization reactor at an LHSV of 1.2, and hydrogen was fed to the reactor at a hydrogen-to-hydrocarbon feed ratio of approximately 3000 standard cubic feet H₂ per barrel of hydrocarbon feed (approximately 540 m³ H₂ / m³ feed). The hydrorefined product was transferred to a distillation unit to separate the fuel and base oil products. [Example] [3]

[0150] Example 2 was repeated, except that 70 ppm N-ethylcarbazole was added to the hydrocarbon feed to produce a combined feed before the hydrocarbon feed was passed to the hydroisomerization reactor. [Example] [4]

[0151] Example 3 was repeated, except that 140 ppm N-ethylcarbazole was added to the hydrocarbon feed to produce a combined feed.

[0152] Table 4 shows the performance results of the hydroisomerization process when N-ethylcarbazole is added to the hydrocarbon feed in Reference Examples 2, 3 and 4. Table 4 process Ethylcarbazole dosage Change in base oil yield compared to 0 ppm ethylcarbazole, wt% Reference Example 2 0 ppm – Example 3 70 ppm +2.0 Example 4 140 ppm +2.3

[0153] Surprisingly, it was observed that adding N-ethylcarbazole to the hydrocarbon feedstock improved the base oil yield produced using the hydroisomerization catalyst in Example 1. After adding 70 ppm of N-ethylcarbazole, the base oil yield increased by 2% by weight. When the N-ethylcarbazole concentration increased to 140 ppm, the base oil yield increased by 2.3% by weight. Not wanting to be bound by theory, it is believed that the addition of nitrogen heterocycles suppresses non-selective side reactions, thereby leading to the improved base oil yield.

[0154] It will be understood that the present 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 in mutually exclusive cases, any feature may be used alone or in combination with any other feature, and the disclosure extends to and includes all combinations and sub-combinations of one or more features described herein. In determining the scope of the present invention, reference should be made to the following numbered paragraphs and technical solutions.

[0155] For the purposes of U.S. patent practice and where permitted by other patent offices, all patents and publications referenced in the preceding description of this invention are incorporated herein by reference, provided that any information contained therein is related to and / or supplements the preceding disclosure.

[0156] For the avoidance of doubt, this application relates to the subject matter described in the following numbered paragraphs: 1. A process for hydroisomerizing a hydrocarbon feedstock, the process comprising: Combined hydrocarbon feedstock and hydroisomerization additives to provide combined feedstock; and This allows the combined feedstock to contact the hydroisomerization catalyst. The hydroisomerization additive is a substituted or unsubstituted nitrogen heterocycle, and the hydroisomerization catalyst contains zeolite SSZ-91. 2. A process for increasing the yield of base oil produced by hydroisomerization of hydrocarbon feedstock, the process comprising: Combined hydrocarbon feedstock and hydroisomerization additives to provide combined feedstock; and The combined feedstock is contacted with a hydroisomerization catalyst containing zeolite SSZ-91 to form a base oil product. The hydrogenated isomerizing additive is a substituted or unsubstituted nitrogen heterocycle, and Compared to the process performed in the absence of the hydroisomerizing additive, the yield of the base oil product is increased by at least 1.0 wt%. 3. According to the process in paragraph 1 or 2, wherein the hydroisomerizing additive has a DBE (double bond equivalent) number in the range of 3 to 10. 4. The process according to any of paragraphs 1 to 3, wherein the hydroisomerizing additive is a substituted or unsubstituted aromatic nitrogen heterocycle. 5. According to any of paragraphs 1 to 4, the hydrogenated isomerizing additive has a molecular weight of less than about 600. 6. The process according to any one of paragraphs 1 to 5, wherein the hydroisomerizing additive is selected from substituted or unsubstituted tricyclic fused-ring aromatic nitrogen heterocycles, substituted or unsubstituted bicyclic fused-ring aromatic nitrogen heterocycles and monocyclic aromatic nitrogen heterocycles. 7. The process according to any of paragraphs 1 to 6, wherein the hydrogenation isomerizing additive is selected from substituted or unsubstituted carbazole, pyrrole, pyridine, indole, quinoline and acridine. 8. The process according to any of paragraphs 1 to 7, wherein the hydroisomerizing additive is a substituted nitrogen heterocycle substituted by one or more substituents independently selected from the following: C1-10 alkyl; hydroxyl; C1-10 alkoxy; C1-10 carboxyl; and -NR'R”, wherein R' and R” are independently H or C1-10 alkyl. 9. A process according to any of paragraphs 1 to 8, wherein the hydroisomerizing additive is a substituted or unsubstituted aromatic nitrogen heterocycle according to formula I: (I) in R1 is selected from hydrogen, C1-10 alkyl, hydroxyl, C1-10 alkoxy, and C1-10 carboxyl; and R2 and R3 are independently selected from hydrogen, C1-10 alkyl, hydroxyl, C1-10 alkoxy, C1-10 carboxyl, and -NR'R". R' and R” are independently H or C1-10 alkyl groups. 10. According to the process described in paragraph 9, R1 is selected from C1-4 alkyl, and R2 and R3 are hydrogen. 11. The process according to any of paragraphs 1 to 10, wherein combining the hydrocarbon feed and the hydroisomerizing additive comprises adding about 10 to about 500 ppm of the hydroisomerizing additive to the hydrocarbon feed based on the weight of the hydrocarbon feed. 12. The process according to any one of paragraphs 1 to 11, wherein the combination of the hydrocarbon feed and the hydroisomerizing additive comprises adding the hydroisomerizing additive to the hydrocarbon feed in an amount providing nitrogen in the range of about 0.1 to about 50 ppm based on the weight of the hydrocarbon feed. 13. A process according to any of paragraphs 1 to 12, wherein the hydrocarbon feed and the hydroisomerization additive are combined to form the combined feed, and then the combined feed is fed into the hydroisomerization reactor. 14. The process according to any of paragraphs 1 to 13, wherein the hydrocarbon feed has a distillation temperature of at least about 900℉ (482°C) of 30%. 15. The process according to any of paragraphs 1 to 14, wherein the hydrocarbon feed has a pour point of about 0°C or higher. 16. The process according to any of paragraphs 1 to 15, wherein the hydroisomerization catalyst further comprises a group 8 to group 10 metal. 17. A process according to any of paragraphs 1 to 16, wherein the combined feed is contacted with the hydroisomerization catalyst and hydrogen under hydroisomerization conditions, the hydroisomerization conditions including temperatures in the range of about 550℉ to about 750℉ (288°C to 399°C). 18. According to the process described in paragraph 17, the hydroisomerization conditions further include: Pressure in the range of approximately 15 to approximately 3000 psig (0.10 to 20.68 MPa gauge); The combined feed rate to the reactor containing the hydroisomerization catalyst is in the range of about 0.1 to about 20 h⁻¹ LHSV; and Hydrogen and combined feed are fed to the reactor at a ratio of approximately 2,000 to approximately 10,000 standard cubic feet H2 per barrel (approximately 360 to approximately 1,800 m3H2 / m3 feed). 19. A process according to any of paragraphs 1 to 18, wherein the hydroisomerized feed stream produced after hydroisomerization of the hydrocarbon feed by contacting the combined feed and the hydroisomerization catalyst is contacted with a hydrorefining catalyst to provide a base oil having a pour point of about -5°C or lower. 20. A process according to any of paragraphs 1 to 19, wherein the yield of base oil produced by contacting the combined feed and the hydroisomerization catalyst is increased by at least 1.0% by weight, for example, at least 2.0% by weight, compared to a process performed in the absence of the hydroisomerization additive. 21. Use of hydroisomerizing additives in increasing the yield of base oils produced by: contacting hydrocarbon feedstocks and hydroisomerizing catalysts; combining the hydrocarbon feedstocks with the hydroisomerizing additives to form a combined feedstock, followed by contacting the combined feedstocks with the hydroisomerizing catalysts. The hydroisomerization additive is a substituted or unsubstituted nitrogen heterocycle, and the hydroisomerization catalyst contains zeolite SSZ-91. 22. As described in paragraph 21, the base oil produced therein has a pour point of about -5°C or lower. 23. As used in paragraph 21 or 22, wherein the yield is increased by at least 1.0% by weight, for example, at least 2.0% by weight, compared to a process performed in the absence of the hydroisomerizing additive. 24. As used in any of paragraphs 21 to 23, wherein the hydroisomerizing additive is carbazole, such as N-ethylcarbazole. 25. As used in any of paragraphs 21 to 24, wherein the hydroisomerization additive is added to the hydrocarbon feed in an amount of at least about 10 ppm. 26. A process for improving the yield of base oil produced by contacting a hydrocarbon feedstock and a hydroisomerization catalyst, the process comprising combining the hydrocarbon feedstock with a hydroisomerization additive to form a combined feedstock, and then contacting the combined feedstock and the hydroisomerization catalyst. The hydroisomerization additive is a substituted or unsubstituted nitrogen heterocycle, and the hydroisomerization catalyst contains zeolite SSZ-91. 27. As described in paragraph 26, the base oil produced therein has a pour point of about -5°C or lower. 28. As used in paragraph 26 or 27, wherein the yield is increased by at least 1.0% by weight, for example, at least 2.0% by weight, compared to a process performed in the absence of the hydroisomerizing additive. 29. The process according to any of paragraphs 26 to 28, wherein the hydroisomerizing additive is carbazole, such as N-ethylcarbazole. 30. The process according to any of paragraphs 26 to 29, wherein the hydroisomerization additive is added to the hydrocarbon feed in an amount of at least about 10 ppm.

[0157] 10: Hydrocarbon feed 11: Hydrogenation isomerization additives 12: Hydrogen 13: Combined feeding 14: Hydrogenation isomerization reactor 16: Hydroisomerization catalyst 18: Hydrogenation isomerization feedstock

Claims

1. A process for hydroisomerizing a hydrocarbon feedstock, the process comprising: combining the hydrocarbon feedstock and a hydroisomerizing additive to provide a combined feedstock; and contacting the combined feedstock with a hydroisomerizing catalyst, wherein the hydroisomerizing additive is a substituted or unsubstituted nitrogen heterocycle according to formula (I), (I) wherein R1 is selected from hydrogen, C1-10 alkyl, hydroxyl, C1-10 alkoxy, C1-10 carboxyl; and R2 and R3 are independently selected from hydrogen, C1-10 alkyl, hydroxyl, C1-10 alkoxy, C1-10 carboxyl and -NR'R", wherein R' and R" are independently H or C1-10 alkyl; and the hydroisomerizing catalyst comprises zeolite SSZ-91.

2. A process for increasing the yield of base oil produced by hydroisomerization of a hydrocarbon feedstock, the process comprising: combining the hydrocarbon feedstock and a hydroisomerizing additive to provide a combined feedstock; and contacting the combined feedstock with a hydroisomerizing catalyst comprising zeolite SSZ-91 to form a base oil product, wherein the hydroisomerizing additive is a substituted or unsubstituted nitrogen heterocycle according to formula (I), (I) wherein R1 is selected from hydrogen, C1-10 alkyl, hydroxyl, C1-10 alkoxy, C1-10 carboxyl; and R2 and R3 are independently selected from hydrogen, C1-10 alkyl, hydroxyl, C1-10 alkoxy, C1-10 carboxyl and -NR'R", wherein R' and R" are independently H or C1-10 alkyl; and wherein the yield of the base oil product is increased by at least 1.0 by weight compared to a process performed in the absence of the hydroisomerizing additive.

3. The process of claim 1 or 2, wherein the hydroisomerizing additive has a DBE (double bond equivalent) number in the range of 3 to 10.

4. The process described in claim 1 or 2, wherein the hydroisomerizing additive has a molecular weight of less than about 600.

5. The process described in claim 1 or 2, wherein R1 is selected from C1-4 alkyl groups, and R2 and R3 are hydrogen.

6. The process of claim 1 or 2, wherein combining the hydrocarbon feed and the hydroisomerizing additive comprises adding about 10 to about 500 ppm of the hydroisomerizing additive to the hydrocarbon feed based on the weight of the hydrocarbon feed.

7. The process of claim 1 or 2, wherein the combination of the hydrocarbon feed and the hydroisomerizing additive comprises adding the hydroisomerizing additive to the hydrocarbon feed in an amount providing nitrogen in the range of about 0.1 to about 50 ppm based on the weight of the hydrocarbon feed.

8. The process of claim 1 or 2, wherein the hydrocarbon feed and the hydroisomerization additive are combined to provide the combined feed, and then the combined feed is fed to the hydroisomerization reactor.

9. The process described in claim 1 or 2, wherein the hydrocarbon feed has a distillation temperature of at least about 900℉ (30%).

10. The process described in claim 1 or 2, wherein the hydrocarbon feed has a pour point of about 0°C or higher.

11. The process of claim 1 or 2, wherein the hydroisomerization catalyst further comprises a group 8 to group 10 metal.

12. The process of claim 1 or 2, wherein the combined feed is contacted with the hydroisomerization catalyst and hydrogen under hydroisomerization conditions, the hydroisomerization conditions including a temperature in the range of about 550℉ to about 750℉.

13. The process of claim 12, wherein the hydroisomerization conditions further include: contacting the combined feed and the hydroisomerization catalyst in the reactor under the following conditions: a pressure in the range of about 15 to about 3000 psig; a feed rate of the combined feed to the reactor in the range of about 0.1 to about 20 h⁻¹ liquid space velocity (LHSV); and hydrogen and combined feed being fed to the reactor at a ratio of about 2000 to about 10,000 standard cubic feet H₂ per barrel of combined feed.

14. The process of claim 1 or 2, wherein the combined feed and the hydroisomerization catalyst are contacted to produce a hydroisomerized feed stream, which is further contacted with a hydrorefining catalyst to provide a base oil having a pour point of about -5°C or lower.

15. The process of claim 1 or 2, wherein the yield of base oil produced by contacting the combined feed and the hydroisomerization catalyst is increased by at least 1.0 by weight compared to the process performed in the absence of the hydroisomerization additive.

16. A process for improving the yield of base oil produced by contacting a hydrocarbon feedstock and a hydroisomerization catalyst, the process comprising combining the hydrocarbon feedstock and a hydroisomerization additive to form a combined feedstock, and contacting the combined feedstock and the hydroisomerization catalyst, wherein the hydroisomerization additive is a substituted or unsubstituted nitrogen heterocycle according to formula (I), (I) wherein R1 is selected from hydrogen, C1-10 alkyl, hydroxyl, C1-10 alkoxy, C1-10 carboxyl; and R2 and R3 are independently selected from hydrogen, C1-10 alkyl, hydroxyl, C1-10 alkoxy, C1-10 carboxyl and -NR'R", wherein R' and R" are independently H or C1-10 alkyl; and the hydroisomerization catalyst comprises zeolite SSZ-91.

17. The process described in claim 16, wherein the base oil produced has a pour point of about -5°C or lower.

18. The process of claim 16, wherein the yield is increased by at least 1.0 wt% compared to the process performed in the absence of the hydroisomerizing additive.

19. The process described in claim 16, wherein R1 is hydrogen.

20. The process of claim 16, wherein the hydroisomerization additive is added to the hydrocarbon feed in an amount of at least about 10 ppm.

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