Processes for producing diesel from unconventional feedstocks

Abstract

This article describes a process for hydroisomerizing unconventional feedstocks to provide diesel fuel using hydroisomerization catalysts containing zeolite SSZ-91, zeolite SSZ-32, or zeolite SSZ-32x.

Description

Technical field

[0001] This paper describes new processes for hydrogenating isomerization of unfamiliar feedstocks such as biofraction feeds or Fischer-Tropsch feeds using hydrogenation isomerization catalysts containing zeolite SSZ-91, zeolite SSZ-32x, zeolite SSZ-32, or combinations thereof. Prior technology

[0002] Unknown feedstocks such as biological fraction feeds or Fey-Tor feeds are known to exhibit poorer cold flow characteristics. It is desirable to produce diesel fuels with improved cold flow characteristics to solve the problem of clogging of fuel filters in cold conditions. Traditionally, the cold flow characteristics of diesel fuels produced from non-known feedstocks have been improved by the addition of additives to reduce the turbidity and / or inclination points of the resulting diesel fuel. However, such a learning procedure may be costly and inefficient, for example thereby reducing diesel fuel yield.

[0003] The invention aims to provide a process for producing diesel with improved cold flow characteristics from non-known feedstocks with improved efficiency and improved yield. Contents of the invention

[0004] []

[0005] The invention relates to the process of efficiently converting non-known feedstocks such as biofraction feeds and Feytoll feeds into premium products, including diesel fuels having low inclination and low turbidity points.

[0006] According to the first state, a process for hydrogenating isomerizing diesel feedstock comprising contacting the diesel feedstock with a hydrogenating isomerizing catalyst is provided, wherein the diesel feedstock contains either a biofraction feed or a Fey-Toll feed, and the hydrogenation isomerization catalyst contains zeolite SSZ-91, zeolite SSZ-32, or zeolite SSZ-32x.

[0007] According to the second state, a process is provided for upgrading the diesel feedstock comprising: a diesel fuel with reduced turbidity and reduced inclination points compared to the turbidity and inclination points of the diesel feedstock in contact with the hydrogenation isomerization catalyst under hydrogenation isomerization conditions, wherein the diesel feedstock contains either a biofraction feed or a Fey-Toll feed, and the hydrogenation isomerization catalyst contains zeolite SSZ-91, zeolite SSZ-32, or zeolite SSZ-32x.

[0008] According to the third state sample, this article provides the use of a hydroisomerization catalyst containing zeolite SSZ-91, zeolite SSZ-32 or zeolite SSZ-32x to provide diesel fuel exhibiting a lower cloud point and lower pour point compared to the cloud point and pour point of the diesel feedstock used to produce diesel fuel, wherein the diesel fuel is produced by contacting the diesel feedstock with the hydroisomerization catalyst, and the diesel feedstock contains bio-component feed or Fischer-Tropsch feed.

[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, unless mutually exclusive, any feature described herein can be applied to any state and / or in combination with any other feature described herein. Simple Explanation of the Diagram

[0010] []

[0011] Figure 1 schematically illustrates a process for hydroisomerizing diesel feedstock according to an embodiment of the present invention; and Figure 2 schematically illustrates a process for hydroisomerizing diesel feedstock according to an embodiment of the present invention. Implementation

[0012] Cross-reference to related applications

[0013] This application claims priority to U.S. Patent Application Serial No. 17 / 138,260, filed on December 30, 2020, the disclosure of which is incorporated herein by reference in its entirety. introduction

[0014] As used herein, the term "unconventional feedstock" refers to both bio-component feedstock and Fischer-Tropsch feedstock. Unconventional feedstocks have boiling ranges suitable for producing diesel fuel from them. In embodiments, the boiling points of unconventional feedstocks are in the range of about 250℉ (121°C) to about 900℉ (482°C), for example, about 300℉ (149°C) to about 900℉ (482°C), or about 250℉ (121°C) to about 800℉ (427°C).

[0015] As used herein, the term "bio-component feedstock" refers to diesel feedstock derived from sources containing bio-components, such as oils or fats based on vegetables, animals, fish, or algae. In embodiments, the bio-component feedstock has a boiling point at atmospheric pressure ranging from about 250℉ (121°C) to about 900℉ (482°C), for example, from about 300℉ (149°C) to about 900℉ (482°C), from about 400℉ to about 900℉ (about 204°C to about 482°C), from about 500℉ to about 900℉ (about 260°C to about 482°C), from about 600℉ (316°C) to about 900℉ (482°C), or from about 700℉ (371°C) to about 900℉ (482°C). In embodiments, the bio-component feedstock has a 90% distillation temperature of less than about 700℉ (371°C), for example, less than about 650℉ (343°C). In an embodiment, the biocomponent feed has a 90% distillation temperature in the range of about 550℉ (288°C) to about 750℉ (399°C), for example, about 550℉ (288°C) to about 700℉ (371°C), or about 600℉ (316°C) to about 700℉ (371°C). The 90% distillation temperature can be determined according to ASTM D 2887. In an embodiment, the biocomponent feed has a 5% distillation temperature in the range of about 250℉ (121°C) to about 600℉ (316°C), for example, about 300℉ (149°C) to about 600℉ (316°C), or about 400℉ (about 204°C) to about 600℉ (316°C). The 5% distillation temperature can be determined according to ASTM D 2887. In one embodiment, the bio-component feed has a 90% distillation temperature ranging from about 550℉ (about 288°C) to about 750℉ (about 399°C) and a 5% distillation temperature ranging from about 250℉ (121°C) to about 600℉ (316°C). In another embodiment, the bio-component feed has a 90% distillation temperature ranging from about 550℉ (288°C) to about 700℉ (371°C) and a 5% distillation temperature ranging from about 300℉ (149°C) to about 600℉ (316°C). In yet another embodiment, the bio-component feed has a 90% distillation temperature greater than about 600℉ (316°C), for example, from about 605℉ (about 318°C) to about 675℉ (357°C) and a 5% distillation temperature less than about 600℉ (316°C), for example, from about 540℉ (282°C) to about 580℉ (304°C). In the embodiments, the bio-component feed has a 90% distillation temperature in the range of about 600℉ (316°C) to about 700℉ (371°C) and a 5% distillation temperature in the range of about 400℉ (204°C) to about 600℉ (316°C).

[0016] As used herein, the term "Fischer-Tropsch feedstock" refers to synthetic diesel feedstock produced by a Fischer-Tropsch process and having a 90% distillation temperature of less than about 750℉ (399°C), for example less than about 700℉ (371°C). In embodiments, the Fischer-Tropsch feedstock has a 90% distillation temperature in the range of about 550℉ (288°C) to about 750℉ (399°C), for example about 550℉ (288°C) to about 700℉ (371°C), or about 600℉ (316°C) to about 700℉ (371°C). The 90% distillation temperature may be determined according to ASTM D 2887. In an embodiment, the Fischer-Tropsch feed has a 5% distillation temperature in the range of about 250℉ (121°C) to about 600℉ (316°C), for example, about 300℉ (149°C) to about 600℉ (316°C), or about 340℉ (171°C) to about 600℉ (316°C), or about 340℉ (171°C) to about 500℉ (260°C), or about 340℉ (171°C) to about 400℉ (204°C). The 5% distillation temperature may be determined according to ASTM D 2887. In an embodiment, the Fischer-Tropsch feed has a 90% distillation temperature in the range of about 550℉ (288°C) to about 750℉ (399°C) and a 5% distillation temperature in the range of about 250℉ (121°C) to about 600℉ (316°C). In one embodiment, the Fischer-Tropsch feed has a 90% distillation temperature ranging from about 550°F (288°C) to about 700°F (371°C) and a 5% distillation temperature ranging from about 300°F (149°C) to about 600°F (316°C). In another embodiment, the Fischer-Tropsch feed has a 90% distillation temperature ranging from about 600°F (316°C) to about 700°F (371°C) and a 5% distillation temperature ranging from about 340°F (171°C) to about 600°F (316°C). In yet another embodiment, the Fischer-Tropsch feed has a 90% distillation temperature ranging from about 600°F (316°C) to about 700°F (371°C) and a 5% distillation temperature ranging from about 340°F (171°C) to about 500°F (260°C). In an embodiment, 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 an embodiment, the Fischer-Tropsch feed may have a boiling point at atmospheric pressure 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).

[0017] The term "diesel fuel" is used herein to refer to hydrocarbon products having a boiling point in the range of about 300℉ to about 800℉ (about 149°C to about 427°C) at atmospheric pressure.

[0018] The term "active source" refers to a reagent or precursor material that can supply at least one element in a reactive form that can be incorporated into the molecular sieve structure. The terms "source" and "active source" are used interchangeably herein.

[0019] The terms "molecular sieve" and "zeolite" are synonymous and include (a) intermediates and (b) final or target molecular sieves, as well as molecular sieves produced by (1) direct synthesis or (2) post-crystallization processing (secondary modification). Secondary synthesis techniques allow the synthesis of target materials from intermediate materials by heteroatom lattice substitution or other techniques. For example, aluminosilicates can be synthesized from intermediate borosilicates by heteroatom lattice substitution of B with Al crystals. Such techniques are known, for example, as described in U.S. Patent No. 6,790,433, issued September 14, 2004, by CY Chen and Stacey Zones.

[0020] The terms "*MRE type molecular sieve", "EUO type molecular sieve" and "MTT type molecular sieve" include all molecular sieves assigned the International Zeolite Association (IZA) framework and their isotypes, such as those described in Atlas of Zeolite Framework Types, edited by Ch. Baerlocher, LB McCusker and DH Olson, Elsevier, 6th revision, 2007, and in the zeolite structure database on the IZA website (http: / / www.iza-online.org).

[0021] The SiO₂ / Al₂O₃ ratio (SAR) is determined by ICP elemental analysis. An infinite (∞) SAR indicates that the zeolite contains no aluminum, that is, the molar ratio of silicon oxide to aluminum oxide is infinite. In that case, the molecular sieve is essentially composed of silicon oxide.

[0022] As used herein, the term "pour point" refers to the temperature at which an oil will begin to flow under controlled conditions. Pour point can be determined by ASTM D5950.

[0023] As used herein, "cloud point" refers to the temperature at which the oil begins to become cloudy when the sample is cooled under specified conditions. The cloud point can be determined by ASTM D5773.

[0024] "Group 2, 8, 9 and 10 metals" refers to metals selected from Groups 2, 8, 9 and 10 of the periodic table and / or metal compounds containing such metals. "Group 6 metals" refers to metals selected from Group 6 of the periodic table and / or metal compounds containing such metals.

[0025] The term "periodic table" refers to the IUPAC version of the periodic table of elements dated December 1, 2018.

[0026] Unless otherwise specified, the “feed rate” of the hydrocarbon feedstock into 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 hourly space velocity (LHSV) in reciprocal hours (h⁻¹).

[0027] The term "hydrotreating" refers to the process or steps of hydrodesulfurizing, hydronitrogenating, hydrometallurgically removing and / or hydrodearomaticizing components (e.g., impurities) of diesel feedstock in the presence of hydrogen, and / or hydrogenating unsaturated compounds in the feedstock.

[0028] For the purposes of this specification and the accompanying claims, unless otherwise indicated, all figures representing quantities, percentages or proportions and other numerical values ​​used in this specification and the claims should be understood to be modified by the term "about" in all cases. Therefore, unless indicated to the contrary, the numerical parameters presented in the following specification and the accompanying claims are approximate values ​​and may vary depending on the desired characteristics sought to be obtained. It should be noted that, unless clearly and explicitly limited to a single designation, the singular forms "a" and "the" as used in this specification and the accompanying claims include a plural of designations. As used herein, the term "comprising" and its grammatical variations are intended to be non-limiting, such that the description of an item in a list does not exclude other similar items that may be substituted for or added to the listed item. 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.

[0029] Unless otherwise specified, the description of the genera of elements, materials or other components of individual components or mixtures thereof may be selected from this document to include all possible subgenera and combinations thereof of the listed components and mixtures thereof. Furthermore, all numerical ranges presented herein include both upper and lower limits.

[0030] If this document refers to a standard test, unless otherwise stated, the version of the test referred to is the latest version at the time of filing this patent application.

[0031] The scope of patent eligibility is defined by the scope of the patent application and may include other instances that may occur to a person skilled in the art. Such other instances are intended to fall within the scope of the patent application if they possess structural elements that are not different from the language of the patent application, or if they include equivalent structural elements that are not substantially different from the language of the patent application. All citations used herein are incorporated herein by reference only to the extent that they do not contradict this document. [Diesel fuel] []

[0032] The diesel feedstock described herein comprises or is a bio-component feedstock or a Fischer-Tropsch feedstock. In embodiments, the diesel feedstock comprises, is substantially composed of, or is composed of a bio-component feedstock. In embodiments, the bio-component feedstock constitutes at least about 5 wt.% of the diesel feedstock, 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 least about 90 wt.%, at least about 95 wt.%, at least about 98 wt.%, or at least about 99 wt.%. In embodiments, the bio-component feedstock constitutes from 5 wt.% to 100 wt.% of the diesel feedstock, for example, from 10 wt.% to 100 wt.%, 50 wt.% to 100 wt.%, 80 wt.% to 100 wt.%, or 95 wt.% to 100 wt.%. In embodiments, the diesel feedstock comprises, is substantially composed of, or consists of Fischer-Tropsch feedstock. In embodiments, the Fischer-Tropsch feedstock constitutes at least about 5 wt.% of the diesel feedstock, 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 least about 90 wt.%, at least about 95 wt.%, at least about 98 wt.%, or at least about 99 wt.%. In embodiments, the Fischer-Tropsch feedstock constitutes from 5 wt.% to 100 wt.% of the diesel feedstock, for example, from 10 wt.% to 100 wt.%, 50 wt.% to 100 wt.%, 80 wt.% to 100 wt.%, or 95 wt.% to 100 wt.%.

[0033] In this embodiment, the diesel feedstock comprises a blended diesel feedstock consisting of a bio-component feed or a Fischer-Tropsch feed and another diesel feedstock such as a blend feed as described below. For example, the blended diesel feedstock may comprise a blend of feedstocks selected from: gasification oil, vacuum gasification oil, long residues, vacuum residues, atmospheric distillates, heavy fuels, oils, waxes and paraffins, waste oil, deasphalted residues or crude oil, feedstock produced by thermal or catalytic conversion processes, or combinations thereof. In the embodiments, the mixed feedstock is selected from whole crude oil, reduced crude oil, vacuum distillation residue, circulating oil, synthetic crude oil, gas-generated oil, vacuum gas-generated oil, scrap oil, Fischer-Tropsch derivative wax, lubricating oil, heating oil, heavy neutral feedstock, hydrotreated gas-generated oil, hydrocracking gas-generated oil, hydrotreated lubricating oil raffinate, bright oil, lubricating oil, synthetic oil, high pour point polyolefins (e.g., polyolefins with a pour point of about 0°C or above); common α-olefin waxes, soft waxes, deoiled waxes, microcrystalline waxes, residue fractions from atmospheric distillation processes, solvent-deasphalted petroleum residue, shale oil, circulating oil, petroleum waxes, soft waxes, and waxes produced in chemical plant processes. In the embodiments, the diesel feedstock is a mixed diesel feedstock comprising biological component feedstock and Fischer-Tropsch feedstock. In the embodiments, the diesel feedstock is a mixed diesel feedstock comprising biological component feedstock, Fischer-Tropsch feedstock, and mixed feedstock (e.g., mixed feedstock as described above).

[0034] In the embodiments, the diesel feedstock is a mixed diesel feedstock comprising a biological component feed and a mixed feed, wherein the mixed diesel feedstock comprises at least about 5 wt.% of the biological component feed and at most about 95 wt.% of the mixed feed, for example, at least about 10 wt.% of the biological component feed and at most about 90 wt.% of the mixed feed, at least about 50 wt.% of the biological component feed and at most about 50 wt.% of the mixed feed, at least about 80 wt.% of the biological component feed and at most about 20 wt.% of the mixed feed, or at least about 95 wt.% of the biological component feed and at most about 5 wt.% of the mixed feed.

[0035] In an embodiment, the diesel feedstock comprises a blended diesel feedstock consisting of a Fischer-Tropsch feed and a mixed feed, wherein the blended diesel feedstock comprises at least about 5 wt.% of Fischer-Tropsch feed and at most about 95 wt.% of mixed feed, for example, at least about 10 wt.% of Fischer-Tropsch feed and at most about 90 wt.% of mixed feed, at least about 50 wt.% of Fischer-Tropsch feed and at most about 50 wt.% of mixed feed, at least about 80 wt.% of Fischer-Tropsch feed and at most about 20 wt.% of mixed feed, or at least about 95 wt.% of Fischer-Tropsch feed and at most about 5 wt.% of mixed feed. [Biological component feed]

[0036] In this embodiment, the diesel feedstock comprises, is substantially composed of, or is composed of a biological component feedstock. Plant-based oils and fats include vegetable oils and fats such as rapeseed (canola) oil, soybean oil, coconut oil, sunflower seed oil, palm oil, palm kernel oil, peanut oil, linseed oil, tallow, corn oil, castor oil, jatropha oil, jojoba oil, olive oil, flaxseed oil, flaxseed oil, safflower oil, babassu oil, tallow, and rice bran oil. Animal oils and fats include beef fat (tallow), pork fat (lard), turkey fat, fish fat / oil, and chicken fat, including algae and fish fat / oil. In this embodiment, the biological component feedstock is selected from vegetable oils and animal fats, comprising or substantially composed of triglycerides and free fatty acids (FFA).

[0037] In the embodiments, the triglycerides and FFA contain an aliphatic hydrocarbon chain having 6-24 carbon atoms (e.g., 8 to 24, 8 to 20, or 10-16 carbon atoms) in their structures. In the embodiments, the biocomponent feed comprises a triglyceride having the general formula (1):

[0038] R, R1, and R2 are independently aliphatic hydrocarbon chains having 6-24 carbon atoms (e.g., 8-24, 8-20, 10-20, 10-18, or 10-16 carbon atoms). In the examples, R, R1, and R2 are independently branched or unbranched, substituted or unsubstituted, fully saturated or containing one or more (e.g., 1-4, 1-3, or 1 or 2) unsaturated carbon-carbon bonds. In the examples, R, R1, and R2 are unsubstituted. In the examples, R, R1, and R2 are independently fully saturated or contain one or more (e.g., 1-4, 1-3, or 1 or 2) unsaturated carbon-carbon bonds. In the examples, R, R1, and R2 are unbranched.

[0039] In embodiments, the biocomponent feed comprises free fatty acids (FFAs) having an aliphatic hydrocarbon tail of 6 to 24 carbon atoms, such as 8 to 24 carbon atoms, 8 to 20 carbon atoms, 10 to 20 carbon atoms, 10 to 18 carbon atoms, or 10 to 16 carbon atoms. In embodiments, the FFA comprises an unsaturated or saturated aliphatic hydrocarbon tail. In embodiments, the FFA comprises an unbranched or branched aliphatic hydrocarbon tail.

[0040] In the embodiments, the biological component feed is selected from rapeseed oil, corn oil, soybean oil, castor oil, linseed oil, palm oil, and combinations thereof.

[0041] In embodiments, the oxygen content of the biological component feed is at least about 0.5 wt.% of the total weight of the biological component 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.%. In embodiments, the oxygen content of the biological component feed is at most about 15 wt.% of the total weight of the biological component feed, for example, at most about 10 wt.% or at most about 5 wt.%. In embodiments, the oxygen content of the biological component feed is in the range of about 1-15 wt.% of the total weight of the biological component feed, for example, in the range of about 5-15 wt.% or about 10-15 wt.%. For example, according to ASTM E385-90 (2002), the oxygen content of biological component feed can be measured by neutron activation analysis.

[0042] In this embodiment, the biocomponent feed is hydrogenated before contact with the hydroisomerization catalyst. In this embodiment, the biocomponent feed has 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 this embodiment, the biocomponent feed has a nitrogen (N) content of less than about 50 ppm, for example, less than about 20 ppm, or less than about 10 ppm. In this embodiment, the oxygen content of the hydrogenated biocomponent feed is typically about 0 wt.%, or alternatively less than about 2 wt.% or 5 wt.%. The nitrogen content of the biocomponent feed can be determined according to ASTM D4629. The sulfur content of the biocomponent feed can be determined according to ASTM D2622. [fee] [-] [Package delivery]

[0043] In the embodiments, the diesel feedstock comprises, is substantially composed of, or consists of Fischer-Tropsch feedstock. The Fischer-Tropsch feedstock will typically have a paraffin content of at least about 90 wt.%, for example, at least about 95 wt.% or at least about 97.5 wt.%. The Fischer-Tropsch feedstock typically contains only very small amounts of olefins and cycloalkanes, for example, less than about 1.0 wt.% of olefins, or less than about 0.5 wt.% of olefins, and / or less than about 1.0 wt.% of cycloalkanes, less than about 0.5 wt.% of cycloalkanes, or less than about 0.1 wt.% of cycloalkanes. In the embodiments, the Fischer-Tropsch feedstock has a sulfur content of less than about 50 ppm, for example, less than about 20 ppm. In the embodiments, the Fischer-Tropsch feedstock has a nitrogen content of less than about 50 ppm, for example, less than about 20 ppm. In the embodiments, the Fischer-Tropsch feedstock has a metal content of less than about 10 ppm, for example, less than about 5 ppm. The paraffin and cycloalkanes content of Fischer-Tropsch feedstocks can be determined by GC-FIMS analysis, as described in "Diesel Fuel Analysis by GC-FIMS: Normal Paraffins, Isoparaffins and Cycloparaffins", Briker, Y., et al., Energy Fuels 2001, 15, 4, 996-1002. The nitrogen content of Fischer-Tropsch feedstocks can be determined according to ASTM D3228-20. The sulfur content of Fischer-Tropsch feedstocks can be determined according to ASTM D4629. The metal content of Fischer-Tropsch feedstocks can be measured by inductively coupled plasma atomic emission spectrometry (ICP-AES). [Hydroisomerization catalyst]

[0044] As used herein, the term "hydroisomerization catalyst" refers to the hydroisomerization catalyst described below, which includes zeolite SSZ-91, zeolite SSZ-32, zeolite SSZ-32x, or combinations thereof.

[0045] In the embodiments, the hydroisomerization catalyst comprises about 5 to about 95 wt.% of zeolite SSZ-91, zeolite SSZ-32, or zeolite SSZ-32x based on the total weight of the hydroisomerization catalyst, for example, about 10 to about 95 wt.% of zeolite SSZ-91, zeolite SSZ-32, or zeolite SSZ-32x, about 20 to about 90 wt.% of zeolite SSZ-91, zeolite SSZ-32, or zeolite SSZ-32x, about 25 to about 85 wt.% of zeolite SSZ-91, zeolite SSZ-32, or zeolite SSZ-32x, about 30 to about 80 wt.% of zeolite SSZ-91, zeolite SSZ-32, or zeolite SSZ-32x, or about 35 to about 75 wt.% of zeolite SSZ-91, zeolite SSZ-32, or zeolite SSZ-32x based on the total weight of the hydroisomerization catalyst. wt.% of zeolite SSZ-91, zeolite SSZ-32 or zeolite SSZ-32x, or about 35 to about 65 wt.% of zeolite SSZ-91, zeolite SSZ-32 or zeolite SSZ-32x, or about 35 to about 55 wt.% of zeolite SSZ-91, zeolite SSZ-32 or zeolite SSZ-32x, or about 45 to about 75 wt.% of zeolite SSZ-91, zeolite SSZ-32 or zeolite SSZ-32x, or about 55 to about 75 wt.% of zeolite SSZ-91, zeolite SSZ-32 or zeolite SSZ-32x.

[0046] The hydroisomerization catalyst further comprises a metal modifier, such as a metal modifier selected from Group 2, 8, 9, and 10 metals or combinations thereof. In embodiments, the metal modifier is selected from Group 8, 9, or 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.

[0047] In the embodiments, the hydroisomerization catalyst comprises about 0.05 to about 2.0 wt.% of a metal modifier (e.g., selected from Group 2, 8, 9 and 10 metals, or Group 8, 9 or 10 metals, such as Group 10 metals (such as platinum)) of the total weight of the hydroisomerization 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.% of the total weight of the hydroisomerization catalyst.

[0048] In the embodiments, the hydroisomerization catalyst comprises an oxide binder. In the embodiments, the oxide binder is an inorganic oxide. In the embodiments, the hydroisomerization catalyst comprises an oxide binder selected from alumina, silicon oxide, cerium oxide, titanium oxide, tungsten oxide, zirconium oxide, and combinations thereof. In the 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 as a matrix material in a catalyst substrate. 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 about 95 wt.% of an oxide binder based on the total weight of the hydroisomerization catalyst, such as about 5 to about 80 wt.% of an oxide binder, about 10 to about 70 wt.% of an oxide binder, about 20 to about 70 wt.% of an oxide binder, such as about 25 to about 65 wt.% of an oxide binder based on the total weight of the hydroisomerization catalyst.

[0049] In the embodiments, the hydroisomerization catalyst comprises: Based on the total weight of the hydroisomerization catalyst, approximately 5 to approximately 95 wt.% of zeolite SSZ-91, zeolite SSZ-32, or zeolite SSZ-32x; Group 8-10 metals, approximately 0.05 to approximately 2.0 wt.%; and Oxide adhesive of about 5 to about 95 wt.%.

[0050] In the embodiments, the hydroisomerization catalyst comprises: Based on the total weight of the hydroisomerization catalyst, approximately 30 to approximately 80 wt.% of zeolite SSZ-91, zeolite SSZ-32, or zeolite SSZ-32x; About 0.1 to about 1.5 wt.% of Group 8-10 metals; and Oxide adhesive of about 20 to about 70 wt.%. [Zeolite] [SSZ-91]

[0051] US-A-9920260 describes zeolite SSZ-91 and its preparation method, which is incorporated herein by reference in its entirety. Zeolite SSZ-91 can also be referred to as SSZ-91 molecular sieve.

[0052] Zeolite SSZ-91 has a SiO2 / Al2O3 molar ratio (SAR) of 40 to 220. In embodiments, zeolite SSZ-91 has a SiO2 / Al2O3 molar ratio (SAR) of 40 to 200, for example 70 to 200, 80 to 200, 70 to 180, 80 to 180, 70 to 160, 80 to 160, 70 to 140, 80 to 140, 100 to 160, 100 to 140, or 120 to 140. SAR is determined by inductively coupled plasma (ICP) elemental analysis.

[0053] Zeolite SSZ-91 consists of at least 70% polymorph 6 of the total ZSM-48 material present in the product. The proportion of polymorph 6 of the total ZSM-48 material present in the product was determined by DIFFAX simulation and, as described by Lobo and Koningsveld in J. Am. Chem. Soc. 2012, 124, 13222-13230, where disorder is adjusted 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 as described by Lobo and Koningsveld (…). [See] J. Am. Chem. Soc. 2002, 124, 13222-13230. In one embodiment, the SSZ-91 material consists of polymorph 6 comprising at least 80% of the total ZSM-48 type material present in the product. In another embodiment, the SSZ-91 material consists of polymorph 6 comprising at least 90% of the total ZSM-48 type material present in the product. The polymorph 6 structure has been assigned architecture code *MRE by the International Zeolite Association Structure Committee.

[0054] Zeolite SSZ-91 has a morphology characterized as a polycrystalline aggregate comprising microcrystals having an average aspect ratio in the range of 1 to 8. In an embodiment, zeolite SSZ-91 has a morphology characterized as a polycrystalline aggregate comprising microcrystals having an average aspect ratio in the range of 1 to 6, for example 1 to 5, 1 to 4, or 1 to 3.

[0055] In an embodiment, zeolite SSZ-91 has a morphology characterized as polycrystalline aggregates with a diameter between approximately 100 nm and 1.5 µm, each aggregate comprising a collection of microcrystals having a common average aspect ratio in the range of 1 to 8. In another embodiment, zeolite SSZ-91 has a morphology characterized as polycrystalline aggregates with a diameter between approximately 100 nm and 1.5 µm, each aggregate comprising a collection of microcrystals having a common 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 at the short end of each microcrystal examined.

[0056] Zeolite SSZ-91 is a substantially phase-pure material. As used herein, the term "substantially phase-pure material" means that the material is completely free of zeolite phases other than those belonging to the ZSM-48 series of zeolites, or that their presence is less than a measurable effect on the material's selectivity or imparts a material disadvantage less than that affecting the material's selectivity. Two common phase systems that co-crystallize with SSZ-91 are EUO-type molecular sieves such as EU-1, as well as Magadiite and Kenyaite. These additional phases can exist as separate phases or can intergrow with the SSZ-91 phase.

[0057] In the embodiments, zeolite SSZ-91 contains EUO-type molecular sieve phase in an amount ranging from 0 to 7 wt.% of the total zeolite SSZ-91 product. In the embodiments, zeolite SSZ-91 contains EUO-type molecular sieve phase in an amount ranging from 0 to 5.0 wt.%, for example, 0 to 4.0 wt.% or 0 to 3.5 wt.%. In the embodiments, zeolite SSZ-91 contains EUO-type molecular sieve phase in an amount ranging from 0.1 to 7.0 wt.%, for example, 0.1 to 5.0 wt.%, 0.1 to 4.0 wt.%, or 0.1 to 3.5 wt.%. In the embodiments, zeolite SSZ-91 contains 0 to 7 wt.% of EU-1, such as 0 to 5.0 wt.% of EU-1, 0 to 4.0 wt.% of EU-1, 0 to 3.5 wt.% of EU-1, 0.1 to 7.0 wt.% of EU-1, 0.1 to 5.0 wt.% of EU-1, 0.1 to 4.0 wt.% of EU-1, 0.1 to 3.5 wt.% of EU-1, 0.1 to 2 wt.% of EU-1, or 0.1 to 1 wt.% of EU-1.

[0058] As is well known, for any two phases in a mixture, the ratio of powder XRD peak intensities changes linearly as a function of weight fraction: (Iα / Iβ) = (RIRα / RIRβ)* (xα / xβ), where the RIR (reference intensity ratio) parameter can be found in The International Centre for Diffraction Data's Powder Diffraction File (PDF) database (http: / / www.icdd.com / products / ). Therefore, the weight percentage of the EUO phase in zeolite SSZ-91 can be calculated by measuring the ratio between the peak intensities of the EUO phase and the SSZ-91 phase.

[0059] 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 the total ZSM-48 material is of the multi-type body 6; EUO type molecular sieve phase, ranging from 0 to 7.0 wt.%. Zeolite SSZ-91 has a morphology characterized as a polycrystalline aggregate containing microcrystals with an average aspect ratio between 1 and 8.

[0060] 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 the total ZSM-48 material is of the multi-type body 6; EUO type molecular sieve phase, ranging from 0 to 4.0 wt.%. Zeolite SSZ-91 has a morphology characterized as a polycrystalline aggregate containing microcrystals with an average aspect ratio between 1 and 8.

[0061] 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 the total ZSM-48 material is of the multi-type body 6; 0 to 3.5 wt.% EUO type molecular sieve phase; Zeolite SSZ-91 has a morphology characterized as a polycrystalline aggregate containing microcrystals with an average aspect ratio between 1 and 8.

[0062] 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 the total ZSM-48 material is of the multi-type body 6; EUO type molecular sieve phase, ranging from 0 to 4.0 wt.%. Zeolite SSZ-91 has a morphology characterized as a polycrystalline aggregate containing microcrystals with an average aspect ratio between 1 and 8.

[0063] 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 the total ZSM-48 material is of the multi-type body 6; EUO type molecular sieve phase, ranging from 0 to 4.0 wt.%. Zeolite SSZ-91 has a morphology characterized as a polycrystalline aggregate containing 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 80 to 200. At least 70% of the total ZSM-48 material is of the multi-type body 6; 0.1 to 7.0 wt.% of EUO type molecular sieve phase; Zeolite SSZ-91 has a morphology characterized as a polycrystalline aggregate containing 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 70% of the total ZSM-48 material is of the multi-type body 6; 0.1 to 4.0 wt.% of EUO type molecular sieve phase; Zeolite SSZ-91 has a morphology characterized as a polycrystalline aggregate containing 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 70% of the total ZSM-48 material is of the multi-type body 6; 0.1 to 4.0 wt.% of EU-1; Zeolite SSZ-91 has a morphology characterized as a polycrystalline aggregate containing microcrystals with an average aspect ratio between 1 and 6.

[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 70% of the total ZSM-48 material is of the multi-type body 6; 0.1 to 4.0 wt.% of EUO type molecular sieve phase; Zeolite SSZ-91 has a morphology characterized as a polycrystalline aggregate containing microcrystals with an average aspect ratio between 1 and 6.

[0068] In this embodiment, zeolite SSZ-91 comprises: The molar ratio (SAR) of silicon oxide (SiO₂) to aluminum oxide (Al₂O₃) in the range of 80 to 160. At least 70% of the total ZSM-48 material is of the multi-type body 6; 0.1 to 4.0 wt.% of EUO type molecular sieve phase; Zeolite SSZ-91 has a morphology characterized as a polycrystalline aggregate containing microcrystals with an average aspect ratio between 1 and 6.

[0069] 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 the total ZSM-48 material is of the multi-type body 6; 0.1 to 4.0 wt.% of EUO type molecular sieve phase; Zeolite SSZ-91 has a morphology characterized as a polycrystalline aggregate containing microcrystals with an average aspect ratio between 1 and 6.

[0070] 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 the total ZSM-48 material is of the multi-type 6; 0.1 to 4.0 wt.% of EUO type molecular sieve phase; Zeolite SSZ-91 has a morphology characterized as a polycrystalline aggregate containing microcrystals with an average aspect ratio between 1 and 6.

[0071] 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 the total ZSM-48 material is of the multi-type 6; 0.1 to 4.0 wt.% of EUO type molecular sieve phase; Zeolite SSZ-91 has a morphology characterized as a polycrystalline aggregate containing microcrystals with an average aspect ratio between 1 and 6.

[0072] 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 the total ZSM-48 material is of the multi-type 6; 0.1 to 7.0 wt.% of EUO type molecular sieve phase; Zeolite SSZ-91 has a morphology characterized as a polycrystalline aggregate containing microcrystals with an average aspect ratio between 1 and 4.

[0073] 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 the total ZSM-48 material is of the multi-type 6; 0.1 to 4.0 wt.% of EUO type molecular sieve phase; Zeolite SSZ-91 has a morphology characterized as a polycrystalline aggregate containing microcrystals with an average aspect ratio between 1 and 4.

[0074] In this embodiment, zeolite SSZ-91 comprises: The molar ratio (SAR) of silicon oxide (SiO₂) to aluminum oxide (Al₂O₃) in the range of 80 to 160. At least 80% of the total ZSM-48 material is of the multi-type 6; 0.1 to 4.0 wt.% of EUO type molecular sieve phase; Zeolite SSZ-91 has a morphology characterized as a polycrystalline aggregate containing microcrystals with an average aspect ratio between 1 and 4.

[0075] 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 the total ZSM-48 material is of the multi-type 6; 0.1 to 4.0 wt.% of EUO type molecular sieve phase; Zeolite SSZ-91 has a morphology characterized as a polycrystalline aggregate containing microcrystals with an average aspect ratio between 1 and 4.

[0076] 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 the total ZSM-48 material is of the multi-type 6; 0.1 to 4.0 wt.% of EU-1; Zeolite SSZ-91 has a morphology characterized as a polycrystalline aggregate containing microcrystals with an average aspect ratio between 1 and 4.

[0077] As described in this paper, the synthesized zeolite SSZ-91 can be characterized by its XRD patterns. The powder XRD lines in Table 1 represent the as-synthesized zeolite SSZ-91. Minor variations in the diffraction pattern can arise from changes in the molar ratio of the structural materials of a particular sample due to alterations in the lattice constant. Furthermore, sufficiently small crystals will affect the shape and intensity of peaks, resulting in significant peak broadening. Minor variations in the diffraction pattern can also arise from variations in the organic compounds used in the preparation and variations in the Si / Al molar ratio between samples. Calcination can also cause minor shifts in the XRD pattern. Despite these minor perturbations, the basic crystal structure remains unchanged. Table 1 Characteristic peaks of SSZ-91 after synthesis 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, wherein 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).

[0078] The X-ray diffraction patterns in Table 2 represent SSZ-91 after calcination. Table 2 Characteristic peaks of SSZ-91 after scorching 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, wherein 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).

[0079] The powder X-ray diffraction patterns presented in this paper were collected using standard techniques. The radiation system is CuK α radiation. Peak height and position, as a function of 2θ (where θ is the Bragg angle), are read from the relative intensity of the peaks (adjusted for background), and the interplanar spacing d corresponding to the recorded lines can be calculated. [Zeolite] [SSZ-91] [Preparation] reaction mixture and crystals

[0080] 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 that can be used to prepare zeolite SSZ-91 is represented by the following structure (1): (1) N,N,N,N′,N′,N′-Hexamethylhexamethylenediammonium Or hexamethonium cation

[0081] 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.

[0082] Generally, zeolite SSZ-91 is prepared by the following method: (a) Preparation of a reaction mixture containing (1) at least one source of silicon oxide; (2) at least one source of aluminum oxide; (3) at least one source of an element selected from Groups 1 and 2 of the periodic table; (4) hydroxide ions; (5) hexamethylammonium cations; and (6) water; and (b) Keep the reaction mixture under crystallization conditions sufficient to form molecular sieve crystals.

[0083] The composition of the reaction mixture that forms zeolite SSZ-91 is determined by 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 M is selected from the group of elements from Group 1 and Group 2 of the periodic table; and Q is the structure guide represented by structure 1 above.

[0084] In the embodiments, the composition of the reaction mixture from which zeolite SSZ-91 is formed is determined according to the following molar ratio: 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 M is selected from the group of elements from Group 1 and Group 2 of the periodic table; and Q is the structure guide represented by structure 1 above.

[0085] In the embodiments, the composition of the reaction mixture from which zeolite SSZ-91 is formed is determined according to the following molar ratio: 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 of elements from Group 1 and Group 2 of the periodic table; and Q is the structure guide represented by structure 1 above.

[0086] In the embodiments, the composition of the reaction mixture from which zeolite SSZ-91 is formed is determined according to 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 M is selected from the group of elements from Group 1 and Group 2 of the periodic table; and Q is the structure guide represented by structure 1 above.

[0087] In the embodiments, the composition of the reaction mixture from which zeolite SSZ-91 is formed is determined according to 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 M is selected from the group of elements from Group 1 and Group 2 of the periodic table; and Q is the structure guide represented by structure 1 above.

[0088] In the embodiments, the composition of the reaction mixture from which zeolite SSZ-91 is formed is determined according to 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 M is selected from the group of elements from Group 1 and Group 2 of the periodic table; and Q is the structure guide represented by structure 1 above.

[0089] The sources of silicon that can be used in this article include fumed silica, precipitated silica, silica hydrogels, silicic acid, colloidal silica, tetraalkyl orthosilicates (e.g., tetraethyl orthosilicate), and silica hydroxides.

[0090] The reaction mixture can be formed containing at least one source of elements selected from Groups 1 and 2 of the periodic table (hereinafter referred to as M). In examples, a source of elements from Group 1 of the periodic table is used to form the reaction mixture. In examples, a source of sodium (Na) is used to form the reaction mixture. Any M-containing compound that is harmless to the crystallization process is suitable. Such sources of Group 1 and 2 elements include their oxides, hydroxides, nitrates, sulfates, halides, oxalates, citrates, and acetates.

[0091] For each embodiment described herein, the molecular sieve reaction mixture may be supplied from more than one source. Similarly, two or more reaction components may be supplied from one source.

[0092] The reaction mixture is maintained at an elevated temperature until molecular sieve crystals are formed. Zeolite hydrothermal crystallization is typically carried out under pressure, usually in an autoclave, where the reaction mixture is subjected to autogenous pressure and stirred for a suitable period of time at a temperature ranging from about 125°C to about 200°C, 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.

[0093] In the embodiments, zeolite SSZ-91 is prepared by a method comprising the following steps: preparing a reaction mixture containing at least one silicon source, at least one aluminum source, at least one source of an element selected from Groups 1 and 2 of the periodic table, hydroxide ions, hexamethylammonium cations, and water; and subjecting the reaction mixture to crystallization conditions; The reaction mixture contains: 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 elements in Groups 1 and 2 of the periodic table; Q is a hexamethylammonium cation, and the crystallization conditions include maintaining the reaction mixture at elevated temperatures ranging from about 125°C to about 200°C.

[0094] In the embodiments, zeolite SSZ-91 is prepared by a method comprising the following steps: preparing a reaction mixture containing at least one silicon source, at least one aluminum source, at least one source of an element selected from Groups 1 and 2 of the periodic table, hydroxide ions, hexamethylammonium cations, and water; and subjecting the reaction mixture to crystallization conditions; The reaction mixture contains: 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 of elements from Groups 1 and 2 of the periodic table; Q is a hexamethylammonium cation, and the crystallization conditions include maintaining the reaction mixture at a temperature ranging from about 125°C to about 200°C, for example, from about 125°C to about 180°C or from about 125°C to about 160°C.

[0095] In the embodiments, zeolite SSZ-91 is prepared by a method comprising the following steps: preparing a reaction mixture containing at least one silicon source, at least one aluminum source, at least one source of an element selected from Groups 1 and 2 of the periodic table, hydroxide ions, hexamethylammonium cations, and water; and subjecting the reaction mixture to crystallization conditions; The reaction mixture contains: 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 of elements from Groups 1 and 2 of the periodic table; Q is a hexamethylammonium cation, and the crystallization conditions include maintaining the reaction mixture at a temperature ranging from about 125°C to about 200°C, for example, from about 125°C to about 180°C or from about 125°C to about 160°C.

[0096] In the embodiments, zeolite SSZ-91 is prepared by a method comprising the following steps: preparing a reaction mixture containing at least one silicon source, at least one aluminum source, at least one source of an element selected from Groups 1 and 2 of the periodic table, hydroxide ions, hexamethylammonium cations, and water; and subjecting the reaction mixture to crystallization conditions; The reaction mixture contains: 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 of elements from Groups 1 and 2 of the periodic table; Q is a hexamethylammonium cation, and the crystallization conditions include maintaining the reaction mixture at a temperature ranging from about 125°C to about 200°C, for example, from about 125°C to about 180°C or from about 125°C to about 160°C.

[0097] In an embodiment, the crystallization conditions include maintaining the reaction mixture at temperatures ranging from about 125°C to about 200°C, such as elevated temperatures in the range of about 125°C to about 180°C, about 125°C to about 180°C, about 125°C to about 170°C, and about 125°C to about 160°C.

[0098] The formation of the EUO phase can be suppressed by selecting hydrogel composition, temperature, and crystallization time conditions that reduce (or minimize) the formation of the EUO phase while increasing (or maximizing) the yield of the SSZ-91 product. The examples provided in US-A-9920260 offer guidance on how changes to 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 level of EU-1 material in the product.

[0099] During the hydrothermal crystallization step, molecular sieve crystals can be allowed to spontaneously nucleate in the reaction mixture. Using molecular sieve crystals as seed materials can help reduce the time required for complete crystallization. Furthermore, seed crystals can improve the purity of the obtained product by promoting the nucleation and / or formation of any unwanted phases by the molecular sieve. However, it has been found that if seed crystals are used, the seed crystals must be of a very pure phase, SSZ-91, to avoid the formation of large amounts of the EUO phase. When used as seed crystals, the amount of seed crystals added is between 0.5% and 5% of the weight of the silicon source used in the reaction mixture.

[0100] The formation of Magadiite and Kenyaite, which are layered sodium silicate components, is minimized by optimizing the hexamethylammonium bromide / SiO2 ratio, controlling the hydroxide concentration, and minimizing the sodium concentration. The example provided in US-A-9920260 offers guidance on how changes in gel conditions can minimize EU-1 formation.

[0101] 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 synthesized molecular sieve crystals. The drying step can be carried out under atmospheric pressure or vacuum. Post-Crystallization treatment

[0102] Zeolite SSZ-91 can be used post-synthesis, but it is typically subjected to heat treatment (calcination). The term "post-synthesis" refers to SSZ-91 zeolite in its crystalline form prior to 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 sufficient to remove SDA from the molecular sieve. SDA can also be removed by ozonation 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.

[0103] Zeolite SSZ-91 can then be calcined in steam, air, or an inert gas at temperatures ranging from 200°C to 800°C for periods from 1 hour to several days, for example, 1 to 48 hours. Typically, it is desirable to remove additional structural cations (e.g., Na+) by ion exchange and replace them with hydrogen, ammonium, or any desired metal ions.

[0104] In the case of intermediate molecular sieves in the formed molecular sieve system, 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.

[0105] The SSZ-91 zeolite prepared by the process disclosed herein can be formed into a wide variety of physical shapes. SSZ-91 zeolite can be in the form of powder, granules, or molded products, such as extrudates that pass through a 2-mesh (Tyler) sieve but remain on a 400-mesh (Tyler) sieve. In cases where the catalyst is molded, such as by extrusion with an organic binder, SSZ-91 zeolite can be extruded before drying, or dried or partially dried before extrusion.

[0106] Zeolite SSZ-91 can be combined with other materials that can withstand the temperatures and other conditions used in organic conversion processes. Such matrix materials include active and inactive materials, as well as synthetic or naturally occurring molecular sieves and inorganic materials such as clay, silicon dioxide, and metal oxides. Examples of such materials and their uses are disclosed in U.S. Patents 4,910,006 and 5,316,753. [SSZ-32] []

[0107] SSZ-32 zeolite is described in US-A-5397454, which is incorporated herein by reference in its entirety. SSZ-32 zeolite may also be referred to as an MTT-structured molecular sieve.

[0108] The SSZ-32 zeolite (also described as SSZ-32 molecular sieve) contains a silicon oxide (SiO2) to aluminum oxide (Al2O3) molar ratio (SAR) of 20 to less than 40, for example, in the ranges of 20-39, 20-38, 20-37, 25-39, 25-38, 25-37, 25-35, or 30-35, and has a crystal size in the range of about 0.1 to about 0.4 µm. In the examples, the SSZ-32 zeolite (also described as SSZ-32 molecular sieve) contains a silicon oxide (SiO2) to aluminum oxide (Al2O3) molar ratio (SAR) in the range of 25-37.

[0109] In the embodiments, zeolite SSZ-32 contains a silicon oxide (SiO2) to aluminum oxide (Al2O3) molar ratio (SAR) of 25 to less than 40, for example, 25 to 35, and has a crystal size in the range of about 0.1 to about 0.4 µm.

[0110] In the embodiments, zeolite SSZ-32 has a crystal size in the range of about 0.1 to about 0.4 µm, about 0.1 to about 0.3 µm, or about 0.15 to about 0.25 µm. The crystal size can be measured by transmission electron microscopy (TEM) and refers to the maximum size of the crystal.

[0111] In the examples, the composition of the synthesized and anhydrous zeolite SSZ-32 is as follows according to the molar ratio of oxides: (0.05 to 2.0)Q₂O:(0.1 to 2.0)M₂O:Al₂O₃:(20 to less than 40)SiO₂, wherein M is an alkali metal cation and Q is an N-lower alkyl-N'-isopropyl-imidazolium cation (e.g., N,N'-diisopropyl-imidazolium cation, or N-methyl-N'-isopropyl-imidazolium cation).

[0112] In the embodiments, the synthesized zeolite SSZ-32 has a crystalline structure, and the X-ray powder diffraction of this crystalline structure shows the following characteristic lines: d / n Int.I / I o 11.05 10.05 7.83 4.545 26 10 17 71 4.277 71 3.915 100 3.726 98

[0113] X-ray powder diffraction patterns were determined using standard techniques. The radiation system was K-α / bimodal copper, and a scintillation counter spectrometer with a strip-chart pen recorder was used. The peak height I and position as a function of 2θ, where θ is the Bragg angle, were read from the spectrometer line plot. Based on these measurements, the relative intensity 100I / Io was calculated, where Io is the intensity of the strongest line or peak, and d is the interplanar spacing in angstroms corresponding to the recorded line. The above X-ray diffraction pattern is characteristic of the novel SSZ-32 zeolite. Zeolites produced by exchanging metals or other cations present in the zeolite with various other cations yield substantially the same diffraction pattern, although slight shifts in interplanar spacing and minor variations in relative intensity may occur. Minor variations in the diffraction pattern can also occur... Variations in the organic compounds used in the preparation and changes in the silicon oxide to aluminum oxide molar ratio between samples were observed. Calcination can also lead to minute shifts in the X-ray diffraction pattern. Despite these minor perturbations, the basic crystal lattice structure remains unchanged. [SSZ-32] [Preparation]

[0114] SSZ-32 zeolite can be prepared as described in US 5,397,454. SSZ-32 zeolite can be prepared from an aqueous solution containing an alkali metal oxide, an N-lower alkyl-N'-isopropyl-imidazolium cation (e.g., N,N'-diisopropyl-imidazolium cation or N-methyl-N'-isopropyl-imidazolium cation), an oxide of aluminum (e.g., wherein the alumina source provides alumina in a covalently dispersed form on silicon oxide), and a source of an oxide of silicon. In examples, the reaction mixture has a composition falling within the following ranges in molar ratio: Components Mörby SiO₂ / Al₂O₃ 20–less than 40 OH- / SiO2 0.1-1.0 Q / SiO 2 0.05-0.50 M+ / SiO2 0.05–0.30 H₂O / SiO₂ Q / Q+M + 20–300 0.25-0.75 The Q series N-lower alkyl-N'-isopropylimidazolium cations (e.g., N,N'-diisopropyl) Imidazolium cations or N-methyl-N'-isopropylimidazolium cations. M-series alkali metal ions (e.g., sodium or potassium). Organic cation compounds that serve as the source of the quaternary ammonium ions employed can provide hydroxide ions.

[0115] In the embodiments, the reaction mixture has components in molar ratios falling within the following ranges: Components Mörby SiO₂ / Al₂O₃ 30-35 OH- / SiO2 0.20-0.40 Q / SiO 2 0.15-0.30 M+ / SiO2 0.15–0.30 H₂O / SiO₂ Q / Q+M + 25-60 0.33-0.67 The Q series consists of N-lower alkyl-N'-isopropylimidazolium cations (e.g., N,N'-diisopropylimidazolium cations or N-methyl-N'-isopropylimidazolium cations). The M series consists of alkali metal ions (e.g., sodium or potassium). Organic cation compounds serving as the source of the quaternary ammonium ions employed can provide hydroxide ions.

[0116] The alumina sources of the reaction mixture include aluminates, alumina, and aluminum compounds, such as aluminum-coated silica colloids, Al₂(SO₄)₃, and other zeolites. In the examples, pentasil-structured zeolites with lower SiO₂ / Al₂O₃ values ​​(approximately 10) can be used as alumina sources, such as mordenite and magnesium alkali zeolite.

[0117] Sources of silica include silicates, silica hydrogels, silicic acid, colloidal silica, fumed silica, tetraalkyl orthosilicates, and silica hydroxides.

[0118] The reaction mixture is maintained at an elevated temperature until zeolite crystals form. The temperature during the hydrothermal crystallization step can be maintained at approximately 140°C to approximately 200°C, for example, approximately 160°C to approximately 180°C, or approximately 170°C to approximately 180°C. The crystallization period can be longer than one day, for example, approximately 5 days to approximately 10 days.

[0119] Hydrothermal crystallization is carried out under pressure, typically in an autoclave, to subject the reaction mixture to autogenous pressure. The reaction mixture may be stirred during crystallization. During the hydrothermal crystallization step, crystals are allowed to spontaneously nucleate within the reaction mixture. The reaction mixture may also be guided and accelerated using SSZ-32 or ZSM-23 crystals to minimize the formation of unwanted aluminosilicate contaminants. If the reaction mixture is guided by crystals, the concentration of organic compounds (e.g., alcohols) can be reduced.

[0120] Once the zeolite crystals have formed, the solid product is separated from the reaction mixture using standard mechanical separation techniques such as filtration or centrifugation. The crystals are washed with water and then dried, for example, at 90°C to 150°C for 8 to 24 hours, to obtain the synthesized SSZ-32x zeolite crystals. The drying step can be carried out under atmospheric pressure or negative pressure.

[0121] Zeolite SSZ-32 can be used after synthesis, or it can be heat-treated (calcined) as described above for zeolite SSZ-91. Typically, it is desirable to remove alkali metal cations by ion exchange and replace them with hydrogen, ammonium, or any desired metal ion. [SSZ-32x]

[0122] Zeolite SSZ-32x is described in US 7,468,126, which is incorporated herein by reference in its entirety. SSZ-32 zeolite may also be referred to as an MTT-structured molecular sieve.

[0123] Zeolite SSZ-32x (also described as SSZ-32x molecular sieve) contains a silicon oxide (SiO2) to aluminum oxide (Al2O3) molar ratio (SAR) in the range of 20 to less than 40 and has a crystal size in the range of about 50 to about 500 angstroms. In embodiments, zeolite SSZ-32x contains a silicon oxide (SiO2) to aluminum oxide (Al2O3) molar ratio (SAR) in the range of 20-39, 20-38, 20-37, 25-39, 25-38, 30-37, 30-35, or 25-35. In embodiments, zeolite SSZ-32x (also described as SSZ-32x molecular sieve) contains a silicon oxide (SiO2) to aluminum oxide (Al2O3) molar ratio (SAR) in the range of 30-35.

[0124] In the embodiments, the zeolite SSZ-32x has a crystal size in the range of about 50 to about 500 angstroms, about 100 to about 500 angstroms, about 100 to about 400 angstroms, or about 200 to about 400 angstroms. The crystal size can be measured by transmission electron microscopy (TEM) and refers to the maximum size of the crystal.

[0125] In the embodiments, zeolite SSZ-32x contains a silicon oxide (SiO2) to aluminum oxide (Al2O3) molar ratio (SAR) in the range of 30-35 and has a crystal size in the range of about 200 to about 400 angstroms.

[0126] As determined by TEM studies, the crystallites of SSZ-32x are elongated. In the embodiments, the crystallites of SSZ-32x have an aspect ratio in the range of about 2.0 to about 2.4.

[0127] In the embodiments, the synthesized zeolite SSZ-32x has a crystalline structure, and the X-ray powder diffraction of this crystalline structure shows the following characteristic lines: 2θ d-Spacing (Å) strength Relative intensity (%) (I / I oX 100) 8.00 11.05 15 26 8.80 10.05 6 10 11.30 7.83 10 17 14.50 6.11 1 2 15.75 5.63 3 5 16.50 5.37 3 5 18.10 4.901 7 12 19.53 4.545 41 71 20.05 4.428 6 acromion 10 acromion 20.77 4.277 41 71 21:30 4.171 7 12 22.71 3.915 58 100 23.88 3.726 57 98 24.57 3.623 30 52 25.08 3.551 25 43 25.88 3.443 27 47 26.88 3.317 5 9 28.11 3.174 6 10 [, zeolite , ] [, SSZ-32x , ] [, Preparation , ] [, , ]

[0128] SSZ-32x zeolite can be prepared as described in US 7,468,126. SSZ-32x can be prepared from an aqueous solution containing an alkali metal oxide, an N-lower alkyl-N'-isopropyl-imidazolium cation (e.g., N,N'-diisopropyl-imidazolium cation or N-methyl-N'-isopropyl-imidazolium cation), an oxide of aluminum (e.g., wherein the alumina source provides alumina in a covalently dispersed form on silicon oxide), and a source of an oxide of silicon. In examples, the reaction mixture has a composition falling within the following ranges in molar ratio: Components Mörby SiO₂ / Al₂O₃ 20–less than 40 OH- / SiO2 0.1-1.0 Q / SiO 2 0.05-0.50 M+ / SiO2 0.05–0.30 H₂O / SiO₂ Q / Q+M + 20–300 0.25-0.75 The Q series is the sum of Qa and Qb, where Qa is an N-lower alkyl-N'-isopropylimidazolium cation (e.g., N,N'-diisopropylimidazolium cation or N-methyl-N'-isopropylimidazolium cation). Qb is an amine. Suitable examples of Qb are isobutyl, neopentyl, or monoethylamine, but other amines may also be used. The molar concentration of the amine Qb must be greater than the molar concentration Qa of the imidazodium compound. In the examples, the molar concentration of Qb is... The concentration of Qa is in the range of two to nine times that of α. M is an alkali metal ion (e.g., sodium or potassium). Organic cation compounds that serve as the source of the quaternary ammonium ions employed can provide hydroxide ions.

[0129] In the embodiments, the reaction mixture has a composition falling within the following range in molar ratio: Components Mörby SiO₂ / Al₂O₃ 30-35 OH- / SiO2 0.20-0.40 Q / SiO 2 0.15-0.30 M+ / SiO2 0.15–0.30 H₂O / SiO₂ Q / Q+M + 25-60 0.33-0.67 The Q series is the sum of Qa and Qb, where Qa is an N-lower alkyl-N'-isopropylimidazolium cation (e.g., N,N'-diisopropylimidazolium cation or N-methyl-N'-isopropylimidazolium cation). Qb is an amine. Suitable examples of Qb are isobutyl, neopentyl, or monoethylamine, but other amines may also be used. The molar concentration of the amine Qb must be greater than the molar concentration Qa of the imidazodium compound. In the examples, the molar concentration of Qb is... The concentration of Qa is in the range of two to nine times that of α. M is an alkali metal ion (e.g., sodium or potassium). Organic cation compounds that serve as the source of the quaternary ammonium ions employed can provide hydroxide ions.

[0130] The alumina sources of the reaction mixture include aluminates, alumina, and aluminum compounds, such as aluminum-coated silica colloids, Al₂(SO₄)₃, and other zeolites. In the examples, pentasil-structured zeolites with lower SiO₂ / Al₂O₃ values ​​(approximately 10) can be used as alumina sources, such as mordenite and magnesium alkali zeolite.

[0131] Sources of silica include silicates, silica hydrogels, silicic acid, colloidal silica, fumed silica, tetraalkyl orthosilicates, and silica hydroxides.

[0132] The reaction mixture is maintained at an elevated temperature until zeolite crystals form. The temperature during the hydrothermal crystallization step can be maintained at approximately 140°C to approximately 200°C, for example, approximately 160°C to approximately 180°C, or approximately 170°C to approximately 180°C. The crystallization period can be longer than one day, for example, approximately 5 days to approximately 10 days.

[0133] Hydrothermal crystallization is carried out under pressure, typically in an autoclave, to subject the reaction mixture to autogenous pressure. The reaction mixture can be stirred during the addition of components and during crystallization. During the hydrothermal crystallization step, crystals are allowed to spontaneously nucleate within the reaction mixture. The reaction mixture can also be guided and accelerated using SSZ-32 crystals to minimize the formation of unwanted aluminosilicate contaminants.

[0134] Once the zeolite crystals have formed, the solid product is separated from the reaction mixture using standard mechanical separation techniques such as filtration or centrifugation. The crystals are washed with water and then dried, for example, at 90°C to 150°C for 8 to 24 hours, to obtain the synthesized SSZ-32x zeolite crystals. The drying step can be carried out under atmospheric pressure or negative pressure.

[0135] Zeolite SSZ-32x can be used after synthesis, or it can be heat-treated (calcined) as described above for zeolite SSZ-91. Typically, it is desirable to remove alkali metal cations by ion exchange and replace them with hydrogen, ammonium, or any desired metal ion. Preparation of hydroisomerization catalysts

[0136] The hydroisomerization catalysts include zeolite SSZ-91, zeolite SSZ-32, or zeolite SSZ-32x. Zeolite SSZ-91, zeolite SSZ-32, or zeolite SSZ-32x can be in their post-synthetic or calcined form.

[0137] In the embodiments, the hydroisomerization catalyst is formed from calcined zeolite SSZ-91, zeolite SSZ-32 or zeolite SSZ-32x.

[0138] In the embodiments, the hydroisomerization catalyst comprises: a molecular sieve selected from zeolite SSZ-91, zeolite SSZ-32 or zeolite SSZ-32x; and a group 2, 8, 9 or 10 metal (e.g. group 8-10 metals, such as Pt).

[0139] In embodiments, the hydroisomerization catalyst is formed by compounding a molecular sieve selected from zeolite SSZ-91, zeolite SSZ-32, and zeolite SSZ-32x (in synthesized or calcined form) with an oxide binder such as alumina. In embodiments, compounding a molecular sieve selected from zeolite SSZ-91, zeolite SSZ-32, and zeolite SSZ-32x (in synthesized or calcined form) with an oxide binder involves mixing a molecular sieve selected from zeolite SSZ-91, zeolite SSZ-32, or zeolite SSZ-32x (in synthesized or calcined form) with an oxide binder and extruding the product. The mixture of molecular sieve and oxide binder can be formed into particles or extrudates having a wide range of solid shapes and sizes. In embodiments, the extrudates or particles may be dried and calcined before metal loading. In one embodiment, the extrudate or granules are impregnated with a metal, such as a Group 2, 8, 9, or 10 metal (e.g., Group 8-10 metals, such as Pt), and then dried and calcined. In another embodiment, the extrudate or granules are dried and calcined before being loaded with metal.

[0140] In the examples, the hydroisomerization catalyst was prepared by the following method: Molecular sieves (selected from zeolite SSZ-91, zeolite SSZ-32 and zeolite SSZ-32x) are combined with oxide binders to form extrudate substrates; The extrudate substrate is impregnated with an impregnation solution containing a metal, such as a Group 2, 8, 9 or 10 metal (e.g., Group 8-10 metals, such as Pt) to form a metal-loaded extrudate; Extrusions of dry loaded metals; and Extrusions of calcined and dried loaded metal.

[0141] In embodiments, the hydroisomerization catalyst is formed by impregnating a molecular sieve selected from zeolites SSZ-91, SSZ-32, and SSZ-32x with a solution containing a metal, such as a Group 2, 8, 9, or 10 metal (e.g., Group 8-10 metals, such as Pt). In embodiments, the hydroisomerization catalyst is formed by impregnating a molecular sieve (selected from SSZ-91, SSZ-32, and SSZ-32x) with a solution containing a Group 2, 8, 9, or 10 metal (e.g., Group 8-10 metals, such as Pt). In embodiments, the hydroisomerization catalyst is formed by impregnating an extrusion substrate comprising a molecular sieve (selected from SSZ-91, SSZ-32, and SSZ-32x) and an oxide binder.

[0142] In an embodiment, the extruded substrate is exposed to an impregnation solution containing a metal (e.g., immersed in an impregnation solution) for 0.1 to 10 hours.

[0143] In an embodiment, the extruded substrate is dried (e.g., for about 0.1 to about 10 hours at a temperature ranging from about 100℉ (38°C) to about 300℉ (149°C)) and calcined (for about 0.1 to about 10 hours at a temperature ranging from about 390℉ (199°C) to about 1200℉ (649°C), or from about 600℉ (316°C) to about 1200℉ (649°C)) before impregnation.

[0144] In an embodiment, an extrudate substrate formed by combining molecular sieves (selected from zeolite SSZ-91, zeolite SSZ-32, and zeolite SSZ-32x) and an oxide binder is dried and calcined before impregnation. In another embodiment, the dried and calcined extrudate substrate is impregnated with an impregnation solution to form a metal-loaded extrudate, and then dried and calcined again to form a hydroisomerization catalyst.

[0145] In an embodiment, the impregnated extruded substrate containing zeolite SSZ-91 was dried for about 0.1 to about 10 hours at a temperature ranging from about 100℉ (38°C) to about 300℉ (149°C).

[0146] In an embodiment, the dried extruded loaded metal is 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, calcination is carried out in air. [Process for Hydroisomerization of Diesel Feedstock]

[0147] The process for hydroisomerizing diesel feedstock involves contacting the diesel feedstock with a hydroisomerization catalyst. In this embodiment, the hydroisomerization of the diesel feedstock occurs in the presence of hydrogen.

[0148] In the embodiment shown in Figure 1, diesel feedstock 10 is fed together with hydrogen 12 into a hydroisomerization reactor 14, which contains a hydroisomerization catalyst 16. Inside the reactor 14, the diesel feedstock 10 is contacted with the hydroisomerization catalyst 16 in the presence of hydrogen under hydroisomerization conditions to provide a hydroisomerized stream 18.

[0149] In an embodiment, the hydroisomerization catalyst 16 is activated before the diesel feedstock is introduced into the hydroisomerization reactor 14. In an embodiment, the activation of the catalyst includes reduction at a temperature of 450 to 650℉ (232 to 343°C) for 1 to 10 hours, for example, reduction at a temperature of 500℉ (260°C) for 2 hours.

[0150] In the embodiments, the hydroisomerization catalyst is a layered catalyst. In the embodiments, the hydroisomerization catalyst comprises a first layer containing a first hydroisomerization catalyst and a second layer containing a second hydroisomerization catalyst.

[0151] In the embodiments, the first or second hydroisomerization catalyst comprises zeolite SSZ-91 as described herein, and the first and second hydroisomerization catalysts are mutually exclusive. In the embodiments, the first and second hydroisomerization catalysts independently comprise zeolite SSZ-91 and group 8-10 metals.

[0152] In the embodiments, the first or second hydroisomerization catalyst comprises zeolite SSZ-32 as described herein, and the first and second hydroisomerization catalysts are mutually exclusive. In the embodiments, the first and second hydroisomerization catalysts independently comprise zeolite SSZ-32 and Group 8-10 metals.

[0153] In the embodiments, the first or second hydroisomerization catalyst comprises zeolite SSZ-32x as described herein, and the first and second hydroisomerization catalysts are mutually exclusive. In the embodiments, the first and second hydroisomerization catalysts independently comprise zeolite SSZ-32x and Group 8-10 metals.

[0154] In embodiments, the first or second hydroisomerization catalyst comprises zeolite SSZ-32 or zeolite SSZ-32x as described herein, and the first and second hydroisomerization catalysts are mutually exclusive. In embodiments, the first and second hydroisomerization catalysts independently comprise zeolite SSZ-32 or zeolite SSZ-32x and Group 8-10 metals.

[0155] In the embodiment shown in Figure 2, diesel feedstock 10 and hydrogen 12 are fed together into a hydroisomerization reactor 14. The hydroisomerization reactor 14 contains a layered hydroisomerization catalyst, which includes a first hydroisomerization catalyst 16a and a second hydroisomerization catalyst 16b, with the first hydroisomerization catalyst 16a located upstream of the second hydroisomerization catalyst 16b. In the embodiment shown in Figure 2, the diesel feedstock is contacted with the first hydroisomerization catalyst 16a in the first hydroisomerization zone 14a of the hydroisomerization reactor 14 in the presence of hydrogen, and then contacted with the second hydroisomerization catalyst 16b in the second hydroisomerization zone 14b in the presence of hydrogen.

[0156] 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).

[0157] 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 pressure), for example, about 100 to about 2500 psig (0.69 to 17.24 MPa).

[0158] In the embodiments, the hydroisomerization conditions (e.g., the hydroisomerization conditions in reactor 14) include a feed rate of diesel feedstock to the reactor containing the hydroisomerization catalyst at a rate of about 0.1 to about 20 h⁻¹ LHSV, for example, about 0.1 to about 5 h⁻¹ LHSV.

[0159] In the embodiments, the hydroisomerization conditions (e.g., the hydroisomerization conditions in reactor 14) include feeding hydrogen and diesel feedstock into the reactor at a ratio of about 2,000 to about 10,000 standard cubic feet H2 / barrel of diesel feedstock (about 360 to about 1,800 m3 H2 / m3 feed), for example, about 2,500 to about 5,000 scf H2 / barrel of diesel feedstock (about 440 to about 890 m3 H2 / m3 feed).

[0160] In the embodiments, the hydroisomerization conditions (e.g., the hydroisomerization conditions in reactor 14) are as follows: Temperatures ranging from approximately 390℉ to approximately 800℉ (199°C to 427°C), for example, from approximately 550℉ to approximately 750℉ (288°C to 399°C) or from 570℉ to approximately 675℉ (299°C to 357°C); Pressures ranging from approximately 15 to approximately 3000 psig (0.10 to 20.68 MPa gauge pressure), for example, from approximately 100 to approximately 2500 psig (0.69 to 17.24 MPa); The diesel feedstock is fed into the reactor containing the hydroisomerization catalyst at a rate ranging from about 0.1 to about 20 h⁻¹ LHSV, for example, from about 0.1 to about 5 h⁻¹ LHSV; and Hydrogen and diesel feedstock are fed into the reactor at a ratio of approximately 2,000 to approximately 10,000 standard cubic feet H2 / barrel of diesel feedstock (approximately 360 to approximately 1,800 m3 H2 / m3 feed), for example, approximately 2,500 to approximately 5,000 scf H2 / barrel of diesel feedstock (approximately 440 to approximately 890 m3 H2 / m3 feed).

[0161] In one embodiment, a diesel feedstock is contacted with a hydroisomerization catalyst, a process that provides diesel fuel with an increased ratio of isoparaffins to n-paraffins compared to the diesel feedstock.

[0162] In the embodiments, contacting the diesel feedstock with the hydroisomerization catalyst provides a diesel fuel with a lower cloud point and a lower pour point compared to the diesel feedstock.

[0163] In the embodiments, contacting the diesel feedstock with the hydroisomerization catalyst provides a diesel fuel exhibiting a lower cloud point and a lower pour point compared to the cloud point and pour point of the diesel feedstock, wherein the diesel fuel exhibits a cloud point and a pour point at least 10°C lower than the cloud point and a pour point at least 10°C lower than the cloud point and a pour point at least 20°C lower than the cloud point and a pour point at least 20°C lower than the cloud point and a pour point at least 3 ... Hydrotreating of diesel feedstock prior to hydroisomerization

[0164] In this embodiment, the diesel feedstock is contacted with the hydrotreating catalyst under hydrotreating conditions before contacting the catalyst. The hydrotreating conditions in this embodiment are as follows: Temperatures ranging from approximately 390℉ to approximately 800℉ (199°C to 427°C), for example, from approximately 550℉ to approximately 750℉ (288°C to 399°C) and from 590℉ to approximately 675℉ (310°C to 357°C); Pressures ranging from approximately 15 to approximately 3000 psig (0.10 to 20.68 MPa gauge pressure), for example, from approximately 100 to approximately 2500 psig (0.69 to 17.24 MPa); The diesel feedstock is fed into the reactor containing the hydroisomerization catalyst at a rate ranging from about 0.1 to about 20 h⁻¹ LHSV, for example, from about 0.1 to about 5 h⁻¹ LHSV; and Hydrogen and diesel feedstock are fed into the reactor at a ratio of approximately 2,000 to approximately 10,000 standard cubic feet H2 / barrel of diesel feedstock (approximately 360 to approximately 1,800 m3 H2 / m3 feed), for example, approximately 2,500 to approximately 5,000 scf H2 / barrel of diesel feedstock (approximately 440 to approximately 890 m3 H2 / m3 feed).

[0165] The hydrotreating catalyst may comprise a refractory inorganic oxide support and a Group 6 metal modifier and / or a Group 8-10 metal modifier. In embodiments, the hydrotreating catalyst comprises a refractory inorganic oxide support, a Group 6 metal 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 comprise alumina, silicon oxide, silicon oxide / alumina, titanium oxide, magnesium oxide, zirconium oxide, or similar materials or combinations thereof, or materials prepared from them. The support of the hydrotreating catalyst may comprise amorphous materials, crystalline materials, or combinations thereof. Examples of amorphous materials include, but are not limited to, amorphous alumina, amorphous silicon oxide, amorphous silicon oxide-alumina, and the like.

[0166] In embodiments, the hydrotreating support may comprise amorphous alumina. When a combination of silicon oxide and alumina is used, the distribution of silicon oxide and alumina within the support may be uniform or non-uniform. In some embodiments, the support may consist of an alumina gel in which silicon oxide, silicon oxide / alumina, or an alumina substrate is dispersed. The support may also comprise refractory materials other than alumina or silicon oxide, such as other inorganic oxides or clay particles, provided that such materials do not adversely affect the hydrogenation activity of the final catalyst or cause harmful cracking of the feedstock.

[0167] In the embodiments, silicon oxide and / or aluminum oxide constitute at least about 90 wt.% of the support of the hydrotreating catalyst, and in some embodiments, the support may be at least substantially all silicon oxide or all aluminum oxide.

[0168] In embodiments, the Group 8-10 metal modifier of the hydrotreating catalyst comprises Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, or combinations thereof. In embodiments, the Group 8-10 metal modifier of the hydrotreating catalyst comprises Group 9 metals, Group 10 metals, or combinations thereof. In embodiments, the Group 8-10 metal modifier of the hydrotreating catalyst comprises or is Co and / or Ni. In embodiments, the Group 8-10 metal modifier of the hydrotreating catalyst comprises or is Ni. In embodiments, the Group 8-10 metal modifier of the hydrotreating catalyst comprises Co and Ni. In embodiments, the Group 8-10 metal modifier is an oxide, hydroxide, or salt. In embodiments, the Group 8-10 metal modifier is a salt. Based on the dry bulk weight of the catalyst, calculated as metal oxides, the amount of the Group 8-10 metal modifier in the hydrotreating catalyst is generally 1 to 20 wt.% (e.g., 2 to 10 wt.%). In the embodiments, the Group 6 metal modifier of the hydrotreating catalyst is selected from Cr, Mo, W, and combinations thereof. In the embodiments, the Group 6 metal modifier of the hydrotreating catalyst comprises or is Mo. In the embodiments, the Group 6 metal modifier is an oxide, an oxyacid, or an ammonium salt containing an oxygen or polyoxyanion. Based on the dry bulk weight of the catalyst, calculated as a metal oxide, the amount of Group 6 metal modifier used in the hydrotreating catalyst is generally 5 to 50 wt.% (e.g., 10 to 40 wt.% or 15 to 30 wt.%). In the embodiments, the hydrotreating catalyst comprises Ni and Mo.

[0169] In the embodiments, Group 8-10 and / or Group 6 metal modifiers of the hydrotreating catalyst may be dispersed on an inorganic oxide support. Various methods are known in the art for depositing Group 8-10 and / or Group 6 metals or compounds containing such metals onto a support; such methods include ion exchange, impregnation, and co-precipitation. In the embodiments, impregnation of the support with Group 8-10 and Group 6 metal modifiers may be carried out at a controlled pH. Group 8-10 and Group 6 metal modifiers may be added to the impregnation solution as metal salts such as halide salts and / or amine complexes and / or salts of inorganic acids. Other examples of metal salts that may be used include nitrates, carbonates, and bicarbonates, as well as carboxylates such as acetates, citrates, and formates.

[0170] Depending on the circumstances, the impregnated support may be allowed to stand with the impregnation solution, for example, for a period ranging from about 2 to about 24 hours. After impregnating the oxide support with a Group 8-10 metal modifier and / or a Group 6 metal modifier, the impregnated support may be dried and / or calcined. After the hydrotreating catalyst has been dried and calcined, the prepared catalyst may be reduced with hydrogen or sulfided with a sulfur-containing compound, as is conventional in the art, and may be put into use, for example, in a hydrotreating reactor located upstream of the hydroisomerization reactor. [Example] []

[0171] The following illustrative examples are intended to be non-restrictive. [Overview of Examples] []

[0172] The following examples demonstrate that the processes and methods described in this paper efficiently provide high-yield diesel fuel exhibiting excellent cold flow characteristics. [Example] [1-] Provides catalyst containing zeolite SSZ-91 – Catalyst E []

[0173] Zeolite SSZ-91 is prepared according to US-A-9920260 (incorporated herein by reference) and as described herein (e.g., paragraph

[0074] above).

[0174] Zeolite SSZ-91 was then compounded with alumina to provide a mixture containing 65 wt.% SSZ-91. The mixture was extruded, dried, and calcined to form an extrudate substrate. The extrudate substrate was impregnated with a platinum-containing solution. The impregnated catalyst was then dried in air and subsequently calcined to provide catalyst (catalyst E). The total platinum loading of the catalyst product (referred to herein as catalyst E) was 0.6 wt.% (based on the total weight of the catalyst). [Example] [2-] Provides a catalyst containing zeolite SSZ-32x – Catalyst A []

[0175] Zeolite SSZ-32x was prepared according to US-A-7468126 (incorporated herein by reference) and as described herein (e.g., paragraph

[0124] above).

[0176] Zeolite SSZ-32x was then compounded with alumina to provide a mixture containing 45 wt.% SSZ-32x. The mixture was extruded, dried, and calcined to form an extrudate substrate. The extrudate substrate was impregnated with a platinum-containing solution. The impregnated catalyst was then dried in air and subsequently calcined to provide catalyst (catalyst A). The total platinum loading of the catalyst product (referred to herein as catalyst A) was 1 wt.%. [Example] [3-] Provides catalyst containing zeolite SSZ-32x – Catalyst B []

[0177] A catalyst containing zeolite SSZ-32x was prepared according to Example 2, except that the dried and calcined extrudate was impregnated with a platinum-containing solution to provide a catalyst with a total platinum loading of 0.325 wt.% (referred to herein as catalyst B). [Example] [4-] Provides a catalyst containing zeolite SSZ-32 – Catalyst C

[0178] Zeolite SSZ-32 is prepared according to US-A-5397454 (incorporated herein by reference) and as described herein (e.g., paragraph

[0108] above).

[0179] Zeolite SSZ-32 was then compounded with alumina to provide a mixture containing 65 wt.% SSZ-32. The mixture was extruded, dried, and calcined to form an extrudate substrate. The extrudate substrate was impregnated with a platinum-containing solution. The impregnated catalyst was then dried in air and subsequently calcined to provide catalyst (catalyst C). The total platinum loading of the catalyst product (referred to herein as catalyst C) was 0.325 wt.%. [Example] [5-] Provides catalyst containing zeolite SSZ-32 – Catalyst D []

[0180] A catalyst containing zeolite SSZ-32 was prepared according to Example 4, except that the mixture contained 45 wt.% zeolite SSZ-32. The dried and calcined extrudate was impregnated with a platinum-containing solution to provide a catalyst with a total platinum loading of 0.325 wt.% (referred to herein as catalyst D). [Example] [6]

[0181] Hydroisomerization was carried out in a micro-unit equipped with a downflow fixed-bed reactor. Each run was operated at a total pressure of 600 psig. The catalyst was activated by a standard reduction process before the feed was introduced. Feed A was passed through the hydroisomerization reactor at an LHSV of 2.6 h⁻¹ (catalyst E) or 2.71 h⁻¹ (catalyst A).

[0182] Raw material A is a Fe-Tropsch feedstock. Its characteristics are listed in Table 3. Table 3 Characteristics of Feed A raw material FT diesel API weight 50.9 Pour point, ℃ -12 Cloud point, ℃ -4 SIMDIST TBP (WT%),℉ 0.5 261 5 347 30 457 50 525 70 601 90 687 99.5 786

[0183] Example 6 tested catalysts A and E to process feedstock A according to the process shown in Figure 1. Table 4 summarizes the diesel yield and product characteristics. Both catalysts A and E successfully hydroisomerized the feedstock and lowered the cloud point to approximately -38°C. The diesel yields for catalysts A and E were 95.9 wt.% and 99.6 wt.%, respectively. Compared to catalyst A, catalyst E, containing zeolite SSZ-91, produced 3.7 wt.% more diesel. Products from both systems exhibited excellent cold-weather properties. Table 4 Diesel Yield and Characteristics catalyst Catalyst A Catalyst E Total pressure, psig 600 600 H2 rate, SCFB 3000 3000 Catalyst temperature,℉ 610 605 LHSV,hr -1 2.71 2.6 Diesel yield%, 395℉+ 95.9 99.6 Diesel pour point, ℃ -44 -43 Diesel cloud point, ℃ -38 -37 [Example] [7]

[0184] Raw material B is derived from animal fat. The characteristics of raw material B are listed in Table 5. Table 5 Characteristics of Feed B raw material biodiesel API 48 S,ppm 1 N,ppm 0 Pour point, ℃ 20 Cloud point, ℃ twenty two Boiling range,℉ 420-890

[0185] Example 7 uses catalysts B and E to process feedstock B according to the process shown in Figure 1. Table 6 summarizes the process conditions, diesel yield, and product characteristics. Both catalysts B and E successfully hydroisomerized the feedstock and lowered the cloud point to <-9°C. The diesel yields for catalysts B and E were 93.3 wt.% and 96.1 wt.%, respectively. This demonstrates the excellent performance of catalyst E, composed of zeolite SSZ-91, in the production of biodiesel (diesel fuel) from animal fats. Table 6 Diesel Yield and Characteristics catalyst Catalyst B Catalyst E Total pressure, psig 1000 1000 H2 rate, SCFB 5000 5000 Catalyst temperature,℉ 613 587 LHSV,hr -1 1.3 1.3 Diesel yield%, 380F+ 93.3 96.1 Diesel cloud point, ℃ -9 -12 [Example] [8]

[0186] Raw material C is hydrogenated linseed oil. Its properties are listed in Table 7. This feedstock has a high cloud point and pour point. Table 7 Feed C Characteristics raw material Hydrogenated linseed oil API weight 46.8 Cloud point, ℃ 30 Pour point, ℃ 26 SIMDIST TBP (WT%),℉ 0.5 549 5 575 30 619 50 620 70 621 90 652 99.5 782

[0187] Example 8 uses catalyst C to process hydrotreated linseed oil according to the process shown in Figure 1. The test was conducted at a total pressure of 1000 psig. The feed was passed through the reactor at an LHSV of 1 hr⁻¹. The hydrogen-to-oil ratio was approximately 5000 scfb.

[0188] Table 8 summarizes the process conditions, diesel yield, and product characteristics. With changes in catalyst temperature, the diesel yield increased from 94 wt.% to 91 wt.%, and the cloud point increased from -11°C to -21°C. Table 8 Diesel Yield and Characteristics catalyst Catalyst C Total pressure, psig 1000 LHSV,hr -1 1 H2 rate, SCFB 5000 Catalyst temperature,℉ 600 605 610 Gas yield, wt% 1.72 2.17 2.81 C5-180℉ Yield, wt.% 4.09 5.23 5.78 Yield (wt.%) 180℉-250℉ 0.63 0.71 1.41 Diesel yield, 250℉+, wt.% 93.97 92.34 90.47 Diesel cloud point, ℃ -11 -16 -twenty one Diesel pour point, ℃ -15 -25 -34 [Example] [9]

[0189] Raw material D is hydrotreated rapeseed diesel feedstock. Its characteristics are listed in Table 9. Table 9 Feed D Characteristics raw material Hydrogenated rapeseed feed API weight 47.3 Cloud point, ℃ 26 Pour point, ℃ 26 SIMDIST TBP (WT%),℉ 0.5 519 5 576 30 608 50 611 70 613 90 615 99.5 897

[0190] Example 9 uses a stratified system (according to the process in Figure 2) with catalyst C in the first hydroisomerization zone and catalyst D in the second hydroisomerization zone to process hydrotreated canola oil. The test was conducted at a total pressure of 1000 psig. The feed was passed through the reactor at an LHSV of 1 h⁻¹. The hydrogen-to-oil ratio was 4000 scfb.

[0191] Table 10 summarizes the process conditions, diesel yield, and product characteristics (for two independent processes operating with feed D via a layered catalyst system containing catalyst C and catalyst D). When the cloud point decreased from -15°C to -23°C, the diesel yield decreased from 88.7 wt.% to 84 wt.%. Table 10 Diesel Yield and Characteristics catalyst Catalyst C / Catalyst D Catalyst temperature,℉ 600 610 Gas yield, wt.% 2.5 3.6 C5-180℉ Yield, wt.% 3.2 4.3 Yield (wt.%) 180℉-350℉ 6.0 8.7 Diesel yield 350℉+, wt.% 88.7 84.0 Diesel cloud point, ℃ -15 -twenty three Diesel pour point, ℃ -31 -45

[0192] It should be understood that the present invention is not limited to the above embodiments, and various modifications and improvements can be made without departing from the concepts described herein. Except in cases of mutual exclusion, any feature may be used alone or in combination with any other feature, and this disclosure extends to and includes all combinations and sub-combinations of one or more features described herein.

[0193] For the avoidance of doubt, this application relates to the subject matter described in the following numbered paragraphs: 1. A process for hydroisomerizing diesel feedstock, the process comprising contacting the diesel feedstock with a hydroisomerization catalyst, The diesel feedstock may contain biological components or Fischer-Tropsch feedstock, and the hydroisomerization catalyst may contain zeolite SSZ-91, zeolite SSZ-32, or zeolite SSZ-32x. [] 2. A process for upgrading diesel feedstock, the process comprising: Under hydroisomerization conditions, diesel feedstock is contacted with a hydroisomerization catalyst to provide diesel fuel with a lower cloud point and lower pour point compared to the original diesel feedstock. The diesel feedstock may contain biological components or Fischer-Tropsch feedstock, and the hydroisomerization catalyst may contain zeolite SSZ-91, zeolite SSZ-32, or zeolite SSZ-32x. 3. According to the process described in paragraph 1 or 2, the hydroisomerization catalyst comprises zeolite SSZ-91 and group 8-10 metals. 4. According to any one of paragraphs 1-3, the hydroisomerization catalyst comprises zeolite SSZ-91, wherein the zeolite SSZ-91, in its calcined form, has substantially the X-ray diffraction pattern shown in the table below: 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, wherein the strongest line in the X-ray pattern is specified as 100: W = weak (>0 to ≤20); M = moderate (>20 to ≤40); S = strong (>40 to ≤60); VS = very strong (>60 to ≤100). 5. The process according to any one of paragraphs 1 to 4, wherein the hydroisomerization catalyst comprises zeolite SSZ-91 having a silica to alumina ratio of 70 to 160, or 80 to 160, or 80 to 140, or 100 to 160. 6. The process according to any one of paragraphs 1 to 5, wherein the hydroisomerization catalyst comprises zeolite SSZ-91, the zeolite having at least about 80% polytype 6 of total ZSM-48 material present in the zeolite SSZ-91, or at least about 90% polytype 6 of total ZSM-48 material present in the zeolite SSZ-91. 7. The process according to any one of paragraphs 1 to 6, wherein the hydroisomerization catalyst comprises zeolite SSZ-91 and the zeolite SSZ-91 comprises 0.1 to 4.0 wt.% of EUO type molecular sieve phase. 8. The process according to any one of paragraphs 1 to 7, wherein the hydroisomerization catalyst comprises zeolite SSZ-91, the zeolite comprising 0.1 to 4.0 wt.% EU-1. 9. The process according to any one of paragraphs 1 to 8, wherein the hydroisomerization catalyst comprises zeolite SSZ-91, the zeolite having a morphology characterized as a polycrystalline aggregate comprising microcrystals having an average aspect ratio of 1 to 4. 10. A process according to any one of paragraphs 1 to 9, wherein the hydroisomerization catalyst comprises zeolite SSZ-91, the zeolite having: A silicon oxide to aluminum oxide ratio of 70 to 160; One morphology is characterized as a polycrystalline aggregate comprising microcrystals having an average aspect ratio in the range of 1 to 4; At least about 80% polytype 6 of the total ZSM-48 type material present in the zeolite SSZ-91; and EUO type molecular sieve phase, 0.1 to 4.0 wt.%. 11. The process according to any one of paragraphs 1 to 10, wherein the hydroisomerization catalyst comprises about 5 to about 95 wt.% of zeolite SSZ-91 and about 0.05 to about 2.0 wt.% of metal modifier. 12. According to the process described in paragraph 1 or 2, the hydroisomerization catalyst comprises zeolite SSZ-32 and group 8-10 metals. 13. The process according to any one of paragraphs 1, 2 or 12, wherein the zeolite SSZ-32 contains a silicon oxide (SiO 2) to aluminum oxide (Al 2O 3) molar ratio (SAR) in the range of 25-37. 14. The process according to any one of paragraphs 1, 2, 12 or 13, wherein the zeolite SSZ-32 has a crystal size in the range of about 0.1 μm to about 0.4 μm. 15. According to the process described in paragraphs 1, 2, or 12-14, the synthesized zeolite SSZ-32 has a crystalline structure, and the X-ray powder diffraction of this crystalline structure shows the following characteristic lines: d / n Int.I / I o 11.05 10.05 7.83 4.545 26 10 17 71 4.277 71 3.915 100 3.726 98 . 16. According to the process described in paragraph 1 or 2, the hydroisomerization catalyst comprises zeolite SSZ-32x and group 8-10 metals. 17. A process according to any one of paragraphs 1, 2 or 16, wherein the zeolite SSZ-32x contains a silicon oxide (SiO 2) to aluminum oxide (Al 2O 3) molar ratio (SAR) in the range of 25-37. 18. A process according to any one of paragraphs 1, 2, 16 or 17, wherein the zeolite SSZ-32x has a crystal size in the range of about 100 to about 400 angstroms. 19. According to the process described in paragraphs 1, 2, or any one of 16-18, the synthesized zeolite SSZ-32x has a crystalline structure, and the X-ray powder diffraction of this crystalline structure shows the following characteristic lines: 2θ d-Spacing (Å) strength Relative intensity (%) (I / I oX 100) 8.00 11.05 15 26 8.80 10.05 6 10 11.30 7.83 10 17 14.50 6.11 1 2 15.75 5.63 3 5 16.50 5.37 3 5 18.10 4.901 7 12 19.53 4.545 41 71 20.05 4.428 6 acromion 10 acromion 20.77 4.277 41 71 21:30 4.171 7 12 22.71 3.915 58 100 23.88 3.726 57 98 24.57 3.623 30 52 25.08 3.551 25 43 25.88 3.443 27 47 26.88 3.317 5 9 28.11 3.174 6 10 . 20. The process according to any one of paragraphs 12-19, wherein the hydroisomerization catalyst comprises zeolite SSZ-32, zeolite SSZ-32x and about 0.05 to about 2.0 wt.% of a metal modifier. 21. The process according to any one of paragraphs 1 to 20, wherein the hydroisomerization catalyst is a layered catalyst. 22. According to the process in paragraph 21, the hydroisomerization catalyst includes a first layer containing a first hydroisomerization catalyst and a second layer containing a second hydroisomerization catalyst, wherein the first hydroisomerization catalyst is located in a first hydroisomerization region and the second hydroisomerization catalyst is located in a second hydroisomerization region. 23. According to the process of paragraph 21 or 22, when belonging to any of paragraphs 1-12, the hydroisomerization catalyst comprises at least one layer containing zeolite SSZ-91. 24. According to any one of paragraphs 21-23, when it belongs to any one of paragraphs 1-11, the layered catalyst comprises a first layer containing a first hydroisomerization catalyst and a second layer containing a second hydroisomerization catalyst, wherein the first hydroisomerization catalyst or the second hydroisomerization catalyst comprises zeolite SSZ-91 and the first hydroisomerization catalyst and the second hydroisomerization catalyst are mutually exclusive. 25. According to the process described in paragraph 24, the first hydroisomerization catalyst and the second hydroisomerization catalyst comprise zeolite SSZ-91 and group 8-10 metals. 26. The process according to any one of paragraphs 1, 2 or 12-22, wherein the hydroisomerization catalyst is a layered catalyst and wherein the hydroisomerization catalyst comprises at least one layer comprising zeolite SSZ-32 or SSZ-32x. 27. A process according to any one of paragraphs 1, 2 or 12-22, wherein the hydroisomerization catalyst is a layered catalyst comprising a first layer containing a first hydroisomerization catalyst and a second layer containing a second hydroisomerization catalyst, wherein the first hydroisomerization catalyst or the second hydroisomerization catalyst comprises zeolite SSZ-32 or SSZ-32x and the first hydroisomerization catalyst and the second hydroisomerization catalyst are mutually exclusive. 28. According to the process described in paragraph 27, the first hydroisomerization catalyst and the second hydroisomerization catalyst comprise zeolite SSZ-32 and group 8-10 metals. 29. According to the process described in paragraph 27, the first hydroisomerization catalyst and the second hydroisomerization catalyst comprise zeolite SSZ-32x and group 8-10 metals. 30. A process according to any of the preceding paragraphs, wherein the diesel feedstock comprises or is a Fischer-Tropsch feedstock and the Fischer-Tropsch feedstock has a 90% distillation temperature of less than about 750℉ (about 399°C), for example less than about 700℉ (about 371°C). 31. The process according to any of the preceding paragraphs, wherein the diesel feedstock comprises or is selected from a biological component feedstock of vegetable oils and animal fats, wherein the vegetable oils and animal fats comprise triglycerides and free fatty acids, for example wherein the biological component feedstock is selected from rapeseed oil, corn oil, soybean oil, castor oil, linseed oil, palm oil, and combinations thereof. 32. A process according to any of the preceding paragraphs, wherein the diesel feedstock is contacted with the hydroisomerization catalyst and hydrogen under hydroisomerization conditions in an isomerization reactor, wherein the hydroisomerization conditions are: Temperatures ranging from approximately 390℉ to approximately 800℉ (199℃ to 427℃); Pressures ranging from approximately 15 to approximately 3000 psig (0.10 to 20.68 MPa gauge pressure); The diesel feedstock is fed into the reactor containing the hydroisomerization catalyst at a rate ranging from about 0.1 to about 20 h⁻¹ LHSV; and Hydrogen and diesel feedstock are fed into the reactor at a ratio of approximately 2,000 to approximately 10,000 standard cubic feet H2 / barrel of diesel feedstock (approximately 360 to approximately 1,800 m3 H2 / m3 feed). 33. The process according to any of the preceding paragraphs further includes contacting the diesel feedstock with the hydrotreating catalyst under hydrotreating conditions before contacting the diesel feedstock with the hydrotreating catalyst. 34. According to the process described in paragraph 33, the conditions for such hydrogenation treatment are: Temperatures ranging from approximately 390℉ to approximately 800℉ (199℃ to 427℃); Pressures ranging from approximately 15 to approximately 3000 psig (0.10 to 20.68 MPa gauge pressure); The diesel feedstock is fed into the reactor containing the hydrotreating catalyst at a rate ranging from about 0.1 to about 20 h⁻¹ LHSV; and Hydrogen and diesel feedstock are fed into the reactor at a ratio of approximately 2,000 to approximately 10,000 standard cubic feet H2 / barrel of diesel feedstock (approximately 360 to approximately 1,800 m3 H2 / m3 feed). 35. According to paragraph 1 or paragraphs 3-34, the process of contacting the diesel feedstock with the hydroisomerization catalyst provides a diesel fuel that exhibits a lower cloud point and a lower pour point compared to the cloud point and pour point of the diesel feedstock. 36. According to the process of paragraph 2 or paragraph 35, the diesel fuel exhibits a cloud point at least 10°C lower than the cloud point of the diesel feedstock and a pour point at least 10°C lower than the pour point of the diesel feedstock, or a cloud point at least 20°C lower than the cloud point of the diesel feedstock and a pour point at least 20°C lower than the pour point of the diesel feedstock, or a cloud point at least 30°C lower than the cloud point of the diesel feedstock and a pour point at least 30°C lower than the pour point of the diesel feedstock. 37. Using a hydroisomerization catalyst comprising zeolite SSZ-91, zeolite SSZ-32, or zeolite SSZ-32x to provide a diesel fuel exhibiting a lower cloud point and a lower pour point compared to the cloud point and pour point of a diesel feedstock for producing diesel fuel, wherein the diesel fuel is produced by contacting the diesel feedstock with the hydroisomerization catalyst, and the diesel feedstock comprises or is a bio-component feed or a Fischer-Tropsch feed. 38. A process for providing diesel fuel exhibiting a lower cloud point and lower pour point compared to the cloud point and pour point of diesel feedstock used to produce diesel fuel, the process comprising contacting the diesel feedstock with a hydroisomerization catalyst comprising zeolite SSZ-91, zeolite SSZ-32 or zeolite SSZ-32x under hydroisomerization conditions to provide diesel fuel exhibiting a lower cloud point and lower pour point compared to the cloud point and pour point of diesel feedstock used to produce diesel fuel, wherein the diesel feedstock comprises or is a bio-component feed or a Fischer-Tropsch feed.

[0194] 10: Diesel fuel 12: Hydrogen 14: Hydroisomerization reactor 14a: First hydroisomerization region 14b: Second hydroisomerization region 16: Hydroisomerization catalyst 16a: First hydroisomerization catalyst 16b: Second hydroisomerization catalyst 18: Streams via hydroisomerization

Claims

1. A process for hydroisomerizing diesel feedstock, the process comprising contacting the diesel feedstock with a hydroisomerization catalyst, wherein the diesel feedstock comprises a bio-component feed selected from vegetable oils and animal fats or a Fischer-Tropsch feedstock having a 90% distillation temperature of less than about 750℉, the vegetable oils and animal fats comprising triglycerides and free fatty acids, and the hydroisomerization catalyst comprising zeolite SSZ-91.

2. The process of claim 1, wherein the hydroisomerization catalyst comprises zeolite SSZ-91 and group 8-10 metals.

3. The process of claim 1, wherein the zeolite SSZ-91, in its calcined form, has substantially the X-ray diffraction pattern shown in the table below: (a) ±0.20 (b) wherein the provided powder XRD pattern is based on a relative intensity scale, wherein the strongest line in the X-ray pattern is specified as 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).

4. The process of claim 1, wherein the hydroisomerization catalyst comprises zeolite SSZ-91, the zeolite having at least about 80% polymorph 6 of total ZSM-48 type material present in the zeolite SSZ-91.

5. The process of claim 1, wherein the zeolite SSZ-91 comprises 0.1 to 4.0 wt.% of EUO type molecular sieve phase.

6. The process of claim 1, wherein the zeolite SSZ-91 contains 0.1 to 4.0 wt.% EU-1.

7. The process of claim 1, wherein the zeolite SSZ-91 has a morphology characterized as a polycrystalline aggregate comprising microcrystals having an average aspect ratio of 1 to 4.

8. The process of claim 1, wherein the zeolite SSZ-91 has: a silica to alumina ratio of 70 to 160; a morphology characterized as a polycrystalline aggregate comprising microcrystals having an average aspect ratio in the range of 1 to 4; at least about 80% polymorph 6 of the total ZSM-48 type material present in the zeolite SSZ-91; and 0.1 to 4.0 wt.% of EUO type molecular sieve phase.

9. The process of claim 1, wherein the hydroisomerization catalyst comprises about 5 to about 95 wt.% of zeolite SSZ-91 and about 0.05 to about 2.0 wt.% of metal modifier.

10. The process of claim 1, wherein the hydroisomerization catalyst further comprises zeolite SSZ-32 and group 8-10 metals.

11. The process of claim 10, wherein the zeolite SSZ-32 contains a silicon oxide (SiO2) to aluminum oxide (Al2O3) molar ratio (SAR) in the range of 25-37.

12. The process of claim 10, wherein the zeolite SSZ-32 has a crystal size in the range of about 0.1 μm to about 0.4 μm.

13. The process of claim 10, wherein the synthesized zeolite SSZ-32 has a crystalline structure, the X-ray powder diffraction of which shows the following characteristic lines: .

14. The process of claim 1, wherein the hydroisomerization catalyst further comprises zeolite SSZ-32x and group 8-10 metals.

15. The process of claim 14, wherein the zeolite SSZ-32x contains a silicon oxide (SiO2) to aluminum oxide (Al2O3) molar ratio (SAR) in the range of 25-37.

16. The process of claim 14, wherein the zeolite SSZ-32x has a crystal size in the range of about 100 to about 400 angstroms.

17. The process of claim 14, wherein the synthesized zeolite SSZ-32x has a crystalline structure, the X-ray powder diffraction of which shows the following characteristic lines: .

18. The process of claim 1, wherein the hydroisomerization catalyst further comprises zeolite SSZ-32 or zeolite SSZ-32x and about 0.05 to about 2.0 wt.% of a metal modifier.

19. The process of claim 1, wherein the hydroisomerization catalyst is a layered catalyst.

20. The process of claim 19, wherein the hydroisomerization catalyst comprises a first layer comprising a first hydroisomerization catalyst and a second layer comprising a second hydroisomerization catalyst, the first hydroisomerization catalyst being located in a first hydroisomerization region and the second hydroisomerization catalyst being located in a second hydroisomerization region.

21. The process of claim 19, wherein the hydroisomerization catalyst comprises at least one layer comprising zeolite SSZ-91.

22. The process of claim 19, wherein the layered catalyst comprises a first layer comprising a first hydroisomerization catalyst and a second layer comprising a second hydroisomerization catalyst, wherein the first hydroisomerization catalyst or the second hydroisomerization catalyst comprises zeolite SSZ-91 and the first hydroisomerization catalyst and the second hydroisomerization catalyst are mutually exclusive.

23. The process of claim 22, wherein the first hydroisomerization catalyst and the second hydroisomerization catalyst comprise zeolite SSZ-91 and group 8-10 metals.

24. The process of claim 1, wherein the hydroisomerization catalyst is a layered catalyst and wherein the hydroisomerization catalyst further comprises at least one layer comprising zeolite SSZ-32 or SSZ-32x.

25. The process of claim 1, wherein the hydroisomerization catalyst is a layered catalyst comprising a first layer containing a first hydroisomerization catalyst and a second layer containing a second hydroisomerization catalyst, wherein the first hydroisomerization catalyst or the second hydroisomerization catalyst further comprises zeolite SSZ-32 or SSZ-32x and the first hydroisomerization catalyst and the second hydroisomerization catalyst are mutually exclusive.

26. The process of claim 25, wherein the first hydroisomerization catalyst and the second hydroisomerization catalyst comprise zeolite SSZ-32 and group 8-10 metals.

27. The process of claim 25, wherein the first hydroisomerization catalyst and the second hydroisomerization catalyst comprise zeolite SSZ-32x and group 8-10 metals.

28. The process of claim 1, wherein the Fischer-Tropsch feed has a 90% distillation temperature of less than about 700℉.

29. The process of claim 1, wherein the diesel feedstock comprises a bio-component feedstock selected from rapeseed oil, corn oil, soybean oil, castor oil, linseed oil, palm oil, and combinations thereof.

30. The process of claim 1, wherein contacting the diesel feedstock with the hydroisomerization catalyst provides a diesel fuel exhibiting a lower cloud point and a lower pour point compared to the cloud point and pour point of the diesel feedstock.

31. A process for hydroisomerizing diesel feedstock, the process comprising contacting a diesel feedstock with a hydroisomerization catalyst, wherein the diesel feedstock comprises a bio-component feed or a Fischer-Tropsch feed, and the hydroisomerization catalyst comprises zeolite SSZ-91, and wherein the diesel feedstock is contacted with the hydroisomerization catalyst and hydrogen in an isomerization reactor under hydroisomerization conditions, the hydroisomerization conditions being: a temperature in the range of about 390℉ to about 800℉; a pressure in the range of about 15 to about 3000 psig; a feed rate of diesel feedstock to the reactor containing the hydroisomerization catalyst at a rate in the range of about 0.1 to about 20 h⁻¹ liquid hourly space velocity (LHSV); and a feed rate of hydrogen and diesel feedstock to the reactor at a ratio of about 2000 to about 10,000 standard cubic feet H₂ / barrel of diesel feedstock.

32. A process for hydroisomerizing diesel feedstock, the process comprising contacting the diesel feedstock with a hydroisomerization catalyst, wherein the diesel feedstock comprises a bio-component feed or a Fischer-Tropsch feedstock, and the hydroisomerization catalyst comprises zeolite SSZ-91, and further comprising contacting the diesel feedstock with a hydrotreating catalyst under hydrotreating conditions prior to contacting the diesel feedstock with the hydrotreating catalyst.

33. As in claim 32, the hydrotreating conditions are: a temperature in the range of about 390℉ to about 800℉; a pressure in the range of about 15 to about 3000 psig; a feed rate of diesel feedstock to the reactor containing the hydrotreating catalyst at a rate in the range of about 0.1 to about 20 h⁻¹ liquid hourly space velocity (LHSV); and a feed rate of hydrogen and diesel feedstock to the reactor at a ratio of about 2000 to about 10,000 standard cubic feet H₂ / barrel of diesel feedstock.

34. A process for upgrading diesel feedstock, the process comprising: contacting a diesel feedstock with a hydroisomerization catalyst under hydroisomerization conditions to provide diesel fuel having a lower cloud point and a lower pour point compared to the cloud point and pour point of the diesel feedstock, wherein the diesel feedstock comprises a bio-component feedstock selected from vegetable oils and animal fats or a Fischer-Tropsch feedstock having a 90% distillation temperature of less than about 750℉, the vegetable oils and animal fats comprising triglycerides and free fatty acids, and the hydroisomerization catalyst comprising zeolite SSZ-91.

35. The process of claim 34, wherein the diesel fuel exhibits a cloud point at least 10°C lower than the cloud point of the diesel feedstock and a pour point at least 10°C lower than the pour point of the diesel feedstock.

36. A process for providing diesel fuel exhibiting a lower cloud point and lower pour point compared to the cloud point and pour point of a diesel feedstock for producing diesel fuel, the process comprising contacting the diesel feedstock with a hydroisomerization catalyst comprising zeolite SSZ-91 under hydroisomerization conditions to provide diesel fuel exhibiting a lower cloud point and lower pour point compared to the cloud point and pour point of the diesel feedstock for producing diesel fuel, wherein the diesel feedstock comprises a bio-component feed selected from vegetable oils and animal fats or a Fischer-Tropsch feedstock having a 90% distillation temperature of less than about 750℉, the vegetable oils and animal fats comprising triglycerides and free fatty acids.

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