Use of SSZ-41x and MTW Zeolites for the Production of Jet and Diesel Fuel

Abstract

A process for producing distillate range hydrocarbons using MTW catalyst and / or SSZ-41x catalyst is disclosed.

Description

[Technical field]

[0001]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Application No. 63 / 314,505, filed February 28, 2022, the disclosure of which is incorporated herein by reference.

[0002] The present invention relates to the use of catalysts comprising SSZ-41x and / or MTW for hydroprocessing (including hydrocracking and hydroisomerization) of hydrocarbon feedstocks for the production of distillate fuels. [Background technology]

[0002]

[0001] As demand for diesel and jet boiling range fuels increases worldwide, there is growing interest in feedstocks other than crude oil.

[0002] MTW and SSZ-41 have the potential to be alternatives or replacements for zeolites such as USY that are commonly used to process non-renewable petroleum hydrocarbons for liquid fuel production. However, of particular interest is the application of MTW and SSZ-41 zeolites to the production of fuels derived from renewable sources. Paraffinic hydrocarbons, including n-hexadecane (n-C16) and n-octadecane (n-C18), can be readily produced by hydrodeoxygenation of free fatty acids (e.g., palmitic acid or linoleic acid) present in the form of free acids or triglycerides in renewable vegetable or animal oils. Such paraffins can then be converted to hydrocarbon species with boiling points in the jet range via catalytic hydrocracking (HCR) and / or hydroisomerization (HIS) to create a route for producing jet fuel from renewable feedstocks.

[0003] The selective conversion of n-C18, readily available from a variety of renewable feedstocks, to products with the desired jet boiling range is difficult. The difficulties have hindered attempts to develop economically viable routes to produce renewable aviation fuels. The use of SSZ-41x and / or MTW zeolites as key components in HCR / HIS catalysts herein may provide such a route in addition to use in conventional HCR / HIS applications. Summary of the Invention

[0004] In one aspect, a process for producing distillate range hydrocarbons is provided, the process comprising: contacting a hydrocarbon feedstock with a hydrotreating catalyst under hydrotreating conditions to produce a hydrotreated effluent; and fractionating the hydrotreated effluent to recover one or more hydrocarbon fractions boiling within a diesel or jet fuel range, the hydrotreating catalyst comprising a support component and a metal component supported on the support component, the support component comprising: (i) an MTW zeolite and / or SSZ-41x zeolite in an amount of 0.1 wt.% to 75 wt.% based on a total weight of the support; (ii) an amorphous silica-alumina in an amount of 15 wt.% to 85 wt.% based on a total weight of the support; and (iii) an alumina binder in an amount of 5 wt.% to 55 wt.% based on a total weight of the support, the metal component comprising a Group 6 metal and a Group 8-10 non-noble metal. [Brief description of the drawings]

[0005] [Figure 1] 1 is a graph of catalyst activation temperature (CAT) versus hydrocracking (HCR) conversion (<500° F.) during n-octadecane hydroconversion over the MTW catalyst and the SSZ-41x catalyst used in Example 1.

[0006] [Diagram 2] 1 is a graph of product fraction yield versus HCR conversion (<500° F.) during n-octadecane hydroconversion over the MTW and SSZ-41x catalysts used in Example 1.

[0007] [Diagram 3] 1 is a graph of the freezing point of the jet product fraction versus HCR conversion (<500° F.) during the hydroconversion of n-octadecane over the MTW and SSZ-41x catalysts used in Example 1.

[0008] [Figure 4A] 1 is a graph of jet product cloud point and pour point versus HCR conversion (<500° F.) during n-octadecane hydroconversion over the SSZ-41x catalyst used in Example 1.

[0009] [Figure 4B] 1 is a graph of jet product cloud point and pour point versus HCR conversion (<500° F.) during n-octadecane hydroconversion over the MTW catalyst used in Example 1.

[0010] [Diagram 5] 1 is a graph of distillate yield versus HCR conversion (<700° F.) during hydroconversion of unconverted oil over the MTW and SSZ-41x catalysts used in Example 2.

[0011] [Figure 6] 1 is a graph of CAT vs. HCR conversion (<700° F.) during hydroconversion of unconverted oil over the MTW catalyst and the SSZ-41x catalyst used in Example 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] definition The boiling range of jet fuel is defined as 140° C. to 300° C. Jet fuel boiling range fractions are defined as those fractions with an initial boiling point equal to or greater than 140° C., a T10 distillation point equal to or less than 205° C., and a final boiling point equal to or less than 300° C. Unless otherwise specified, distillation and boiling points may be determined according to ASTM D2887.

[0013] The boiling range of diesel is defined as 140° C. to 375° C. The diesel boiling range fraction is defined as the fraction having a T10 distillation point equal to or greater than 140° C., a final boiling point equal to or greater than 300° C., and a T90 distillation point equal to or less than 375° C.

[0014] The boiling range of distillate fuels (jet plus diesel) is defined as about 140°C to about 427°C.

[0015] The "T10" boiling point of a feedstock means the temperature at which 10% by weight of the feedstock vaporizes. Similarly, the "T90" boiling point means the temperature at which 90% by weight of the feedstock vaporizes. Any suitable ASTM method, such as ASTM D86 or ASTM D2887, can be used to measure boiling points (including fractional boiling points).

[0016] The term "hydrotreating" is intended to refer to the process of converting hydrocarbons into more valuable products in the presence of a hydrotreating catalyst and hydrogen.

[0017] The terms "hydrocracking" ("HCR") and "hydroconversion" are intended to refer to any process in which a hydrocarbon feedstream is contacted with a catalyst and hydrogen at high pressure and temperature to convert at least a portion of the hydrocarbon feedstream to lower boiling point products, thereby resulting in an overall lower average boiling point product stream on a weight percent basis. Hydrocracking is a part of the hydrotreating process. Of course, "hydrocracking" or "hydroconversion" can also include hydroisomerization ("HIS") of long chain paraffins present in the hydrocarbon stream. Hydroisomerization can improve cold flow properties by increasing the proportion of branched paraffins.

[0018] The term "MTW" includes all molecular sieves and their isotypes designated as MTW framework by the Structure Commission of the International Zeolite Association. MTW framework molecular sieves have a unique pore system consisting of one-dimensional channels containing 12-membered T-atom rings. Molecular sieves having the MTW framework type include CZH-5, NU-13, Theta-3, TPZ-12, and ZSM-12.

[0019] The term "SSZ-41x" refers to a zincoaluminosilicate molecular sieve having the framework structure of SSZ-41 and characterized in that (a) the SiO2 / Al2O3 molar ratio is less than 30-100 (e.g., 50-90 or 60-80), (b) the SiO2 / ZnO molar ratio is 15-75 (e.g., 20-40), and (c) the average crystal size is less than 500 nm (e.g., 50-500 nm, or 50-250 nm, or 75-500 nm, or 75-250 nm). As conventionally synthesized according to the teachings of U.S. Patent No. 5,591,421, SSZ-41 has an average crystal size of at least 1000 nm. SSZ-41 has a structure similar to VPI-8 (VET framework), a material with unique one-dimensional channels containing 12-membered T-atom rings, but differs from VPI-8 in that SSZ-41 has a greater argon retention (e.g., up to about three times) than reported for VPI-8. SSZ-41 may contain aluminum in its framework structure, whereas VPI-8 does not contain framework aluminum.

[0020] The term "zincoaluminosilicate" refers to synthetic molecular sieves having a framework structure constructed from zinc, alumina, and silica (i.e., repeating tetrahedral units of ZnO4, AlO4, and SiO4).

[0021] The term "unconverted oil" and its acronym "UCO" refer to a highly paraffinic fraction from a hydrocracker that contains hydrocarbons with low nitrogen, sulfur, and Ni content and an initial boiling point that corresponds to the end point of atmospheric gas oil (AGO) range hydrocarbons. In certain embodiments, the initial boiling point is in the range of 340°C to 370°C (e.g., 340°C, or 360°C, or 370°C) and the end point is in the range of about 510°C to 560°C (e.g., 540°C, or 550°C, or 560°C). UCO is also known in the industry by other synonyms such as "hydrowax".

[0022] The term "Cn hydrocarbons" or "Cn" (where n is an integer value) means hydrocarbons having that number of carbon atoms. The term "Cn+ hydrocarbons" or "Cn+" refers to hydrocarbons having that number of carbon atoms or more. The term "Cn- hydrocarbons" or "Cn-" refers to hydrocarbons having that number of carbon atoms or less.

[0023] The terms "wt. %, "vol. %, "or "mol. %" refer to the weight percentage, volume percentage, or molar percentage, respectively, of a component relative to the total weight, volume, or moles of a material that contains that component. In a non-limiting example, 100 grams of a material containing 10 grams of a particular component contains 10% by weight of that component.

[0024] The term "SiO2 / Al2O3 molar ratio" is sometimes abbreviated as "SAR."

[0025] Hydrocarbon Feedstock A wide range of petroleum and chemical feedstocks can be hydrotreated in accordance with the present disclosure. Suitable feedstocks include whole and reduced crude oils, atmospheric oils, cycle oils, gas oils including vacuum gas oils and coker gas oils, as well as light to heavy distillates including unrefined fractions, hydrocrackates, hydrotreated oils, slack waxes, Fischer-Tropsch waxes, raffinates, and mixtures of these materials.

[0026] In some embodiments, at least a portion of the feedstock may represent a feedstock derived from a biocomponent source. As used herein, biocomponent feed refers to a hydrocarbon feedstock derived from a biological feedstock component, derived from a biocomponent source such as a plant, animal, fish, and / or algae. Biocomponent feedstocks can be obtained, for example, by hydrodeoxygenation and optionally isomerization of renewable oils.

[0027] A feedstock comprises at least about 10% by weight (e.g., at least 25% by weight, or at least 40% by weight, or at least 50% by weight, or at least 75% by weight, or at least 90% by weight, or at least about 95% by weight) of the raw material relative to the biocomponent source or sources. Additionally or alternatively, the feedstock can be entirely raw material from the biocomponent source, or the feedstock can comprise about 99% or less by weight (e.g., 90% or less, or 75% or less, or 50% or less) of the raw material relative to the biocomponent source.

[0028] One way to define the feedstock is based on the boiling range of the feedstock. Typical feedstocks include, for example, feedstocks having an initial boiling point and / or T5 boiling point of at least about 400°F (204°C) (e.g., at least about 450°F (232°C)). Additionally or alternatively, the end, T95 and / or T90 boiling points of the feedstock may be about 850°F (454°C) or less, e.g., 800°F (427°C) or less, or about 750°F (399°C) or less. It is noted that feedstocks with lower T5 boiling points may also be suitable. However, the resulting yield of such low boiling feedstocks may be determined relative to the 400°F+ (204°C+) portion of the feedstock.

[0029] In some embodiments, the feedstock may have a higher n-paraffin content. The n-paraffin content of the feedstock may be at least 40% by weight (e.g., at least 50% by weight, or at least 75% by weight, or at least 90% by weight, or at least 95% by weight).

[0030] Hydrotreating Hydrotreating can be carried out by exposing the feed to a hydrotreating catalyst under effective hydrotreating conditions.

[0031] Hydrotreating can be carried out in one or more fixed-bed, ebullated-bed, slurry-bed, moving-bed, continuous stirred tank (CSTR), or tubular reactors in series and / or parallel configurations. Fixed-bed reactors can include multiple vessels, single or multiple catalyst beds in each vessel, and various combinations of hydrotreating catalysts in one or more vessels.

[0032] The reaction conditions during hydroprocessing can be selected to provide a desired level of conversion of the feedstock. The conversion of the feedstock can be defined in terms of converting molecules boiling above a threshold temperature to molecules boiling below that threshold. The conversion temperature can be any convenient temperature, such as 260° C. (500° F.) or 371° C. (700° F.). For example, the process conditions can be selected to achieve at least 10% conversion of the 260° C.+ portion of the feedstock. That is, the conditions are selected to convert at least about 10% by weight of the portion of the feedstock boiling above 260° C. to a portion boiling below 260° C. In some embodiments, the single pass conversion to 260° C. can be at least 20% (e.g., at least 30%, or at least 40%, or at least 50%). Additionally or alternatively, the conversion percentage can be about 80% or less (e.g., 70% or less, or 60% or less). An example of a suitable conversion amount may be a conversion percentage of 30% to 80% (eg, 40% to 70%).

[0033] The process conditions include a reaction temperature in the range of 300°C to 500°C (e.g., 300°C to 450°C, or 330°C to 450°C), a total pressure in the range of 6 MPa to 30 MPa (e.g., 10 MPa to 20 MPa, or 12 MPa to 18 MPa), a hydrogen supply rate (standard liters per liter of hydrocarbon feedstock) in the range of 800 SL / L to 2000 SL / L (e.g., 1000 SL / L to 2000 SL / L, or 1000 SL / L to 1500 SL / L), and a reaction time of 0.1 h. -1 ~10h -1 (For example, 0.5h -1 ~5h -1 , or 0.5h -1 ~2h -1 ) liquid hourly space velocity (LHSV) in the range

[0034] Hydroprocessing is carried out in the presence of hydrogen. Thus, a hydrogen stream is fed or injected into the reactor or reaction zone or hydroprocessing zone where the hydroprocessing catalyst is located. The hydrogen contained in the hydrogen "treat gas" can be either pure hydrogen or a hydrogen-containing gas. A hydrogen-containing gas is a gas stream containing a sufficient amount of hydrogen for the intended reaction(s) and optionally containing one or more other gases (e.g., nitrogen and light hydrocarbons such as methane). The treat gas stream introduced into the reaction stage can contain at least 50% by volume (e.g., at least 75% by volume) of hydrogen. Optionally, the hydrogen treat gas can be substantially free (less than 1% by volume) of impurities such as H2S and NH3, and / or such impurities can be substantially removed from the treat gas before use. Hydrogen can be fed to the hydroprocessing reactor and / or reaction zone simultaneously with the input feed or separately through a separate gas conduit.

[0035] Following hydrotreating, the hydrotreated effluent can then be passed through a gas-liquid separator to remove the gas phase portion from the effluent. The liquid phase effluent from the separator can then be fractionated to produce at least a converted fraction comprising products in the distillate range and an unconverted fraction comprising higher boiling range products typically obtained from the unconverted portion. For example, a fractionator can be used to produce at least a diesel fraction and a jet hydrocarbon fraction. The unconverted portion can then be hydrocracked and optionally the remaining unconverted portion can be recycled for further hydrocracking. Optionally, a common fractionator or other separator can be used to separate the distillate fuel boiling range products from the unconverted portion of the feedstock having a boiling range above the distillate fuel boiling range. Fractionation can be performed using a distillation unit, such as, for example, an atmospheric distillation unit.

[0036] Optionally, the hydrotreated product can be dewaxed to provide a distillate fuel boiling range product with improved cold flow properties.

[0037] The diesel and jet range hydrocarbon fractions obtained herein can be used as drop-in fuel compositions or can be blended with existing fuel compositions.

[0038] Hydrotreating Catalyst The catalyst used in carrying out the hydrotreating process comprises a support component and a metal component supported on the support component. The support component comprises (i) MTW zeolite and / or SSZ-41x zeolite in an amount of 0.1 wt.% to 75 wt.% based on the total weight of the support, (ii) amorphous silica-alumina in an amount of 15 wt.% to 85 wt.% based on the total weight of the support, and (iii) an alumina binder in an amount of 5 wt.% to 55 wt.% based on the total weight of the support. The metal component comprises a Group 6 metal and a Group 8-10 non-noble metal.

[0039] In some embodiments, the MTW zeolite is ZSM-12.

[0040] Preferably, the zeolite has a low SiO2 / Al2O3 molar ratio. For example, the SiO2 / Al2O3 molar ratio of the MTW zeolite may be in the range of 25-100 (e.g., 25-75, or 25-50, or 30-100, or 30-75, or 30-50). SSZ-41x may have a SiO2 / Al2O3 molar ratio in the range of less than 30-100 (e.g., 50-90), and may further have a SiO2 / Al2O3 molar ratio in the range of 15-75 (e.g., 20-40). / The SiO2 / Al2O3 and SiO2 / ZnO molar ratios of zeolites may be determined by means and methods known in the art and include atomic absorption spectroscopy (AAS), inductively coupled plasma-atomic emission spectroscopy (ICP-AES), and X-ray fluorescence (XRF) techniques.

[0041] Preferably, the zeolite is in the hydrogen form or NH4 + type (i.e., at least some of the original cations bound to the zeolite are H + ion or NH4 + ions). The first method involves direct treatment with an acid, e.g., a mineral acid (HNO3, HCl, etc.). The second method involves direct exchange using an ammonium salt (e.g., NH4NO3) followed by calcination. Zeolites can optionally contain at most trace amounts of other cations (e.g., Na + ) (wherein a trace amount is 0.05% by weight or less based on the total weight of the zeolite).

[0042] The amount of zeolite in the carrier can be within the range of 0.1% by weight to 75% by weight (eg, 0.5% by weight to 25% by weight) relative to the total weight of the carrier.

[0043] The amorphous silica-alumina (ASA) may comprise a porous amorphous silica-alumina, such as SIRAL high pore volume ASA, although high pore volume is not necessary for the catalyst to be effective. The ASA may comprise 20% to 50% silica by weight, with the remainder being alumina.

[0044] Before being incorporated into the catalyst, the ASA powder had a surface area of ​​0.5 cm as measured by N2 adsorption at 77 K. 3 / g~2.0cm 3 / g (e.g., 0.6 cm 3 / g~1.6cm 3 The ASA powder, prior to incorporation into a support, may have a total pore volume of 100 nm to 200 nm (e.g., 100 nm to 250 nm) as measured by the BJH method. ... BET surface area of ​​400 m 2 / g~550m 2 / g (e.g., 410m 2 / g~510m 2 / g).

[0045] The amount of ASA in the carrier can be in the range of 15% to 85% by weight (eg, 50% to 80% by weight) based on the total weight of the carrier.

[0046] Any of α-alumina, η-alumina, θ-alumina, or γ-alumina is a suitable alumina binder for the support, with γ-alumina being preferred. The amount of alumina in the support can be in the range of 5% to 55% by weight (e.g., 15% to 35% by weight) based on the total weight of the support.

[0047] The carrier may optionally include a refractory binder or matrix other than alumina used to facilitate manufacture and provide strength. Suitable binders may include at least one of inorganic oxides, such as silica, magnesia, zirconia, chromia, titania, boria, thoria, and zinc oxide.

[0048] The carrier used may be in the form of shaped particles. The shaped carrier may be prepared by any suitable method known to those skilled in the art. The particles may be of various shapes, such as cylindrical, multilobed, etc., and may have nominal dimensions, such as 1 / 16 inch, 1 / 8 inch, 3 / 16 inch, etc.

[0049] After the support particles are shaped, they can be impregnated with a metal salt using an impregnation solution. Impregnation, for example by incipient wetness or ion exchange in solution, is a commonly used technique for introducing metals into catalysts that include supports. Suitable metal salts can include common salts used in aqueous impregnation of support particles for catalysts.

[0050] The hydrotreating process includes at least one Group 6 metal and at least one Group 8-10 non-noble metal as the hydrogenation or catalytic metal.

[0051] The Group 6 metal may include chromium, molybdenum, tungsten, or any combination thereof, preferably molybdenum and / or tungsten. The Group 6 metal may be present in the form of an oxide, typically in an amount ranging from 2% to 70% by weight (e.g., 5% to 40% by weight, or 10% to 30% by weight) based on the total weight of the catalyst.

[0052] The non-noble metals of Groups 8-10 may include iron, cobalt, nickel, or any combination thereof, preferably nickel. The non-noble metals of Groups 8-10 may be present in the form of an oxide, typically in an amount ranging from 1% to 40% by weight (2% to 15% by weight) based on the total weight of the catalyst.

[0053] In some embodiments, the total metal content (Groups 6 and 8-10 metals), in the form of oxides, can be in the range of 15% to 55% by weight (e.g., 20% to 40% by weight) based on the total weight of the catalyst. The amount of metal in the catalyst can be measured, for example, by subjecting the catalyst to XRF or ICP analysis.

[0054] The hydrotreating catalyst may further include an organic dispersant. The organic dispersant may be an organic compound containing 2-10 carbons and having a ratio of the number of carbon atoms to the number of oxygen atoms of 0.6-2. The organic dispersant may also be a chelating agent. Examples of suitable organic dispersants include glycols (e.g., ethylene glycol) and organic acids (e.g., citric acid, gluconic acid). In some cases, the organic dispersant may be a nitrogen-containing organic compound such as nitrilotriacetic acid. Without being bound to any particular theory, it is believed that the organic dispersant may be removed from the catalyst precursor / catalyst during the heating, calcination, and / or sulfidation steps performed after impregnation to form metal oxides and / or metal sulfides. It is believed that the dispersant may assist in adjusting the metal distribution throughout the catalyst support.

[0055] When the metal is added to the catalyst by impregnation, the amount of organic dispersant in the impregnation solution can be selected based on the amount of metal in the solution. In some embodiments, the molar ratio of the organic additive to the total metal in the solution can be 0.1 to 5.0 (e.g., 0.1 to 2.0, or 0.1 to 1.0, or 0.2 to 5.0, or 0.2 to 2.0, or 0.2 to 1.0, or 0.3 to 5.0, or 0.3 to 2.0, or 0.3 to 1.0, or 0.4 to 5.0, or 0.4 to 2.0, or 0.4 to 1.0). Additionally or alternatively, the molar ratio of the organic additive to the Group 8-10 metal (e.g., Ni) can be 0.5 to 10 (e.g., 0.5 to 5.0, or 0.5 to 3.0, or 1.0 to 10, or 1.0 to 5.0, or 1.0 to 3.0).

[0056] Optionally, in addition to the metal components already added, further materials may be added, such as any material that can be added during the preparation of a conventional hydroprocessing catalyst. Suitable examples of such additional materials may include phosphorus compounds, boron compounds, fluorine-containing compounds, additional transition metals, rare earth metals, fillers, or any combination thereof.

[0057] In some embodiments, the catalyst further comprises a phosphorus compound. Suitable phosphorus compounds can include ammonium phosphate, phosphoric acid, or an organic phosphorus compound. The phosphorus compound can be added at any stage of the catalyst preparation process. The amount of phosphorus in the catalyst can be at least 1 wt% (calculated as P2O5) based on the total weight of the catalyst, and more preferably can be in the range of 1-10 wt% (calculated as P2O5) based on the total weight of the catalyst.

[0058] After shaping of the support and further impregnation with the metals, the support / catalyst composition is suitably dried and calcined. The drying temperature may be in the range of 50°C to 200°C, with a drying time of 0.5 to 5 hours being suitable. The calcination temperature may be in the range of 200°C to 800°C (e.g., 300°C to 600°C). Calcination of the support requires a relatively short time, e.g., 0.5 to 3 hours. For calcination of the catalyst composition, a controlled temperature ramp with a low heating rate may have to be used to ensure optimal dispersion of the metals. Such calcination may require 5 to 20 hours.

[0059] The catalyst may be pre-sulfided to form a sulfided metal catalyst prior to contact with the hydrocarbon feedstock. Sulfiding of the metal may be carried out by any convenient method, such as gas phase sulfiding or liquid phase sulfiding. Sulfiding is typically carried out by contacting a catalyst precursor (e.g., a catalyst precursor comprising a metal complexed with a dispersing agent and / or in the form of a metal oxide) with a sulfur-containing compound (e.g., elemental sulfur, hydrogen sulfide, or a polysulfide). Hydrogen sulfide is a convenient sulfiding agent for gas phase sulfiding and may be added to a gas phase sulfiding atmosphere containing hydrogen in an amount of 0.1% to 10% by weight. Sulfiding may also be carried out in the liquid phase utilizing a combination of hydrogen and a polysulfide, such as a dimethyl disulfide-added hydrocarbon stream. Sulfiding may be carried out at any convenient sulfiding temperature, for example, from 150° C. to 500° C. Sulfiding may be carried out at any convenient sulfiding pressure, for example, from 100 psig to 1000 psig (689.5 kPa to 6.895 MPa) or higher. The sulfurization time may vary depending on the sulfurization conditions, so a sulfurization time of 1 hour to 72 hours may be appropriate. The resulting catalyst may be steam-treated before use. EXAMPLES

[0060] The following illustrative examples are intended to be non-limiting.

[0061] Example 1 Production of jet-boiling range hydrocarbons from n-octadecane. SSZ-41x catalyst was screened together with MTW catalyst for the hydroconversion of n-octadecane to jet-boiling range hydrocarbons. The catalysts were prepared by conventional means. A mixed extrusion substrate containing zeolite, alumina binder, and amorphous silica-alumina (ASA) was mixed with NiCO3, citric acid, MoO3, (NH4)6H2W, and 100% NaCl. 12 O 40The catalysts were co-impregnated with an aqueous solution containing SSZ-41x, SiO2, and H3PO4, and then calcined at 450 °C for 60 min in air. The SiO2 / Al2O3 molar ratio of the SSZ-41x was 75. The SiO2 / Al2O3 molar ratio of the MTW zeolite (CBV8014, Zeolyst International) was 80–90. The catalyst properties are summarized in Table 1. [Table 1]

[0062] The catalytic performance was evaluated in a bench-scale unit operating in a single-stage once-through mode at the conditions shown in Table 2. [Table 2]

[0063] Figure 1 is a graph of catalyst activation temperature (CAT) versus hydrocracking (HCR) conversion (<500°F) during n-octadecane hydroconversion over SSZ-41x and MTW catalysts. As shown, over the range of synthetic HCR conversions tested (about 20-50% for <500°F), the difference in activity for catalysts containing MTW and SSZ-41 was about 5°F or less, averaging about 2°F, so that within the precision of the test method the catalysts had substantially the same activity. The results are summarized in Table 3. [Table 3]

[0064] Figure 2 is a graph of product fraction yields versus HCR conversion during the hydroconversion of n-octadecane over SSZ-41x and MTW catalysts. As shown, the MTW and SSZ-41 catalysts produced approximately the same product yields for jet (300°F-550°F), heavy naphtha (180°F-300°F), light naphtha (C5-180°F), and gas (C4-) over the range of conversions tested. The jet and gas yields are of particular interest since they are the most and least wanted products, respectively. The results are summarized in Table 4. [Table 4]

[0065] Furthermore, cracking n-octadecane (normal boiling point, i.e., nBP=603°F) to produce n-C8 hydrocarbons (nBP=257°F) or lower produces compounds below the jet boiling range (300°F-550°F). Without being bound by any theory, it is believed that the high yields of jet product fractions observed relative to lower boiling product fractions such as heavy naphtha (see, e.g., FIG. 2) indicate that n-octadecane is primarily or predominantly converted by isomerization to species boiling within the jet range by the MTW and SSZ-41x catalysts. This is a desirable result that avoids excessive cracking to less desirable light fractions and demonstrates the feasibility of using MTW and / or SSZ-41x in the selective production of jet fuel from n-octadecane.

[0066] FIG. 3 is a graph of the freezing point of the jet product fraction versus HCR conversion during hydroconversion of n-octadecane over MTW and SSZ-41x catalysts. The lowest freezing point detectable by the analytical method used was −60° C. As shown in FIG. 3, the freezing points of the jet fractions produced by the catalysts (300° F. to 550° F.) tend to decrease as HCR conversion increases. At similar conversions, samples containing MTW produced jet fractions that freezing at lower temperatures than those produced by catalysts with SSZ-41x, with the MTW and SSZ-41x catalysts resulting in jet freezing points of −31.1° C. and −5.4° C. at HCR conversions of 19.6 wt.% and 21.7 wt.%, respectively.

[0067] Figures 4A-4B are graphs of the cloud point and pour point of the jet product versus HCR conversion during the hydroconversion of n-octadecane over SSZ-41x and MTW catalysts, respectively. As shown in Figures 4A-4B, the pour / cloud points of products boiling at 300°F+ and 500°F+ were generally lower for catalysts containing MTW than for SSZ-41x.

[0068] In summary, catalysts containing MTW and SSZ-41x generally delivered similar n-C18 HCR performance in terms of activity and product selectivity, but the catalysts containing SSZ-41x were prepared with significantly lower metal content than the catalysts containing MTW. As a result, SSZ-41x may be more advantageous overall than MTW for the purpose of producing jet fuel from renewable feedstocks, given its ability to deliver comparable HCR yields with fewer metals overall and its lower propoxy hydrogenation activity. However, the freezing point of the jet fuel produced by SSZ-41x is higher than that derived from MTW, which is generally less desirable. Catalysts containing either MTW or SSZ-41x zeolite have the ability to convert n-C18 to products within the boiling range of 300°F to 550°F with sufficiently high yields and satisfactory activity, indicating that they can be utilized to produce jet fuel from renewable feedstocks.

[0069] Example 2 Production of middle distillates from conventional petroleum feedstocks SSZ-41x catalyst was screened together with MTW catalyst for hydroconversion of unconverted oil (UCO) to middle distillate boiling range hydrocarbons. SSZ-41x catalyst and MTW catalyst were prepared as described in Example 1, except that MTW zeolite (SAR=80) was self-prepared. The catalyst properties are summarized in Table 2. [Table 2]

[0070] The petroleum feedstock was unconverted oil (UCO) having the properties listed in Table 6. [Table 6]

[0071] The catalytic performance was evaluated in a bench-scale unit operating in a single-stage once-through mode at the conditions shown in Table 7. [Table 7]

[0072] Figure 5 is a graph of fraction yield versus HCR conversion during the hydroconversion of UCO over MTW and SSZ-41x catalysts. As shown in Figure 5, catalysts including MTW and SSZ-41x provided similar fraction yields (380°F to 700°F) over the range of conversions tested, with the MTW catalyst providing approximately 1 wt% higher yields at any given conversion. These results are summarized in Table 8. [Table 8]

[0073] FIG. 6 is a graph of CAT vs. HCR conversion (<700° F.) during the hydroconversion of UCO over MTW and SSZ-41x catalysts. As shown in FIG. 6, the SSZ-41x catalyst exhibited significantly better activity than the MTW catalyst by about 18° F. within the range of HCR conversions tested. The yields of fractions produced by each catalyst were relatively similar, but a substantial activity advantage is observed for SSZ-41x (FIG. 5). The significant activity advantage of one hydroprocessing catalyst over another generally comes with a corresponding penalty in the form of lower HCR selectivity or lower product yield. In the particular case of the present SSZ-41x catalyst, such a penalty is disproportionately small, suggesting that SSZ-41x has a substantial activity advantage over MTW.

[0074] In summary, both the MTW and SSZ-41x catalysts were excellent at producing middle distillates (boiling points between 380° F. and 700° F.) in similar yields at comparable conversions, however, the SSZ-41x catalyst has a substantial advantage over MTW in HCR activity.

Claims

1. 1. A process for producing distillate range hydrocarbons comprising the steps of: contacting a hydrocarbon feedstock with a hydrotreating catalyst under hydrotreating conditions to produce a hydrotreated effluent; and fractionating the hydrotreated effluent to recover one or more hydrocarbon fractions boiling within the diesel or jet fuel range; 13. The hydrotreating catalyst comprising a support component and a metal component supported on the support component, the support component comprising: (i) an MTW zeolite and / or an SSZ-41x zeolite in an amount of 0.1 wt.% to 75 wt.%, based on the total weight of the support; (ii) an amorphous silica-alumina in an amount of 15 wt.% to 85 wt.%, based on the total weight of the support; and (iii) an alumina binder in an amount of 5 wt.% to 55 wt.%, based on the total weight of the support; and the metal component comprises a Group 6 metal and a Group 8-10 non-noble metal.

2. The method of claim 1 , wherein the hydrocarbon feedstock comprises at least 10% by weight of a biological component.

3. 3. The method of claim 2, wherein the biocomponent is obtained from the hydrodeoxygenation of renewable oils.

4. The method of claim 1 , wherein the hydrocarbon feedstock comprises at least 40 wt.% n-paraffins.

5. The hydrogenation conditions are a reaction temperature of 300° C. to 500° C., a total pressure of 6 MPa to 30 MPa, a hydrogen supply rate of 800 SL / L to 2000 SL / L, and a hydrogen supply time of 0.1 h －１ ~10h －１ 2. The method of claim 1 , comprising a liquid hourly space velocity of

6. The MTW zeolite has a SiO ２ / Al ２ O ３ The method of claim 1 having a molar ratio.

7. 2. The method of claim 1, wherein the MTW zeolite is ZSM-12.

8. The SSZ-41x zeolite has a SiO content of 30 to less than 100. ２ / Al ２ O ３ Molar ratio, and 15 to 75 SiO ２ The method of claim 1 having a molar ratio of ZnO to ZnO.

9. 2. The method of claim 1, wherein the MTW zeolite and / or the SSZ-41x zeolite is present in an amount of 0.5% to 25% by weight based on the total weight of the support.

10. The method of claim 1, wherein the amorphous silica-alumina is present in an amount of from 50% to 80% by weight based on the total weight of the support.

11. Prior to being incorporated into the support, the amorphous silica-alumina was ３ / g to 2.0 cm ３ / g total pore volume, average pore diameter of 4 nm to 14 nm, and ２ / g~550m ２ 13. The method of claim 1, wherein the crystalline silica has one or more of the following properties: BET surface area of ​​100 / g.

12. The method of claim 1, wherein the alumina binder is present in an amount of from 15% to 35% by weight based on the total weight of the support.

13. 2. The method of claim 1, wherein the Group 6 metal is present in an amount of 5 to 40% by weight, calculated as oxide, based on the total weight of the catalyst.

14. 2. The method of claim 1, wherein the Group 8-10 metal is present in an amount of 1-10 wt. % calculated as oxide based on the total weight of the catalyst.

15. 2. The method of claim 1, wherein the Group 6 metal is selected from molybdenum and / or tungsten and the Group 8-10 metal is selected from cobalt and / or nickel.

16. 2. The method of claim 1, wherein the hydrotreating catalyst further comprises an organic dispersant having from 2 to 10 carbons and a ratio of the number of carbon atoms to the number of oxygen atoms of from 0.6 to 2.

17. 17. The method of claim 16, wherein the organic additive is selected from citric acid, gluconic acid, nitrilotriacetic acid, ethylene glycol, or any combination thereof.

18. The hydrotreating catalyst has a content of P based on the total weight of the catalyst. ２ O ５ The method of claim 1 further comprising phosphorus in an amount of 1 to 10% by weight calculated.

19. 10. The method of claim 1, wherein the hydrotreating catalyst is further sulfided under sulfiding conditions prior to contacting the hydrocarbon feed with the hydrotreating catalyst.

20. 10. The method of claim 1, wherein the diesel fuel or the jet fuel is used as a drop-in fuel composition or is blended with an existing fuel composition.

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