Middle distillate hydrocracking catalyst containing zeolite beta with low OD acidity and large domain size

Abstract

To provide improved hydrocracking catalysts and processes for using and making them.SOLUTION: A hydrocracking catalyst is provided comprising: a. 0.5 to 10 wt.% zeolite beta having an OD acidity of 20 to 400 μmol / g and an average domain size of 800 to 1500 nm2; b. 0 to 5 wt.% zeolite USY having an ASDI between 0.05 and 0.12, where the weight percentage of the zeolite beta is greater than the weight percentage of the zeolite USY; c. a catalyst support; and d. at least one metal selected from the group consisting of elements from Group 6 and Groups 8-10 of the Periodic Table. A process for hydrocracking using the hydrocracking catalyst to produce middle distillates is provided. A method for making the hydrocracking catalyst is also provided.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This application is related to two concurrently filed applications entitled "Middle Distillate Hydrocracking Catalyst Comprising Zeolite USY and Zeolite Beta Having Low Acidity and Large Domain Size" and "Improved Noble Metal Zeolite Catalyst for Second Stage Hydrocracking to Produce Middle Distillates," which are incorporated herein in their entireties.

[0002] FIELD OF THE INVENTION This application is directed to hydrocracking catalysts, processes for hydrocracking hydrocarbonaceous feedstocks, and methods for making hydrocracking catalysts. [Background technology]

[0003] There is a need for improved hydrocracking catalysts, and processes for their use and for their manufacture. Previous hydrocracking catalysts have not provided the desired levels of activity and selectivity necessary for optimizing the production of middle distillates. Summary of the Invention [Means for solving the problem]

[0004] This application is a. OD acidity of 20-400 μmol / g and 800-1500 nm 2 0.5 to 10 wt. % zeolite beta having an average domain size of b. 0-5 wt. % zeolite USY having an ASDI between 0.05-0.12, wherein the wt. % of zeolite beta is greater than the wt. % of zeolite USY; c. a catalyst support; d. at least one metal selected from the group consisting of elements of groups 6 and 8 to 10 of the periodic table; The present invention provides a hydrocracking catalyst comprising:

[0005] The present application also includes a process for hydrocracking a hydrocarbonaceous feedstock, comprising the steps of contacting the hydrocarbonaceous feedstock with a hydrocracking catalyst under hydrocracking conditions to produce a hydrocracking effluent comprising middle distillates, the hydrocracking catalyst comprising: a. OD acidity of 20-400 μmol / g and 800-1500 nm 2 0.5 to 10 wt. % zeolite beta having an average domain size of b. 0-5 wt. % zeolite USY having an ASDI between 0.05-0.12, wherein the wt. % of zeolite beta is greater than the wt. % of zeolite USY; c. a catalyst support; d. at least one metal selected from the group consisting of elements of groups 6 and 8 to 10 of the periodic table; Also provided is a process including:

[0006] The present application also provides a method for producing a hydrocracking catalyst, comprising: a. OD acidity of 20-400 μmol / g and 800-1500 nm 2 and an optional USY zeolite having an ASDI between 0.05 and 0.12, a catalyst support, and sufficient liquid to form an extrudable paste, wherein the weight percent of the zeolite beta is greater than a second weight percent of the USY zeolite; b. extruding the extrudable paste to produce an extrusion base; c. impregnating the extrusion base with a metal impregnation solution containing at least one metal selected from the group consisting of elements of Groups 6 and 8 to 10 of the Periodic Table to prepare metal-loaded extrudates; and d. post-treating the metal-loaded extrudates by drying and calcining the metal-loaded extrudates, wherein the hydrocracking catalyst has improved selectivity for producing a hydrocracked effluent having a TBP of 380-700°F (193-371°C).

[0007] As described herein, the invention may suitably comprise, consist of, or consist essentially of the elements of the claims. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a transmission electron microscopy (TEM) image showing agglomerated crystals of H-BEA-150 zeolite beta used in the preparation of hydrocracking catalysts in the examples. [Figure 2] 1 is a graph of domain measurements made on two samples of zeolite beta. [Figure 3] 1 is a graph of the average domain size of two samples of zeolite beta. DETAILED DESCRIPTION OF THE INVENTION

[0009] Glossary "Hydrocracking" refers to processes in which hydrogenation and dehydrogenation involve the cracking / breaking of hydrocarbons, for example, converting heavier hydrocarbons into lighter hydrocarbons or converting aromatics and / or cycloparaffins (naphthenes) into acyclic branched paraffins.

[0010] "Cut point" refers to the temperature on the true boiling point ("TBP") curve at which a given degree of separation is reached.

[0011] "TBP" refers to the boiling point of a hydrocarbonaceous feed or product as determined by ASTM D2887-13.

[0012] "Hydrocarbon-based" means a compound or substance that contains hydrogen and carbon atoms, and may contain heteroatoms such as oxygen, sulfur, or nitrogen.

[0013] The "fraction" includes the following products: [Table 1]

[0014] "Middle distillates" includes jet fuel, kerosene and diesel products, as defined by their typical cut points above.

[0015] "Heavy middle distillates" refers to products having a TBP between 380 and 700°F (193 and 371°C).

[0016] "Finished catalyst" refers to a hydrocracking catalyst composition including all of its components and after all processing steps used to prepare it and any post-treatment steps.

[0017] "LHSV" means liquid hourly space velocity.

[0018] "SCF / B" refers to the unit of standard cubic feet of gas (e.g., nitrogen, hydrogen, air, etc.) per barrel of hydrocarbon feed.

[0019] "Zeolite beta" has a three-dimensional crystal structure with straight 12-membered ring channels and crossed 12-membered ring channels, and has a size of approximately 15.3T / 1000Å. 3 Zeolite Beta refers to a zeolite having a framework density of 1000 MPa. Zeolite Beta has the BEA framework described in Ch. Baerlocher and L.B. McCusker, Database of Zeolite Structures: http: / / www.iza-structure.org / databases / .

[0020] The SiO2 / Al2O3 molar ratio (SAR) is determined by ICP elemental analysis. An infinite SAR means that there is no aluminum in the zeolite, i.e., the molar ratio of silica to alumina is infinite. In that case, the zeolite is composed essentially entirely of silica.

[0021] "Zeolite USY" refers to an ultrastabilized Y zeolite. Y zeolite is a synthetic faujasite (FAU) zeolite with an SAR of 3 or greater. Y zeolite can be ultrastabilized by one or more of hydrothermal stabilization, dealumination, and isomorphous substitution. Zeolite USY can be any FAU-type zeolite with a higher framework silicon content than the starting (as-synthesized) Na-Y zeolite precursor.

[0022] "Catalyst support" refers to a material, usually a solid with a high surface area, on which a catalyst is immobilized.

[0023] "Periodic Table" refers to the IUPAC Periodic Table of the Elements edition dated June 22, 2007, where the numbering system for the Periodic Table Groups is as set forth in Chemical And Engineering News, 63(5), 27 (1985).

[0024] "OD acidity" refers to the amount of bridging hydroxyl groups exchanged with deuterated benzene at 80° C. by Fourier transform infrared spectroscopy (FTIR). OD acidity is a measure of the Bronsted acid site density in the catalyst. 1 The extinction coefficient of the OD signal was determined by analysis of a standard zeolite beta sample calibrated by H magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. The correlation between the extinction coefficients of OD and OH was obtained as follows: ε (-OD) =0.62*ε (-OH) .

[0025] "Domain size" is the calculated area (nm) of a structural unit observed and measured in a zeolite beta catalyst. 2 ). Domains are described by Paul A. Wright et al., "Direct Observation of Growth Defects in Zeolite Beta," JACS Communications, published on the web on December 22, 2004. The method used to measure domain size in zeolite beta is further described herein.

[0026] The "Acid Site Distribution Index (ASDI)" is a measure of the ultra-high active site concentration of a zeolite. In some embodiments, the smaller the ASDI, the more likely the zeolite will have a higher selectivity for producing heavier middle distillate products.

[0027] "Amorphous silica aluminate (ASA)" refers to a synthetic material that has some alumina present in a tetrahedral coordination as shown by nuclear magnetic resonance imaging. ASA can be used as a catalyst or catalyst support. Amorphous silica alumina contains sites called Bronsted acid (or protic) sites with ionic hydrogen atoms, Lewis acid (aprotic) sites, electron-accepting sites, and these various types of acid sites can be distinguished, for example, by the way pyridine is bonded.

[0028] "Pseudoboehmite alumina refers to an aluminum compound with the chemical composition AlO(OH). Pseudoboehmite alumina is composed of microcrystalline boehmite, which has a higher water content than boehmite.

[0029] "API gravity" refers to the specific gravity of a petroleum feedstock or product relative to water as determined by ASTM D4052-11.

[0030] "Multi-ring index (PCI)" refers to a measure of the content of compounds with several aromatic rings. PCI is useful in evaluating feedstocks for hydroprocessing. PCI is measured using ultraviolet spectroscopy and calculated as follows: PCI = {[absorbance @ 385 nm - (0.378 × absorbance @ 435 nm)] / 115 × c} × 1000, where c is the original concentration of the sample in the solvent (g / cm 3 ) is).

[0031] Without being limited by theory, it is believed that the unique combination of zeolite Beta, defined OD acidity, and defined average domain size, optionally combined with zeolite USY having a defined acid site distribution index (ASDI) and combined in specified proportions, results in a hydrocracking catalyst with much improved hydrocracking performance. The unique combination of these two zeolites in the hydrocracking catalyst provides improved selectivity for producing a hydrocracking effluent having a TBP of 380-700°F (193-371°C). The hydrocracking catalyst can also provide improved activity, such as 1-20°F at 60% conversion, compared to other hydrocracking catalysts that do not have the unique combination of zeolites disclosed herein.

[0032] Hydrocracking catalyst composition - zeolite beta: Zeolite Beta has an OD acidity of 20-400 μmol / g and a pH of 800-1500 nm 2 In one embodiment, the OD acidity is 30 to 100 μmol / g.

[0033] In one embodiment, zeolite beta is synthetically produced using an organic template. Examples of three different zeolite betas are shown in Table 1.

[0034] Table 1 [Table 2]

[0035] The acidic hydroxyl groups were subjected to H / D exchange and the total OD acidity was determined by FTIR spectroscopy. The method for determining the total OD acidity was adapted from the method described in the publication by Emiel J. M. Hensen et al., J. Phys. Chem., C2010, 114, 8363-8374. Prior to FTIR measurements, the samples were diluted to 1 × 10 -5The sample was heated at 400-450 °C under a vacuum of less than Torr for 1 hour. The sample was then doped with C6D6 and equilibrated at 80 °C. Spectra were collected in the OH and OD stretching regions before and after dosing with C6D6.

[0036] The average domain size was measured by a combination of transmission electron (TEM) and digital image analysis as follows:

[0037] I. Zeolite Beta Sample Preparation: Zeolite beta samples were prepared by embedding a small amount of zeolite beta in epoxy and sectioning it with a microtome. Descriptions of suitable procedures can be found in many standard microscopy textbooks.

[0038] Step 1. A small representative portion of zeolite beta powder was embedded in epoxy. The epoxy was allowed to harden.

[0039] Step 2. The epoxy containing a representative portion of the zeolite beta powder was cut with a microtome to a thickness of 80-90 nm. Microtome sections were collected on a 3 mm copper mesh with 400 mesh, available from microscope suppliers.

[0040] Step 3. A sufficient layer of conductive carbon was vacuum deposited onto the microtome section to prevent the zeolite beta sample from charging under the electron beam in the TEM.

[0041] II. TEM Imaging: Step 1. The zeolite beta samples prepared above were examined at low magnification, e.g., 250,000 to 1,000,000 times, to select crystals in which zeolite beta channels were visible.

[0042] Step 2. Selected zeolite beta crystals were tilted relative to their zone axis and images were recorded at >2,000,000x magnification, focused near the Scherzer defocus.

[0043] III. Average domain size (nm 2) image analysis: Step 1. The previously recorded TEM digital images were analyzed using a commercially available image analysis software package.

[0044] Step 2. Separate individual domains and measure the domain size in nm 2 Measurements were made in units of . Domains where the projection was not clearly under the channel view were not included in the measurements.

[0045] Step 3. A statistically relevant number of domains were measured. The raw data was saved in a computer spreadsheet program.

[0046] Step 4. Descriptive statistics and frequencies were calculated - arithmetic mean (d av ), i.e., the average domain size, and the standard deviation (s) were calculated using the following formula: Average domain size, d av =(an i d i ) / (an i ) Standard deviation, s=(a(d i -d av ) 2 / (an i )) 1 / 2

[0047] In one embodiment, the average domain size is 1000 to 1150 nm 2 etc., 900~1250nm 2 is.

[0048] Hydrocracking catalyst composition - zeolite USY: When included in a hydrocracking catalyst composition, the USY zeolite has an acid site distribution index (ASDI) between 0.05 and 0.12. In one embodiment, the USY zeolite has an ASDI that is favorable for the production of heavy middle distillates.

[0049] ASDI is determined by FTIR spectroscopy after H / D exchange of the acidic hydroxyl groups as previously described. The first high frequency OD(HF) is at 2676 cm-1 The second highest frequency OD(HF') is 2653 cm -1 The first low frequency OD (LF) is 2632 cm -1 and 2620 cm -1 The second lowest frequency OD (LF') is 2600 cm -1 The Bronsted acid site density was calculated using the integrated area of ​​the peaks. The acid site distribution index factor was calculated by the following formula: ASDI=(HF'+LF') / (HF+LF), which reflects the ultra-high active acid site content in the zeolite sample. In one embodiment, zeolite USY has a total Bronsted acid site range of 0.080-0.200 mmol / g as determined by FTIR after H / D exchange.

[0050] In one embodiment, the weight percent of zeolite beta is higher than the weight percent of zeolite USY in the hydrocracking catalyst. For example, the weight percent of zeolite beta can be 0.45 to 9.95 weight percent higher than the weight percent of zeolite USY. In one embodiment, the weight percent of zeolite beta is 1 to 5 weight percent higher than the weight percent of zeolite USY. In one embodiment, the hydrocracking catalyst has a weight ratio of zeolite beta to zeolite USY that is less than 0.90, such as 0.01 to 0.80 or 0.02 to 0.48.

[0051] Hydrocracking catalyst composition - catalyst support: The hydrocracking catalyst comprises a catalyst support. The catalyst support may be inert or may participate in the catalytic reaction carried out by the hydrocracking catalyst. Typical catalyst supports include various types of carbon, alumina, and silica. In one embodiment, the catalyst support comprises amorphous silica aluminate. In one embodiment, the catalyst support comprises amorphous silica aluminate and a second support material.

[0052] In one embodiment, amorphous silica aluminate (ASA) has higher thermal stability than high purity alumina. An example of a suitable amorphous silica aluminate is SIRAL® ASA, described below:

[0053] Table 2 [Table 3] *After activation at 550°C for 3 hours.

[0054] SIRAL® is a registered trademark of SASOL.

[0055] When used, examples of the second support material can include diatomaceous earth, alumina, silica, and silica-alumina. Other examples of the second support material include alumina-boria, silica-alumina-magnesia, silica-alumina-titania, and materials obtained by adding zeolites and other composite oxides. In one embodiment, the second support material is porous and includes natural clays or synthetic oxides. The second support material can be selected to have sufficient mechanical strength and chemical stability under the reaction conditions in which the hydrocracking catalyst will be used.

[0056] In one embodiment, the second support material comprises pseudoboehmite alumina. An example of pseudoboehmite alumina is CATAPAL® high purity alumina. CATAPAL® is a registered trademark of SASOL. Typical properties of CATAPAL high purity alumina are summarized below:

[0057] Table 3 [Table 4] *Surface area and pore volume were measured after activation at 550°C for 3 hours.

[0058] Hydrocracking catalyst composition - metal: The hydrocracking catalyst comprises at least one metal selected from the group consisting of elements from Groups 6 and 8 through 10 of the periodic table. In one embodiment, the hydrocracking catalyst comprises at least one Group 6 metal and at least one metal selected from Groups 8 through 10 of the periodic table. In one embodiment, each metal is selected from the group consisting of nickel (Ni), palladium (Pd), platinum (Pt), cobalt (Co), iron (Fe), chromium (Cr), molybdenum (Mo), tungsten (W), and mixtures thereof. Exemplary mixtures of metals include Ni / Mo / W, Ni / Mo, Ni / W, Co / Mo, Co / W, Co / W / Mo, Ni / Co / W / Mo, and Pt / Pd. In another embodiment, the hydrocracking catalyst comprises at least one Group 6 metal and at least one metal selected from Groups 8 through 10 of the periodic table. Exemplary metal combinations include Ni / Mo / W, Ni / Mo, Ni / W, Co / Mo, Co / W, Co / W / Mo and Ni / Co / W / Mo.

[0059] In one embodiment, at least one metal is a metal oxide. In one embodiment, the total amount of metal oxides in the hydrocracking catalyst is 0.1 wt.% to 90 wt.%, based on the bulk dry weight of the finished hydrocracking catalyst. In one embodiment, the hydrocracking catalyst comprises 2 wt.% to 10 wt.% nickel oxide and 8 wt.% to 40 wt.% tungsten oxide, based on the bulk dry weight of the finished hydrocracking catalyst.

[0060] In one embodiment, the finished hydrocracking catalyst will have the following composition: OD acidity of 20-400 μmol / g and 800-1500 nm 20.5-10 wt% zeolite beta having an average domain size of 0.05-0.12, 0-5 wt% zeolite USY having an ASDI between 0.05-0.12 (the wt% of zeolite beta is higher than the wt% of zeolite USY), 3-6 wt% nickel oxide, and 15-35 wt% tungsten oxide. Further, in one embodiment, the finished hydrocracking catalyst can include an organic acid in an amount such that the organic acid / Ni molar ratio is 0-2.

[0061] The hydrocracking catalyst may further comprise one or more promoters selected from the group consisting of phosphorus (P), boron (B), fluorine (F), silicon (Si), aluminum (Al), zinc (Zn), manganese (Mn), and mixtures thereof. The amount of promoter in the hydrocracking catalyst can be from 0 wt. % to 10 wt. % based on the bulk dry weight of the finished hydrocracking catalyst. In one embodiment, the amount of promoter in the hydrocracking catalyst is from 0.1 wt. % to 5 wt. % based on the bulk dry weight of the finished hydrocracking catalyst.

[0062] In one embodiment, the hydrocracking catalyst is in the form of extruded pellets (extrudates) having an extruded pellet diameter of 10 mm or less, such as 1.0 to 5.0 mm. In one embodiment, the extruded pellets have a length to diameter ratio of 10 to 1. Examples of other types and sizes of pellets used in hydrocracking catalysts are spheres of 1 to 10 mm diameter, cylinders of 1 to 10 mm diameter with a length to diameter ratio of 4 to 1, asymmetric shapes (including four-lobes) of 1 to 10 mm, and hollow cylinders or rings up to 10 mm in diameter.

[0063] Preparation of Hydrocracking Catalyst The hydrocracking catalyst can be prepared by a) mixing zeolite beta, zeolite USY (when used), a catalyst support, and sufficient liquid to form an extrudable paste to produce an extrusion base; b) impregnating the extrusion base with a metal impregnation solution containing at least one metal to prepare metal-loaded extrudates; and c) post-treating the metal-loaded extrudates by drying and calcining the metal-loaded extrudates.

[0064] In one embodiment, the method for producing a hydrocracking catalyst comprises: a. OD acidity of 20-400 μmol / g and 800-1500 nm 2 a zeolite beta having an average domain size of 0.05 to 0.12, a zeolite USY having an ASDI between 0.05 and 0.12, a catalyst support, and sufficient liquid to form an extrudable paste, wherein the weight percent of the zeolite beta is greater than a second weight percent of the zeolite Y; b. extruding the extrudable paste to produce an extrusion base; c. impregnating the extrusion base with a metal impregnation solution containing at least one metal selected from the group consisting of elements of Groups 6 and 8 to 10 of the periodic table to prepare metal-loaded extrudates; and d. post-treating the metal-loaded extrudates by drying and calcining the metal-loaded extrudates, wherein the hydrocracking catalyst has improved selectivity for producing a hydrocracked effluent having a TBP of 380-700°F (193-371°C).

[0065] The liquid used in step a) can be water or a mild acid. In one embodiment, the liquid used in step a) is a dilute HNO3 acid solution of 0.5-5 wt% HNO3.

[0066] Prior to impregnation, the extruded base may be dried at a temperature between 90°C (194°F) and 150°C (302°F) for 30 minutes to 3 hours. The dried extruded base may then be calcined at one or more temperatures between 350°C (662°F) and 700°C (1292°F).

[0067] In one embodiment, the metal impregnation solution is prepared by dissolving the metal precursor in a solvent. Suitable solvents include water, C1-C3 alcohols, ethers, and amines. In one embodiment, the solvent is deionized water. The concentration of the impregnation solution can be determined by the pore volume of the catalyst support and the selected metal loading. In one embodiment, the extruded base is exposed to the impregnation solution for 0.1 to 10 hours. When the hydrocracking catalyst contains two or more metals, these metals can be impregnated sequentially or simultaneously.

[0068] In one embodiment, the impregnation of at least one of the metals is achieved in the presence of a modifier that may be selected from the group consisting of compounds represented by the following structures (1) to (4), including condensed forms thereof: [ka] [ka] [ka] [ka] (In the formula, (1) R1, R2, and R3 are independently selected from the group consisting of hydrogen, hydroxyl, methyl, amine, and straight or branched chain, substituted or unsubstituted C1-C3 alkyl groups, C1-C3 alkenyl groups, C1-C3 hydroxyalkyl groups, C1-C3 alkoxyalkyl groups, C1-C3 aminoalkyl groups, C1-C3 oxoalkyl groups, C1-C3 carboxyalkyl groups, C1-C3 aminocarboxyalkyl groups, and C1-C3 hydroxycarboxyalkyl groups; (2) R4 through R10 are independently selected from the group consisting of hydrogen, hydroxyl, and straight or branched, substituted or unsubstituted C2-C3 carboxyalkyl groups; (3) R11 is selected from the group consisting of linear or branched, saturated and unsaturated, substituted or unsubstituted C1-C3 alkyl groups, C1-C3 hydroxyalkyl groups, and C1-C3 oxoalkyl groups.

[0069] Representative examples of modifiers useful in this embodiment include 2,3-dihydroxysuccinic acid, ethanedioic acid, 2-hydroxyacetic acid, 2-hydroxypropanoic acid, 2-hydroxy-1,2,3-propanetricarboxylic acid, methoxyacetic acid, cis-1,2-ethylenedicarboxylic acid, hydroethane-1,2-dicarboxyic acid, ethane-1,2-diol, propane-1,2,3-triol, propanedioic acid, and α-hydro-ω-hydroxypoly(oxyethylene).

[0070] In an alternative embodiment, deposition of at least one of the metals is achieved in the presence of a modifier selected from the group consisting of N,N'-bis(2-aminoethyl)-1,2-ethanediamine, 2-amino-3-(1H-indol-3-yl)propanoic acid, benzaldehyde, [[(carboxymethyl)imino]bis(ethylenenitrilo)]tetraacetic acid, 1,2-cyclohexanediamine, 2-hydroxybenzoic acid, thiocyanate, thiosulfate, thiourea, pyridine, and quinoline.

[0071] When used, modifiers can prevent metal agglomeration, thereby increasing the activity and selectivity of the catalyst.

[0072] For each embodiment described herein, the amount of modifier in the pre-calcined hydrocracking catalyst can be from 0% to 18% by weight, based on the bulk dry weight of the hydrocracking catalyst.

[0073] In one embodiment, the metal impregnation solution can further include a deflocculating agent. Examples of deflocculating agents include pyruvic acid, levulinic acid, acetic acid, 2-ketogluconic acid, ketogluconic acid, thioglycolic acid, 4-acetylbutyric acid, 1,3-acetonedicarboxylic acid, 3-oxopropanoic acid, 4-oxobutanoic acid, 2,3-diformylsuccinic acid, citric acid, 5-oxopentanoic acid, 4-oxopentanoic acid, formic acid, propionic acid, butyric acid, valeric acid, caproic acid, enantic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, benzoic acid, salicylic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, phtalic acid, and isophtalic acid. Organic acids such as lactic acid, ethyl glyoxylate, glycolic acid, glucose, glycine, oxamic acid, glyoxylic acid, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid, N-methylaminodiacetic acid, iminodiacetic acid, diglycolic acid, malic acid, gluconic acid, acetylacetone, tartaric acid, aconitic acid, suberic acid, tricarballylic acid, malonic acid, succinic acid, and glycolic acid.

[0074] In one embodiment, the metal-bearing extrudates are dried for 0.1 to 10 hours at one or more temperatures in the range of 38°C (100°F) to 149°C (300°F). The dried metal-bearing extrudates may be further calcined at one or more temperatures in the range of 316°C (600°F) to 649°C (1200°F) for 0.1 to 10 hours while purging with excess dry air.

[0075] Overview of Hydrocracking The hydrocracking catalyst has improved selectivity for producing a hydrocracked effluent having a TBP of 380-700°F (193-371°C) from a wide variety of hydrocarbonaceous feedstocks. Examples of hydrocarbonaceous feedstocks include those that would normally be considered disadvantaged feedstocks that would not be suitable for producing a hydrocracked effluent having a TBP of 380-700°F (193-371°C) using conventional one-stage or two-stage hydrocracking processes. Suitable hydrocarbonaceous feedstocks that can be used include visbroken gas oil, heavy coker gas oil, gas oil derived from hydrocracking or desulfurization residues, other pyrolysis oils, deasphalted oils, Fischer-Tropsch-derived feedstocks, cycle oils from FCC units, heavy distillates derived from coal, coal gasification by-product tar, heavy oil derived from shale, and organic waste oils such as those from pulp or paper mills or waste biomass pyrolysis units.

[0076] Table 4 lists some typical physical properties of hydrocarbonaceous feedstocks that can be used.

[0077] Table 4 [Table 5]

[0078] Table 5 lists some typical hydrocracking process conditions that can be used.

[0079] Table 5 [Table 6]

[0080] Depending on the feedstock, potential target products and amount of available hydrogen, the catalysts described herein can be used alone or in combination with other conventional hydrocracking catalysts.

[0081] In one embodiment, a process for hydrocracking a hydrocarbonaceous feedstock comprises contacting the hydrocarbonaceous feedstock with a hydrocracking catalyst under hydrocracking conditions in either a single-stage or two-stage hydrotreating configuration to produce a hydrocracked effluent comprising a middle distillate. In one embodiment, the catalyst is disposed in one or more fixed beds in a single-stage hydrocracking unit with or without recycle (single-flow). Optionally, the single-stage hydrocracking unit may employ multiple single-stage units operated in parallel.

[0082] In one embodiment, the catalyst is disposed in one or more beds or units within a two-stage hydrocracking unit, with or without intermediate stage separation, with or without recycle. The two-stage hydrocracking unit can be operated using a full conversion configuration (meaning that all of the hydrotreating and hydrocracking is accomplished within the hydrocracking loop via recycle). In this embodiment, one or more distillation units within the hydrocracking loop may be used to remove products prior to the second stage hydrocracking step or before recycling the distillate bottoms back to the first and / or second stage.

[0083] The two-stage hydrocracking unit can also be operated in a partial conversion configuration (meaning that one or more distillation units are placed within the hydrocracking loop for the purpose of stripping one or more of the passing streams for further hydroprocessing). Such operation of the hydrocracking unit allows for highly unfavorable feedstock hydroprocessing by refineries by diverting undesirable feed components, such as polynuclear aromatics, nitrogen and sulfur species (which can deactivate the hydrocracking catalyst), from the hydrocracking loop for processing by units better suited to handling these components, such as an FCC unit.

[0084] In one embodiment, the catalyst is used in a first stage and optionally in a second stage of partial conversion that is a two-stage hydrocracking configuration suitable for the production of at least one middle distillate and heavy vacuum gas fluid catalytic cracking feedstock (HVGO FCC) by: (a) hydrocracking a hydrocarbonaceous feedstock to produce a first-stage hydrocracking effluent; (b) distilling the hydrocracked feedstock by atmospheric distillation to produce at least one middle distillation fraction and an atmospheric resid fraction; (c) further distillation by vacuum distillation of the atmospheric resid fraction to produce a side cut vacuum gas oil fraction and a heavy vacuum gas oil FCC feedstock; (d) hydrocracking the sidecut vacuum gas oil fraction to produce a second-stage hydrocracking effluent; and (e) Combining the second stage hydrocracking effluent with the first stage hydrocracking effluent.

[0085] The refinery configuration described above has several advantages over conventional two-stage hydrocracking schemes. First, in this configuration, the first-stage catalyst and operating conditions are selected to obtain an HVGO FCC stream with only the minimum feed quality necessary to produce an FCC product that meets established commercial specifications. This contrasts with conventional two-stage hydrocracking schemes, where the first-stage hydrocracking unit is operated at the severity required to maximize distillate yields, necessitating operation of the unit at even more severe conditions (requiring more hydrogen and shortening catalyst life).

[0086] Second, in this optional configuration, the sidecut VGO sent to the second-stage hydrocracker unit is cleaner and easier to hydrocrack than conventional second-stage hydrocracker feed. Therefore, higher quality middle distillate products can be obtained using a smaller volume of second-stage hydrocracking catalyst, which allows for a smaller hydrocracker reactor configuration and less hydrogen consumption. The second-stage hydrocracking unit configuration reduces construction costs, catalyst loading costs, and operating costs.

[0087] Products produced by hydrocracking The hydrocracking catalyst can significantly increase the yield of middle distillates. In one embodiment, the hydrocracking catalyst can also reduce the yield of products having a cut point below 380°F. In one embodiment, the hydrocracking effluent contains greater than 30% by volume, up to 50% by volume, heavy middle distillates having a TBP of 380-700°F (193-371°C). In one embodiment, the hydrocracking effluent contains at least 35% to 50% by volume hydrocarbons having a TBP of less than 700°F (371°C).

[0088] In one embodiment, the hydrocracking catalyst produces light and heavy naphthas and has an OD acidity of 20-400 μmol / g and an OD of 800-1500 nm 2 The yields of light naphtha and heavy naphtha can be reduced compared to previous hydrocracking catalysts that do not include zeolite beta having an average domain size of 0.15 to 0.25. [Example]

[0089] [Example 1] Preparation of catalyst sample DJ-4 Catalyst sample DJ-4 was prepared by combining 2.9 wt% H-BEA-150 zeolite, 1.1 wt% USY zeolite, 74.5 wt% amorphous silica-alumina (ASA) powder, and 21.5 wt% pseudoboehmite alumina and mixing them thoroughly. The H-BEA-150 zeolite was zeolite beta obtained from SUD CHEMIE. The USY zeolite was obtained from Zeolyst. The USY zeolite had an acid site distribution index (ASDI) of 0.086. Additional properties of the USY zeolite are summarized in Table 6.

[0090] Table 6 [Table 7]

[0091] The ASA powder was SIRAL-40 obtained from Sasol. The pseudoboehmite alumina was CATAPAL B from Sasol.

[0092] To this mixture, a dilute aqueous HNO3 acid solution (2 wt%) was added to produce an extrudable paste. The extrudable paste was extruded into 1 / 16" (1.59 mm) asymmetric quadrilobular shapes and dried at 248°F (120°C) for 1 hour. The dried extrudates were calcined at 1100°F (593°C) for 1 hour while purging excess dry air, and then cooled to room temperature.

[0093] The dried extruded catalyst was impregnated with Ni and W using a solution containing ammonium metatungstate and nickel nitrate at concentrations to achieve a target metal loading of 4.1 wt. % NiO and 25.2 wt. % WO, based on the bulk dry weight of the finished catalyst. The metal-impregnated extruded catalyst was dried at 270°F (132°C) for 1 hour. The dried catalyst was then calcined at 950°F (510°C) for 1 hour with an excess dry air purge and cooled to room temperature. The composition of this finished catalyst sample, DJ-4, is shown in Table 7.

[0094] [Example 2] Preparation of catalyst sample DJ-5 Catalyst sample DJ-5 was prepared using a process similar to that described in Example 1. 5.7 wt. % H-BEA-150 zeolite, 2.1 wt. % USY zeolite, 70.7 wt. % ASA powder, and 21.5 wt. % pseudoboehmite alumina powder were combined and mixed thoroughly. To this mixture was added a dilute aqueous HNO acid solution (2 wt. %) to produce an extrudable paste. The extrudable paste was extruded into 1 / 16" asymmetric quadrilobular shapes and dried at 248°F (120°C) for 1 hour. The dried extrudates were calcined at 1100°F (593°C) for 1 hour while purging excess dry air, and then cooled to room temperature.

[0095] The dried extruded catalyst was impregnated with Ni and W using a solution containing ammonium metatungstate and nickel nitrate at concentrations to achieve a target metal loading of 4.1 wt. % NiO and 25.2 wt. % WO, based on the bulk dry weight of the finished catalyst. The metal-impregnated extruded catalyst was dried at 270°F (132°C) for 1 hour. The dried catalyst was then calcined at 950°F (510°C) for 1 hour with an excess dry air purge and cooled to room temperature. The composition of this finished catalyst sample, DJ-5, is shown in Table 7.

[0096] [Example 3] Preparation of catalyst sample YY-8 Catalyst sample YY-8 was prepared by combining 1.6 wt.% H-BEA-150 zeolite, 58.4 wt.% amorphous silica-alumina (ASA) powder, and 40 wt.% pseudoboehmite alumina and mixing them thoroughly. A dilute aqueous HNO3 acid solution (2 wt.%) was added to the mixture to produce an extrudable paste. The extrudable paste was extruded into 1 / 16" asymmetric quadrilobular shapes and dried at 248°F (120°C) for 1 hour. The dried extrudates were calcined at 1100°F (593°C) for 1 hour while purging excess dry air, and then cooled to room temperature.

[0097] The dried extruded catalyst was impregnated with Ni and W using a solution containing ammonium metatungstate and nickel carbonate at concentrations to achieve a target metal loading of 5 wt. % NiO and 29 wt. % WO, based on the bulk dry weight of the finished catalyst. The solution also contained 12.7 grams of citric acid as a chelating agent. The metal-impregnated extruded catalyst was dried at 212°F (100°C) for 2 hours. The dried catalyst was then calcined at 500°F (260°C) for 1 hour while purging with excess dry air and cooled to room temperature. The composition of this finished comparative catalyst sample YY-8 is shown in Table 7.

[0098] [Example 4] Preparation of catalyst sample YY-9 Catalyst sample YY-9 was prepared using the same process as described in Example 1. 7.1 wt. % H-BEA-150 zeolite, 0.7 wt. % USY zeolite, 70.7 wt. % ASA powder, and 21.5 wt. % pseudoboehmite alumina powder were combined and mixed thoroughly. A dilute aqueous HNO3 acid solution (2 wt. %) was added to the mixture to produce an extrudable paste. The extrudable paste was extruded into a 1 / 16" asymmetric quadrilobate and dried at 248°F (120°C) for 1 hour. The dried extrudates were calcined at 1100°F (593°C) for 1 hour while purging excess dry air, and then cooled to room temperature.

[0099] The dried extruded catalyst was impregnated with Ni and W using a solution containing ammonium metatungstate and nickel nitrate at concentrations to achieve a target metal loading of 4.1 wt. % NiO and 25.2 wt. % WO, based on the bulk dry weight of the finished catalyst. The metal-impregnated extruded catalyst was dried at 270°F (132°C) for 1 hour. The dried catalyst was then calcined at 950°F (510°C) for 1 hour with an excess dry air purge and cooled to room temperature. The composition of this finished catalyst sample, YY-9, is shown in Table 7.

[0100] [Example 5] Preparation of Comparative Catalyst Samples A comparative catalyst sample was prepared by combining 5.7 wt% USY zeolite, 71.3 wt% amorphous silica alumina (ASA) powder and 23 wt% pseudoboehmite alumina and mixing them thoroughly.

[0101] To this mixture above, a dilute aqueous HNO acid solution (2 wt%) was added to produce an extrudable paste. The extrudable paste was extruded into 1 / 16" asymmetric quadrilobular shapes and dried at 248°F (120°C) for 1 hour. The dried extrudates were calcined at 1100°F (593°C) for 1 hour while purging excess dry air, and then cooled to room temperature.

[0102] The dried extruded catalyst was impregnated with Ni and W using a solution containing ammonium metatungstate and nickel nitrate at concentrations to achieve a target metal loading of 3.8 wt. % NiO and 25.3 wt. % WO, based on the bulk dry weight of the finished catalyst. The metal-impregnated extruded catalyst was dried at 270°F (132°C) for 1 / 2 hour. The dried catalyst was then calcined at 950°F (510°C) for 1 hour with an excess dry air purge and cooled to room temperature. The composition of the catalyst sample for this comparative example is shown in Table 7.

[0103] Table 7 Catalyst Composition [Table 8]

[0104] [Example 6] Comparison of catalyst performance The example catalysts described above were used to process a typical Middle Eastern VGO feedstock. The example catalysts were not pre-sulfided.

[0105] The characteristics of the Middle Eastern VGO feedstock are shown in Table 8.

[0106] Table 8 [Table 9]

[0107] Hydrocracking tests were conducted in the pilot plant unit at a total pressure of 2300 psig (18,858 kPa), an LHSV of 1.0-2.0, and a single-flow rate of 5000 SCF / B of hydrogen gas. The test results are summarized in Table 9 below.

[0108] Table 9 [Table 10]

[0109] Catalyst samples DJ-4, DJ-5, YY-8, and YY-9 significantly increased the yield of middle distillates and decreased the yield of products with cut points below 380° F. compared to the commercial comparative catalyst samples. Catalyst examples containing similar 4.0-5.5 wt.% total zeolite loadings were 8-12° F. more active than the commercial comparative catalyst samples.

[0110] The hydrocracking catalyst sample containing H-BEA-150, which has a unique distribution of larger domain sizes (and therefore fewer defects), appears to have reduced nonselective cracking, resulting in more gas production. Combination with zeolite USY, which has minimal ultra-high active sites (i.e., an ASDI between 0.05 and 0.12), also improved activity.

[0111] [Example 7] Domain size analysis of two different beta zeolites Domain size measurements were performed on two samples of commercially available zeolite beta. One sample was the same H-BEA-150 zeolite beta (ZE0090) used in the previous examples. The other sample was a comparative zeolite beta (CP811C-300, ZE0106) from Zeolyst International, which has a higher SAR than H-BEA-150. The raw data from the domain size analysis and a statistical analysis of the data are summarized in Table 10 below.

[0112] Table 10 [Table 11]

[0113] The data from these domain size analyses are also plotted in Figures 2 and 3. Figure 2 shows the frequency difference in domain size between the two zeolite betas. Figure 3 shows that the domain sizes of H-BEA-150 were larger and more widely distributed than those seen in the comparative zeolite beta. The standard deviation of the domain sizes of H-BEA-150 was 700 nm. 2The standard deviation of the domain size of the comparative zeolite beta is 500 nm. 2 In addition, H-BEA-150 zeolite beta had a particle size of 200 to 600 nm. 2 The domain size was 1200-2000 nm, much smaller than the smaller domains. 2 This is significantly different from the domain size distribution in the comparative zeolite beta. H-BEA-150 had large domains with a domain size of 1500-3200 nm. 2 Oversized domains with domain sizes of 200-600 nm 2 The two samples had a similar distribution of small domains (9 vs. 8) with domain sizes of 1.5 to 1.2. In this context, similar distribution means that the ratio of the number of domains in the two different domain size ranges was between 0.8:1 and 1.2:1.

[0114] The transitional term "comprising" is synonymous with "including," "containing," or "characterized by" and is inclusive or open-ended and does not exclude other unrecited elements or method steps. The transitional phrase "consisting of" excludes any element, step, or ingredient not specified in the claim. The transitional phrase "consisting essentially of" limits the claim to specified materials or steps, and "materials or steps that do not materially affect the basic and novel characteristic(s)" of the claimed invention.

[0115] In this specification and the appended claims, unless otherwise specified, all numbers expressing amounts, percentages, or proportions, as well as other numerical values ​​used in the specification and claims, should be understood to be modified by the term "about." Moreover, all ranges disclosed herein are inclusive of their endpoints and independently combinable. Whenever a numerical range with a lower and upper limit is disclosed, any number falling within that range is also specifically disclosed. Unless otherwise specified, all percentages are by weight.

[0116] Any term, abbreviation, or shorthand not defined is understood to have its ordinary meaning as used by one of ordinary skill in the art at the time this application is filed. The singular forms "a," "an," and "the" include plural referents unless clearly and unambiguously limited to one instance.

[0117] All publications, patents, and patent applications cited in this application are herein incorporated by reference in their entirety to the same extent as if each individual publication, patent application, or patent disclosure was specifically and individually indicated to be incorporated by reference in its entirety.

[0118] This specification uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to make and use the invention. Many modifications of the exemplary embodiments of the invention disclosed above will be readily apparent to those skilled in the art. Accordingly, the invention is to be construed as including all structure and methods that fall within the scope of the appended claims. Unless otherwise specified, any recitation of a genus of elements, materials or other components from which individual components or mixtures of components may be selected is intended to include all possible subgeneric combinations of the listed components and mixtures thereof.

[0119] The invention illustratively disclosed herein suitably may be practiced in the absence of any element not specifically disclosed herein.

Claims

1. a. OD acidity of 20-400 μmol / g and 800-1500 nm ２ 0.5 to 10 wt. % zeolite beta having an average domain size of b. 0-5 wt. % USY zeolite having an ASDI between 0.05-0.12, wherein the wt. % of zeolite beta is greater than the wt. % of USY zeolite; c. a catalyst support; d. at least one metal selected from the group consisting of elements of groups 6 and 8 to 10 of the periodic table; A hydrocracking catalyst comprising:

2. The zeolite beta has a SiO content of 50 to 200. ２ / Al ２ O ３ 10. The hydrocracking catalyst of claim 1 having a molar ratio (SAR):

3. 2. The hydrocracking catalyst according to claim 1, wherein the OD acidity is 30 to 100 μmol / g.

4. The average domain size is 900 to 1250 nm ２ 2. The hydrocracking catalyst according to claim 1, wherein

5. 200 to 600 nm ２ 1200-2000 nm than the small domains with domain sizes of ２ 2. The hydrocracking catalyst of claim 1, wherein the zeolite beta has large domains having a domain size of 0.1 to 0.

5.

6. The zeolite beta is 700 nm ２ 2. The hydrocracking catalyst of claim 1, having a standard deviation of domain sizes greater than

7. 2. The hydrocracking catalyst of claim 1, wherein the weight percent of zeolite beta is 1 to 5 weight percent higher than the weight percent of zeolite USY.

8. 2. The hydrocracking catalyst according to claim 1, wherein the weight ratio of said USY zeolite to said beta zeolite is 0 to 0.

48.

9. 2. The hydrocracking catalyst of claim 1, wherein the zeolite USY has a total Bronsted acidity of 0.080 to 0.200 mmol / g as determined by FTIR after H / D exchange.

10. 10. The hydrocracking catalyst of claim 1, comprising at least one Group 6 metal and at least one metal selected from Groups 8 to 10 of the Periodic Table.

11. 1. A process for hydrocracking a hydrocarbonaceous feedstock, comprising contacting the hydrocarbonaceous feedstock with a hydrocracking catalyst under hydrocracking conditions to produce a hydrocracking effluent comprising middle distillates, the hydrocracking catalyst comprising: a. OD acidity of 20-400 μmol / g and 800-1500 nm ２ 0.5 to 10 wt. % zeolite beta having an average domain size of b. 0-5 wt. % USY zeolite having an ASDI between 0.05-0.12, wherein the wt. % of zeolite beta is greater than the wt. % of USY zeolite; c. a catalyst support; d. at least one metal selected from the group consisting of elements of groups 6 and 8 to 10 of the periodic table; The above process, comprising:

12. 12. The process of claim 11, wherein the hydrocarbonaceous feedstock has a TBP range within 700 to 1200°F (371 to 649°C).

13. The zeolite beta has a SiO content of 50 to 200. ２ / Al ２ O ３ 12. The process of claim 11, having a molar ratio (SAR).

14. 12. The process of claim 11, wherein the OD acidity is 30 to 100 μmol / g.

15. The average domain size is 900 to 1250 nm ２ 12. The process of claim 11, wherein

16. 200 to 600 nm ２ 1200-2000 nm than the small domains with domain sizes of ２ 12. The process of claim 11, wherein the zeolite beta has large domains having a domain size of

17. The zeolite beta is 700 nm ２ 12. The process of claim 11 , wherein the domain size has a standard deviation greater than

18. 12. The process of claim 11, wherein the weight percent of zeolite beta is 1 to 5 weight percent higher than the weight percent of zeolite USY.

19. 12. The process of claim 11, wherein the weight ratio of said zeolite USY to said zeolite beta is from 0 to 0.

48.

20. 12. The process of claim 11, wherein the zeolite USY has a total Bronsted site content of 0.080 to 0.200 mmol / g as determined by FTIR after H / D exchange.

21. 12. The process of claim 11, comprising at least one Group 6 metal and at least one metal selected from Groups 8 to 10 of the Periodic Table.

22. 12. The process of claim 11, wherein the hydrocracking effluent comprises greater than 30% by volume and up to 50% by volume of heavy middle distillates having a TBP of 380-700°F (193-371°C).

23. 1. A method for producing a hydrocracking catalyst, comprising: a. OD acidity of 20-400 μmol / g and 800-1500 nm ２ a catalyst support and sufficient liquid to form an extrudable paste, wherein the weight percent of zeolite beta is greater than a second weight percent of zeolite USY; b. extruding the extrudable paste to produce an extrusion base; c) impregnating the extrusion base with a metal impregnation solution containing at least one metal selected from the group consisting of elements of Groups 6 and 8 to 10 of the Periodic Table to prepare metal-loaded extrudates; d. post-treating the metal-loaded extrudates by drying and calcining the metal-loaded extrudates, wherein the hydrocracking catalyst has improved selectivity for producing a hydrocracked effluent having a TBP of 380-700°F (193-371°C). method.

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