Use of MTW zeolite as a support for hydrogenocrack catalysts with improved selectivity and low-temperature fluidity characteristics for middle distillates.

Abstract

The process involves hydrocracking a hydrocarbon feed in a single stage. The catalyst comprises a substrate impregnated with a metal from Groups 6 and 8-10 of the periodic table. Catalyst substrates used in the hydrocracking process include alumina, amorphous silica-alumina (ASA) materials, USY zeolite, optionally beta zeolite, and zeolite ZSM-12.

Description

[Background technology] 【0001】 background Catalytic hydrogenation refers to a petroleum refining process in which carbonaceous raw materials are brought into contact with hydrogen and a catalyst at high temperatures and pressures for the purpose of removing undesirable impurities and / or converting carbonaceous raw materials into desired products. Examples of hydrogenation processes include hydrogenation heating, hydrogenation demetallation, hydrocracking, and hydrogen isomerization processes. 【0002】 Hydrogenation catalysts typically consist of one or more metals attached to a support or substrate made of amorphous oxides and / or crystalline microporous materials (e.g., zeolites). The choice of support and metals depends on the specific hydrogenation process in which the catalyst is used. 【0003】 Zeolites play a crucial role in hydrocracking and hydrogen isomerization reactions, and it is well known that the pore structure of zeolites largely determines their catalyst selectivity. The two processes yield different results and require different catalysts. 【0004】 Hydrocracking refers to a process in which hydrogenation and dehydrogenation are accompanied by the cracking / decomposition of hydrocarbons, such as converting heavier hydrocarbons to lighter hydrocarbons, or converting aromatic compounds and / or cycloparaffins (naphthenes) to acyclic branched paraffins. Hydrogen isomerization refers to the process in which normal paraffins isomerize to more branched counterparts in the presence of hydrogen on a catalyst. 【0005】 Hydrocracking is extremely useful for the production of distillate fuels. Developing novel catalyst combinations that can improve the conversion and yield of desired fraction products through the hydrocracking process would be highly beneficial to the industry. [Overview of the Initiative] 【0006】 summary In the hydrocracking process, it has been discovered that by using the novel catalyst described in this process, the middle distillate product is improved. The process involves hydrocracking a hydrocarbon feed in a single stage. The catalyst used in this single stage of the hydrocracking process comprises a substrate impregnated with metals from Group 6 and Groups 8 - 10 of the Periodic Table. The substrates of the catalyst used in the single hydrocracking stage include alumina, amorphous silica - alumina (ASA) materials, USY zeolite, and zeolite ZSM - 12. The substrate also includes beta zeolite. 【0007】 Among other factors, it has been discovered that the use of this catalyst substrate, including ZSM - 12, realizes many advantages in a single hydrocracking unit. The catalyst system provides an improved selectivity for the desired middle distillate product while also improving the low - temperature flow properties of the product. In connection with the present invention, the following is further disclosed. [1] A hydrocracking process comprising passing a hydrocarbon feed through a single-stage hydrocracking unit, wherein the feed is hydrocracking under hydrocracking conditions, and the catalyst in the hydrocracking unit comprises a substrate composed of alumina, amorphous silica-alumina material, USY zeolite, ZSM-12, and β-zeolite. [2] The process according to [1], wherein the substrate comprises 5 to 40% by weight of alumina, 30 to 80% by weight of ASA, 0.5 to 40% by weight of USY zeolite, 0.1 to 40% by weight of ZSM-12, and 0 to 40% by weight of β-zeolite. [3] The process described in [2], wherein the amount of alumina is in the range of approximately 20 to approximately 30% by weight. [4] The process described in [2], wherein the amount of ASA is in the range of approximately 45 to approximately 75% by weight. [5] The process described in [2], wherein the amount of USY zeolite is in the range of approximately 4 to approximately 20% by weight. [6] The process described in [2], wherein the amount of β-zeolite is in the range of approximately 4 to 20% by weight. [7] The process described in [2], wherein the amount of ZSM-12 is in the range of approximately 2 to approximately 20% by weight. [8] The process according to [1], wherein the supply comprises VGO. [9] The process according to [1], wherein the selectivity of the intermediate distillate (380-530°F) is at least 28% by weight in apparent conversion (<700°F) of about 60% by weight.

[10] The process according to [1], wherein the catalyst comprises metallic nickel (Ni) and tungsten (W) impregnated into the substrate.

[11] The process according to

[10] , wherein the catalyst comprises about 2% to about 10% by weight of nickel material and about 8% to about 40% by weight of tungsten material, based on the bulk dry weight of the hydrocracking catalyst.

[12] The process according to [1], wherein the catalyst comprises a modifier.

[13] The modifier has the structure (1) to (4), 【change】 During the ceremony, (1)R 1 、R 2 and R 3 This includes hydrogen, hydroxyl, methyl, amine, and linear or branched, substituted or unsubstituted C 1 -C 3 Alkyl alkyl group, C 1 -C 3 Alkenyl group, C 1 -C 3 Hydroxyalkyl group, C 1 -C 3 Alkylalkyl group, C 1 -C 3 Aminoalkyl group, C 1 -C 3 Oxoalkyl group, C 1 -C 3 Carboxyalkyl group, C 1 -C 3 aminocarboxyalkyl groups, and C 1 -C 3 Independently selected from the group consisting of hydroxycarboxyalkyl groups, (2)R 4 ~R 10 This includes hydrogen, hydroxyl, and linear or branched substituted or unsubstituted C. 2 -C 3 Independently selected from the group consisting of carboxyalkyl groups, (3)R 11 C is a linear or branched, saturated and unsaturated, substituted or unsubstituted C 1 -C 3 Alkyl alkyl group, C 1 -C 3 Hydroxyalkyl groups, and C 1 -C 3 Selected from the group consisting of oxoalkyl groups, The process described in

[12] , which is selected from the group consisting of compounds represented by the structures (1) to (4) and their condensation forms.

[14] The process according to

[13] , wherein the modifier comprises citric acid.

[15] The catalyst in the hydrocracking unit is (a) To form an extrudeable mass containing the catalyst substrate, (b) Extruding the mass to form a shaped extruded product, (c) The lump is fired to form a fired extruded product, (d) Prepare an impregnation solution containing at least one metal nitrate or metal carbonate, a solvent, a modifier and an ammonium-containing component, and adjust the pH of the impregnation solution to 1 to 5.5 (including both ends) with a hydroxide base, (e) bringing the shaped extruded product into contact with the impregnation solution, (f) The process according to [1], wherein the impregnated extruded product is prepared by removing the impregnation solution solvent and drying it at a temperature sufficient to form a dry impregnated extruded product.

[16] The process according to

[15] , wherein the impregnation solution comprises nickel carbonate.

[17] The modifier has the structure (1) to (4), 【change】 During the ceremony, (1)R 1 、R 2 and R 3 This includes hydrogen, hydroxyl, methyl, amine, and linear or branched, substituted or unsubstituted C 1 -C 3 Alkyl alkyl group, C 1 -C 3 Alkenyl group, C 1 -C 3 Hydroxyalkyl group, C 1 -C 3 Alkylalkyl group, C 1 -C 3 Aminoalkyl group, C 1 -C 3 Oxoalkyl group, C 1 -C 3 Carboxyalkyl group, C 1 -C 3 aminocarboxyalkyl groups, and C 1 -C 3 Independently selected from the group consisting of hydroxycarboxyalkyl groups, (2)R 4 ~R 10 This includes hydrogen, hydroxyl, and linear or branched substituted or unsubstituted C. 2 -C 3 Independently selected from the group consisting of carboxyalkyl groups, (3)R 11 C is a linear or branched, saturated and unsaturated, substituted or unsubstituted C 1 -C 3 Alkyl alkyl group, C 1 -C 3 Hydroxyalkyl groups, and C 1 -C 3 Selected from the group consisting of oxoalkyl groups, A process according to

[15] , selected from the group consisting of compounds represented by the above structures (1) to (4), and their condensation forms.

[18] The process according to

[17] , wherein the modifier comprises citric acid.

[19] A hydrogenolysis catalyst comprising alumina, amorphous silica-alumina, USY zeolite, β-zeolite, and ZSM-12 substrates.

[20] The hydrocracking catalyst according to

[19] , wherein the substrate comprises 5 to 40% by weight of alumina, 30 to 70% by weight of ASA, 0.5 to 40% by weight of USY zeolite, 0.5 to 40% by weight of β-zeolite, and 0.1 to 40% by weight of ZSM-12.

[21] The hydrogenocrack catalyst described in

[20] , wherein the amount of alumina is in the range of approximately 20 to approximately 30% by weight.

[22] The hydrogen cracking catalyst described in

[20] , wherein the amount of ASA is in the range of approximately 45 to approximately 75% by weight.

[23] The hydrogenocrack catalyst described in

[20] , wherein the amount of USY zeolite is in the range of approximately 4 to approximately 20% by weight.

[24] The hydrogenocrack catalyst described in

[20] , wherein the amount of β-zeolite is in the range of approximately 4 to 20% by weight.

[25] A hydrocracking catalyst as described in

[20] , wherein the amount of ZSM-12 is in the range of approximately 2 to approximately 20% by weight.

[26] The hydrocracking catalyst according to

[19] , wherein the catalyst comprises metallic nickel (Ni) and tungsten (W) impregnated into the substrate.

[27] The hydrocracking catalyst according to

[26] , wherein the catalyst comprises 2% to 10% by weight of nickel material and 8 to 40% by weight of tungsten material based on the bulk dry weight of the hydrocracking catalyst.

[28] The hydrocracking catalyst according to

[19] , wherein the catalyst comprises a reforming agent.

[29] The modifier has the structure (1) to (4), 【change】 During the ceremony, (1)R 1 、R 2 and R 3 This includes hydrogen, hydroxyl, methyl, amine, and linear or branched, substituted or unsubstituted C 1 -C 3 Alkyl alkyl group, C 1 -C 3 Alkenyl group, C 1 -C 3 Hydroxyalkyl group, C 1 -C 3 Alkylalkyl group, C 1 -C 3 Aminoalkyl group, C 1 -C 3 Oxoalkyl group, C 1 -C 3 Carboxyalkyl group, C 1 -C 3 aminocarboxyalkyl groups, and C 1 -C 3 Independently selected from the group consisting of hydroxycarboxyalkyl groups, (2)R 4 ~R 10 This includes hydrogen, hydroxyl, and linear or branched substituted or unsubstituted C. 2 -C 3 Independently selected from the group consisting of carboxyalkyl groups, (3)R11 C is a linear or branched, saturated and unsaturated, substituted or unsubstituted C 1 -C 3 Alkyl alkyl group, C 1 -C 3 Hydroxyalkyl groups, and C 1 -C 3 Selected from the group consisting of oxoalkyl groups, A hydrogen cracking catalyst process according to

[28] , comprising the group of compounds represented by the structures (1) to (4) and selected from their condensation forms.

[30] The hydrocracking catalyst according to

[28] , wherein the modifier comprises citric acid.

[31] The catalyst in the hydrocracking unit is (a) To form an extrudeable mass containing the catalyst substrate, (b) Extruding the mass to form a shaped extruded product, (c) The lump is fired to form a fired extruded product, (d) Prepare an impregnation solution containing at least one metal nitrate or metal carbonate, a modifier, a solvent, and an ammonium-containing component, and adjust the pH of the impregnation solution to 1 to 5.5 (including both ends) with a hydroxide base, (e) bringing the shaped extruded product into contact with the impregnation solution, (f) The hydrogen cracking catalyst according to

[19] , which is prepared by removing the impregnation solvent from the impregnation extruded product and drying it at a temperature sufficient to form a dry impregnation extruded product.

[32] The hydrocracking catalyst according to

[31] , wherein the impregnation solution contains nickel carbonate.

[33] The modifier has the structure (1) to (4), 【change】 During the ceremony, (1)R 1 、R 2 and R 3 This includes hydrogen, hydroxyl, methyl, amine, and linear or branched, substituted or unsubstituted C 1 -C 3 Alkyl alkyl group, C 1 -C 3 Alkenyl group, C 1 -C 3 Hydroxyalkyl group, C 1 -C 3 Alkylalkyl group, C 1 -C 3 Aminoalkyl group, C 1 -C 3 Oxoalkyl group, C 1 -C 3 Carboxyalkyl group, C 1 -C 3 aminocarboxyalkyl groups, and C 1 -C 3 Independently selected from the group consisting of hydroxycarboxyalkyl groups, (2)R 4 ~R 10 This includes hydrogen, hydroxyl, and linear or branched substituted or unsubstituted C. 2 -C 3 Independently selected from the group consisting of carboxyalkyl groups, (3)R 11 C is a linear or branched, saturated and unsaturated, substituted or unsubstituted C 1 -C 3 Alkyl alkyl group, C 1 -C 3 Hydroxyalkyl groups, and C 1 -C 3 Selected from the group consisting of oxoalkyl groups, A hydrogen cracking catalyst according to

[31] , selected from the group consisting of compounds represented by the above structures (1) to (4), and their condensation forms.

[34] The hydrocracking catalyst according to

[33] , wherein the modifier comprises citric acid. [Brief explanation of the drawing] 【0008】 Simple description of the drawing [Figure 1] Figure 1 shows the improvement in the low-temperature flow characteristics of the middle distillate when comparing the performance of hydrocracking catalysts prepared with and without ZSM-12. 【0009】 [Figure 2] Figure 2 shows the improvement in the low-temperature flow characteristics of unconverted oil when comparing the performance of hydrocracking catalysts prepared with and without ZSM-12. [Modes for carrying out the invention] 【0010】 Description of preferred form This process relates to the single-stage hydrocracking of hydrocarbon feedstocks. The process is designed to improve selectivity in the conversion of middle distillates (380-530°F, 193-277°C), or even lighter distillates (300-380°F, 149-193°C). The process is also designed to improve the low-temperature flow characteristics of the distillates. The process uses a specific catalyst in a single-stage hydrocracking process, the catalyst comprising a substrate composed of alumina, amorphous silica-aluminate (ASA), USY zeolite, optionally β-zeolite, and ZSM-12 zeolite. The substrate is impregnated with a catalyst metal selected from Group 6 and Groups 8-10 of the periodic table, preferably nickel (Ni) and tungsten (W). The term "periodic table" refers to the IUPAC periodic table of elements as of June 22, 2007, and the numbering scheme for the groups of the periodic table is as described in Chemical and Engineering News, 63(5), 27 (1985). 【0011】 The catalyst substrate can contain, based on the dry weight of the substrate, from about 0.1 to about 40 wt% alumina substrate, in another embodiment from about 5 to about 40 wt%, or in another embodiment from about 20 to about 30 wt% alumina. In another embodiment, 25 wt% alumina can be used. The catalyst substrate can also contain, based on the dry weight of the substrate, from about 30 to about 80 wt% ASA, or in another embodiment from about 45 to about 75 wt% ASA. Y zeolite can account for from 0.5 to about 40 wt% of the substrate, based on the dry weight of the substrate. In another embodiment, Y zeolite can account for from about 1 to about 30 wt% of the substrate, or in another embodiment from about 4 to about 20 wt%. Beta zeolite can optionally account for from 0 to about 40 wt% of the substrate, or from 0.5 to about 40 wt%, based on the dry weight of the substrate. In another embodiment, beta zeolite can account for from about 1 to about 30 wt% of the substrate, or in another embodiment from about 4 to about 20 wt%. The ZSM-12 component of the substrate can account for from about 0.1 to about 40 wt% of the substrate, or in another embodiment from about 0.5 to about 30 wt%, or from about 2 to about 20 wt%, based on the dry weight of the substrate. When beta zeolite is present, the amount of ZSM-12 can be decreased. 【0012】 The alumina can be any alumina known for use in catalyst substrates. For example, the alumina can be γ-alumina, η-alumina, θ-alumina, δ-alumina, χ-alumina, or mixtures thereof. 【0013】 The ASA of the catalyst support is an amorphous silica-alumina material having an average mesopore diameter typically of 70 Å to 130 Å. 【0014】 In one embodiment, the amorphous silica-alumina material contains SiO2 in an amount of 5 to 70 wt% of the bulk dry weight of the support, a BET surface area of 300 to 550 m 2 / g, and a total pore volume of 0.95 to 1.55 mL / g, as measured by ICP elemental analysis. 【0015】 In another embodiment, the catalyst support is an amorphous silica-alumina material containing SiO2 in an amount of 5-70% by weight of the bulk dry weight of the support, as measured by ICP elemental analysis, and is 300-550 m 2 The BET surface area per g includes a total pore volume of 0.95 to 1.55 mL / g, and the average mesopore diameter is 70 Å to 130 Å. 【0016】 In another lower embodiment, the catalyst support comprises a highly homogeneous amorphous silica-alumina having a bulk silica:alumina ratio (S / B ratio) of 0.7 to 1.3 on its surface, and a crystalline alumina phase present in an amount of about 10% by weight or less. 【number】 【0017】 To measure the S / B ratio, the Si / Al atomic ratio of the silica-alumina surface is measured using X-ray photoelectron spectroscopy (XPS). XPS is also known as electron spectroscopy for chemical analysis (ESCA). Since the transmittance of XPS is less than 50 Å, the Si / Al atomic ratio measured by XPS is relative to the surface chemical composition. 【0018】 The use of XPS for characterizing silica-alumina has been documented by W. Daneiell et al. in Applied Catalysis A, 196, 247-260, 2000. Therefore, XPS techniques are effective for measuring the chemical composition of the outer layer of the catalyst particle surface. Other surface measurement methods, such as Auger electron spectroscopy (AES) and secondary ion mass spectrometry (SIMS), can also be used to measure surface composition. 【0019】 Separately, the bulk Si / Al ratio of the composition is measured by ICP elemental analysis. Next, the S / B ratio and homogeneity of silica-alumina are measured by comparing the surface Si / Al ratio with the bulk Si / Al ratio. The following explains how the S / B ratio defines particle homogeneity: An S / B ratio of 1.0 means that the material is perfectly homogeneous throughout the entire particle. An S / B ratio less than 1.0 means that aluminum is abundant on the particle surface (or silicon is depleted), and aluminum is mainly located on the outer surface of the particle. An S / B ratio greater than 1.0 means that silicon is abundant on the particle surface (or aluminum is depleted), and aluminum is mainly located on the inner surface of the particle. 【0020】 "Zeolite USY" refers to super-stabilized Y zeolite. Y zeolite is a synthetic faujasite (FAU) zeolite having a SAR (silica:alumina molar ratio) of 3 or higher. Y zeolites can be super-stabilized by one or more of the following: hydrothermal stabilization, dealuminization, and isomorphic substitution. Zeolite USY can be any FAU-type zeolite having a higher framework silicon content than the starting material's (synthesized) Na-Y zeolite precursor. Such suitable Y zeolites are commercially available, for example, from Zeolyst, Tosoh, and JGC. 【0021】 The "β" in β-zeolite refers to a three-dimensional crystal structure with a linear chain of 12-membered ring channels intersecting each other, with a frequency of approximately 15.3T / 1000Å. 3 This refers to zeolite with a framework density of β. Zeolite β is described in Ch. Baerlocher and LB McCusker, Database of Zeolite Structures: http: / / www.iza-structure.org / databases / It has the BEA framework described above. 【0022】 In one embodiment, zeolite β has an OD acidity of 20-400 μmol / g and a wavelength of 800-1500 nm. 2It has an average domain size of . In one embodiment, the OD acidity is 30 to 100 μmol / g. 【0023】 In one embodiment, zeolite β is produced by synthesis using an organic template. Three different examples of zeolite β are shown in Table 1. [Table 1] 【0024】 Total OD acidity was measured by FTIR spectroscopy, specifically by H / D exchange of acidic hydroxyl groups. The method for measuring total OD acidity was as described in the publication by Emiel JM Hensen et al., J. Phys. Chem., C2010, 114, 8363-8374. Prior to FTIR measurement, the sample was subjected to a 1 × 10⁻⁶ measurement. -5 The samples were heated at 400-450°C for 1 hour under a vacuum of less than Torr. Next, C6D6 was added to the samples, and they were brought to equilibrium at 80°C. Spectra for the OH and OD stretching regions were collected before and after C6D6 addition. 【0025】 The average domain size was measured using a combination of transmission electron (TEM) and digital image analysis, as follows: 【0026】 I. Preparation of Zeolite β Samples: 【0027】 Zeolite β samples were prepared by embedding a small amount of zeolite β in epoxy and performing microstorm treatment. A description of the preferred procedure can be found in many standard microscopy textbooks. 【0028】 Step 1. A small amount of typical zeolite β powder was embedded in epoxy. The epoxy was then cured. 【0029】 Step 2. An epoxy containing a typical amount of zeolite β powder was thinned to a thickness of 80-90 nm by microstorming. Microtome sections were collected on a 400-mesh, 3 mm copper grid available from the microscope supplier. 【0030】 Step 3. A sufficient amount of conductive carbon layer was vacuum deposited onto the microtome-processed section to prevent the zeolite β sample from becoming charged under electron beam in the TEM. 【0031】 II. TEM Imaging: 【0032】 Step 1. The zeolite β sample prepared as described above can be examined at a low magnification, for example, 250,000 to 1,000,000 times, by selecting crystals in which zeolite β channels can be observed. 【0033】 Step 2. The selected zeolite β crystal was tilted along its crystal zone axis, focused to the vicinity of the Scherzer defocus, and the image was recorded at a magnification of over 2,000,000 times. 【0034】 III. Average domain size (nm) 2 Image analysis to obtain: 【0035】 Step 1. The recorded TEM digital images, as described above, were analyzed using commercially available image analysis software packages. 【0036】 Step 2. Separate individual domains and set the domain size to nm 2 The measurements were taken using [a specific method / system]. Domains where the projection did not significantly reduce the channel view were not included in the measurements. 【0037】 Step 3. A statistically relevant number of domains were measured. The raw data was saved to a computer spreadsheet program. 【0038】 Step 4. Descriptive statistics and frequency were measured - arithmetic mean (d avThe mean domain size and standard deviation (s) were calculated using the following formula: 【number】 【0039】 In one embodiment, the average domain size is 900-1250 nm 2 For example, 1000~1150nm 2 That is the case. 【0040】 The final component of the catalyst substrate is an MTW zeolite specifically known as ZSM-12. ZSM-12 zeolite is a silica-rich zeolite composed of a one-dimensional 12-membered ring channel system with intrinsic pore openings ranging from 5.7 angstroms to 6.1 angstroms. ZSM-12 zeolite is described in detail in U.S. Patents No. 3,832,449 and No. 4,391,785, the entirety of which is incorporated herein by reference. 【0041】 ZSM-12 prepares a solution containing at least one cyclic tetravalent amine halide, sodium oxide, silica oxide, and optionally alumina oxide and water, with a composition that falls within the following range in terms of the molar ratio of oxides. [Table A] [wherein R is dimethylpyrrolidinium, dimethylpiperidinium, or dimethylpyridinium halide, and M is an alkali metal.] The mixture can be suitably prepared by maintaining it until zeolite crystals are formed. The crystals are then separated from the liquid and recovered. Typical reaction conditions consist of heating the reaction mixture to a temperature of about 80°C to 180°C for a predetermined period ranging from about 6 hours to 150 days. A more preferred temperature range is about 100°C to about 150°C for a predetermined period ranging from about 2 to 40 days. 【0042】 ZSM-12 zeolite has a clearly distinguishable crystal structure, as its X-ray diffraction pattern shows the following prominent lines: [Table B] 【0043】 These values ​​were measured using standard techniques. The radiation was measured using a copper K-α doublet and a scintillation counter-spectrometer equipped with a strip chart pen recorder. Peak height, I, and position as a function of 2θ (where θ is the Bragg angle) were read from the spectrometer chart. From these, the relative intensity of 100 I / I was calculated. o [In the formula, I o is the intensity of the strongest line or peak. The lattice plane spacing at A, d(obs.), corresponding to the recorded line, was calculated. In Table 1, relative intensity is given using the terms m = intermediate, w = weak, and vs = very strong. This X-ray diffraction pattern should be understood to characterize all types of ZSM-12 compositions. By ion-exchange of sodium ions with cations, substantially identical patterns are revealed, with some minute shifts in lattice plane spacing and changes in relative intensity. Other minute changes may occur depending on the silicon:aluminum ratio in a particular sample, as well as whether or not it has been subjected to heat treatment. 【0044】 ZSM-12 zeolite is commercially available from companies such as Clariant, Zeolyst, and China Catalyst Group. 【0045】 As described herein, the hydrocracking catalyst for this single-stage hydrocracking process contains one or more metals, which are impregnated into the substrate or support described above. For each embodiment described herein, each metal used is selected from the group consisting of elements from Group 6 and Groups 8-10 of the periodic table, and mixtures thereof. 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. In another embodiment, the hydrocracking catalyst contains at least one Group 6 metal and at least one metal selected from Groups 8-10 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. 【0046】 The total amount of metallic material in the hydrocracking catalyst is 0.1% to 90% by weight, based on the bulk dry weight of the hydrocracking catalyst. In one embodiment, the hydrocracking catalyst contains 2% to 10% by weight of nickel material and 8% to 40% by weight of tungsten material, based on the bulk dry weight of the hydrocracking catalyst. 【0047】 Diluents can be used in the formation of the hydrocracking catalyst. Suitable diluents include inorganic oxides such as aluminum oxide, silicon oxide, titanium oxide, clay, ceria, and zirconia, as well as mixtures thereof. The amount of diluent in the hydrocracking catalyst is 0% to 35% by weight, based on the bulk dry weight of the hydrocracking catalyst. In one embodiment, the amount of diluent in the hydrocracking catalyst is 0.1% to 25% by weight, based on the bulk dry weight of the hydrocracking catalyst. 【0048】 The hydrocracking catalyst for this process may also contain 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 is 0% to 10% by weight, based on the bulk dry weight of the hydrocracking catalyst. In one embodiment, the amount of promoter in the hydrocracking catalyst is 0.1% to 5% by weight, based on the bulk dry weight of the hydrocracking catalyst. 【0049】 Preparation of hydrocracking catalysts In one embodiment, metal deposition is achieved by bringing at least the catalyst support into contact with the impregnation solution. The impregnation solution contains at least one metal salt, such as a metal nitrate or metal carbonate, a solvent, and has a pH of 1 to 5.5 (including both ends / 1 ≤ pH ≤ 5.5). In one embodiment, the impregnation solution further contains a modifier described herein. In one embodiment, the shaped hydrocracking catalyst is (a) To form an extrudeable mass containing a catalyst substrate composed of alumina, amorphous silica-alumina (ASA), USY zeolite, ZSM-12 zeolite, and optionally β-zeolite, (b) Extruding the above mass to form a shaped extruded product, (c) The above mass is fired to form a fired extruded product, (d) The shaped extruded product is brought into contact with an impregnation solution containing at least one metal salt and a solvent, having a pH of 1 to 5.5 (including both ends / 1 ≤ pH ≤ 5.5), (e) The impregnated extruded product is prepared by removing the impregnation solution solvent and drying it at a temperature sufficient to form a dry impregnated extruded product. 【0050】 In another embodiment, the shaped hydrogen cracking catalyst is (a) To form an extrudeable mass containing a catalyst substrate composed of alumina, amorphous silica-alumina (ASA), USY zeolite, ZSM-12 zeolite, and optionally β-zeolite, (b) Extruding the above mass to form a shaped extruded product, (c) The above mass is fired to form a fired extruded product, (d) Contacting the shaped extruded product with an impregnation solution containing at least one metal, a solvent, and a modifier, wherein the impregnation solution has a pH of 1 to 5.5 (including both ends / 1 ≤ pH ≤ 5.5), (e) The impregnated extruded product is prepared by drying it at a temperature below the decomposition temperature of the modifier, but at a temperature sufficient to remove the impregnation solution and form a dry impregnated extruded product. 【0051】 In another embodiment, the shaped hydrogen cracking catalyst is (a) To form an extrudeable mass containing a catalyst substrate composed of alumina, amorphous silica-alumina (ASA), USY zeolite, ZSM-12 zeolite, and optionally β-zeolite, (b) Extruding the above mass to form a shaped extruded product, (c) The above mass is fired to form a fired extruded product, (d) Contacting the shaped extruded product with an impregnation solution containing at least one metal, a solvent, and a modifier, wherein the impregnation solution has a pH of 1 to 5.5 (including both ends / 1 ≤ pH ≤ 5.5), (e) Drying the impregnated extruded product at a temperature below the decomposition temperature of the modifier, but at a temperature sufficient to remove the impregnation solution solvent and form a dry impregnated extruded product. (f) The above-mentioned dried impregnated extruded product is prepared by thoroughly firing it to remove the above-mentioned modifier and converting at least one metal into an oxide. 【0052】 In one embodiment, a weak acid is used to form an extrudeable mass containing a catalyst substrate. For example, in one embodiment, a diluted aqueous solution of HNO3 acid containing 0.5 to 5% by weight of HNO3 is used. 【0053】 In one embodiment, the impregnation solution comprises a metal carbonate and a modifier. Nickel carbonate is a preferred metal carbonate for use in the preparation of this catalyst. 【0054】 Diluents, promoters, and / or molecular sieves (if used) can be combined with the carrier to form an extrudeable mass. In another embodiment, the carrier and (optionally) diluents, promoters, and / or molecular sieves can be impregnated before or after shaping into the desired form. 【0055】 For each embodiment described herein, the impregnation solution has a pH of 1 to 5.5 (including both ends / 1 ≤ pH ≤ 5.5). In one embodiment, the impregnation solution has a pH of 1.5 to 3.5 (including both ends / 1.5 ≤ pH ≤ 3.5). 【0056】 Depending on the metal nitrates and other components used to form the impregnation solution, the pH of the impregnation solution is typically less than 1, and more typically about 0.5, before the addition of basic components. By adding basic components to the impregnation solution to adjust the pH to 1-5.5 (including both ends / 1 ≤ pH ≤ 5.5), the acid is removed or the acid concentration is reduced to a level that does not cause acid-catalyzed decomposition of ammonium nitrate at a rate fast enough to have a detrimental effect on the hydrocracking catalyst during calcination. In one embodiment, the acid is removed or the acid concentration is reduced to a level that does not cause acid-catalyzed decomposition of ammonium nitrate at a rate fast enough to have a detrimental effect on the hydrocracking catalyst at a rate exceeding 10% by weight of the bulk dry weight during calcination (e.g., does not produce fine powder or fragmented extruded products that account for more than 10% by weight of the bulk dry weight of the hydrocracking catalyst after calcination). 【0057】 The basic component can be any base that is soluble in a solvent of choice relative to the impregnation solution and is substantially harmless to catalyst formation or to the hydrocracking performance of the catalyst, meaning that the base does not have an immeasurable effect on the performance of the hydrocracking catalyst or impart any material defects. A base that is substantially harmless to catalyst formation does not reduce catalytic activity beyond 10°F (5.5°C) based on the performance of the hydrocracking catalyst without pH correction. 【0058】 If a hydrocracking catalyst is to be used in this hydrocracking process, a suitable monobase is ammonium hydroxide. Other exemplary bases include potassium hydroxide, sodium hydroxide, calcium hydroxide, and magnesium hydroxide. 【0059】 In one embodiment, the deposition of at least one metal is achieved in the presence of a modifier selected from the group consisting of compounds represented by structures (1) to (4), including their condensed forms: [ka] 【0060】 In the above formula, (1) R1, R2 and R3 are independently selected from the group consisting of hydrogen; hydroxyl; methyl; amine; and linear or branched 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. 【0061】 (2) R4~R 10 These are independently selected from the group consisting of hydrogen; hydroxyl; and linear or branched, substituted or unsubstituted C2-C3 carboxyalkyl groups. 【0062】 (3)R11 The group 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. 【0063】 Typical examples of modifiers useful in this embodiment include 2,3-dihydroxysuccinic acid, ethanedioic acid, 2-hydroxyacetic acid, 2-hydroxypropanoic acid, 2-hydroxypropane-1,2,3-tricarboxylic acid, methoxyacetic acid, cis-1,2-ethylenedicarboxylic acid, hydroxyethane-1,2-dicarboxylic acid, ethane-1,2-diol, propane-1,2,3-triol, propanedioic acid, and α-hydro-ω-hydroxypoly(oxyethylene). 【0064】 In one embodiment, the modifier used is 2-hydroxypropane-1,2,3-tricarboxylic acid (citric acid). Such modifiers yield excellent results, are economical, and are readily available. 【0065】 In alternative embodiments, the attachment 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-indole-3-yl)-propanoic acid, benzaldehyde, [[(carboxymethyl)imino]bis(ethylenenitrilo)]-tetraacetic acid, 1,2-cyclohexanediamine, 2-hydroxybenzoic acid, thiocyanates, thiosulfates, thiourea, pyridine, and quinoline. 【0066】 The modifier improves the activity and selectivity of the catalyst by inhibiting metal aggregation. 【0067】 For each embodiment described herein, when used, the amount of the modifier in the hydrocracking catalyst before calcination is 2% to 18% by weight, based on the bulk dry weight of the hydrocracking catalyst. 【0068】 The firing of extruded lumps can vary. Typically, extruded lumps can be fired for 1 to 3 hours at temperatures ranging from 752°F (400°C) to 1200°F (650°C). 【0069】 Non-limiting examples of suitable solvents include water and C1-C3 alcohols. Other suitable solvents include polar solvents such as alcohols, ethers, and amines. Water is a preferred solvent. Metal compounds are water-soluble, and it is also preferable that solutions of each metal be formed, or that a single solution containing both metals is formed. The modifier can be prepared in a suitable solvent, preferably in water. 【0070】 The three solvent components can be mixed in any order. That is, all three can be blended together simultaneously, or they can be mixed sequentially in any order. In one embodiment, it is preferable to first mix one or more metal components in an aqueous medium, and then add the modifier. 【0071】 The amounts of the metal precursor and modifier (if used) in the impregnation solution must be selected to achieve a preferred metal:modifier ratio in the catalyst precursor after drying. 【0072】 Typically, the fired extruded parts are exposed to the impregnation solution for 0.1 to 100 hours (more typically 1 to 5 hours) at room temperature ~212°F (100°C) while rotating, until the initial level of moisture is achieved, followed by aging for 0.1 to 10 hours, usually about 0.5 to 5 hours. 【0073】 The drying process is carried out at a temperature sufficient to remove the impregnation solution solvent but below the decomposition temperature of the modifier. In another embodiment, the dried impregnated extruded product is then calcined for an effective time at a temperature above the decomposition temperature of the modifier, typically around 500°F (260°C) to 1100°F (590°C). The present invention observes that when the impregnated extruded product is calcined, the temperature rises to or while drying occurs. This effective time is in the range of about 0.5 to about 24 hours, typically about 1 to about 5 hours. Calcination can be carried out in the presence of an oxygen-containing gas stream such as air, an inert gas stream such as nitrogen, or a combination of oxygen-containing and inert gases. 【0074】 In one embodiment, the impregnated extruded product is fired at a temperature that does not convert the metal to a metal oxide. In yet another embodiment, the impregnated extruded product can be fired at a temperature that is sufficient to convert the metal to a metal oxide. 【0075】 The drying and calcined hydrocracking catalyst of the present invention can be sulfurized to form an active catalyst. Forming the catalyst by sulfurizing the catalyst precursor can be carried out before introducing the catalyst into the reactor (i.e., pre-sulfurization ex-situ) or can be carried out in the reactor (in-situ sulfurization). 【0076】 Suitable sulfiding agents include elemental sulfur, ammonium sulfide, and polyammonium sulfide ((NH4)2S x Examples include ammonium thiosulfate ((NH4)2S2O3), sodium thiosulfate (Na2S2O3), thiourea (CSN2H4), carbon disulfide, dimethyl disulfide (DMDS), dimethyl sulfide (DMS), dibutyl polysulfide (DBPS), mercaptan, tertiary butyl polysulfide (PSTB), tertiary nonyl polysulfide (PSTN), and aqueous ammonium sulfide. 【0077】 Generally, the sulfidating agent is present in excess of the theoretical amount required to form the sulfidation catalyst. In another embodiment, the amount of sulfidating agent represents a sulfur:metal molar ratio of at least 3:1 in order to produce the sulfidation catalyst. 【0078】 The catalyst is converted into an active sulfidation catalyst upon contact with the sulfidating agent at a temperature of 150°F to 900°F (66°C to 482°C), for 10 minutes to 15 days, and under an H2-containing gas pressure of 101 kPa to 25,000 kPa. If the sulfidation temperature is below the boiling point of the sulfidating agent, the process is generally carried out at atmospheric pressure. If it is above the boiling point of the sulfidating agent / optional component, the reaction is generally carried out under pressure. As used herein, completion of the sulfidation process means that at least 95% of the stoichiometric amount of sulfur required to convert the metal to, for example, CO9S8, MoS2, WS2, Ni3S2, etc., has been consumed. 【0079】 In one embodiment, sulfidation can be completed in a gaseous phase comprising hydrogen and a sulfur-containing compound decomposed into H2S. Examples include mercaptans, CS2, thiophene, DMS, DMDS, and suitable sulfur-containing purified effluent gases. The gaseous mixture of H2 and the sulfur-containing compound may be identical or different in its process. Sulfidation in the gaseous phase can be carried out in any preferred manner, including fixed-bed processes and fluidized-bed processes (where the catalyst moves in accordance with the reactor (e.g., an evaporation process and a rotary furnace)). 【0080】 Contact of the catalyst precursor with hydrogen and sulfur-containing compounds can be carried out in a single step over a period of 1 to 100 hours at a temperature of 68°F to 700°F (20°C to 371°C) and a pressure of 101 kPa to 25,000 kPa. Typically, sulfidation is carried out over a set period of time, with the temperature increasing or gradually rising and maintained over a set period until completion. 【0081】 In another embodiment of sulfidation, sulfidation may be carried out in a gaseous phase. Sulfidation is carried out in two or more steps, the first step being carried out at a lower temperature compared to the subsequent steps(s). 【0082】 In one embodiment, sulfidation is carried out in the liquid phase. First, the catalyst precursor is brought into contact with an organic liquid in an amount ranging from 20% to 500% of the total pore volume of the catalyst. Contact with the organic liquid can take place at a temperature ranging from the ambient temperature to 248°F (120°C). After incorporating the organic liquid, the catalyst precursor is brought into contact with hydrogen and sulfur-containing compounds. 【0083】 In one embodiment, the organic liquid has a boiling range of 200°F to 1200°F (93°C to 649°C). Examples of organic liquids include petroleum fractions such as heavy oil, lubricating oil fractions such as mineral lubricating oil, intermediate distillates such as atmospheric diesel fuel, vacuum diesel fuel, straight-run diesel fuel, white spirit, diesel, jet fuel, and kerosene, naphtha, and gasoline. In one embodiment, the organic liquid contains less than 10% by weight, and preferably less than 5% by weight, of sulfur. 【0084】 This process is a single-stage hydrocracking process. The feed to the single-stage hydrocracker often contains significant concentrations of nitrogen and sulfur, in the form of ammonia and hydrogen sulfide. Therefore, the catalyst must be resistant to such contaminated feed, as the presence of nitrogen and sulfur can affect the reaction rate, thereby resulting in selectivity and catalytic activity for different products. 【0085】 This single-stage hydrocracking process involves contacting hydrocarbon feedstock with the catalyst under hydrocarbon conditions to produce an eluate containing middle distillates in a single stage. In one embodiment, the catalyst is used in one or more fixed beds within a single-stage hydrocracking unit, either reused or not (through flow). Optionally, multiple single-stage units operating in parallel may be used. 【0086】 Suitable hydrocarbon raw materials include viscracking gas oil (VGB), heavy coker gas oils, gas oils obtained from hydrocracking residues or desulfurization residues, other thermal cracking oils, deasphaltized oils, Fischer-Tropsch-derived raw materials, FCC unit-derived cycle oils, heavy coal-derived fractions, tar (a by-product of coal vaporization), heavy shale-derived oils, pulp or paper mills, or organic waste oils from waste biomass pyrolysis units. 【0087】 Hydrocracking conditions include a temperature in the range of 175°C to 485°C, a hydrogen:hydrocarbon packing molar ratio of 1 to 100, a pressure in the range of 0.5 to 350 bar, and a liquid-space velocity (LHSV) in the range of 0.1 to 30. In a single-stage hydrocracking process, the use of this catalyst substrate containing ZSM-12 has been observed to improve the selectivity (in the corresponding conversion) of the more desirable intermediate distillate (380 to 530°F) product. With respect to the intermediate distillate product, the selectivity can be at least 20% by weight. In other embodiments, selectivity for the intermediate distillate product can be at least 25% by weight, at least 28% by weight, or even further, at least 30% by weight. The light distillate can also show an increase. Beneficial improvements in the low-temperature flow characteristics of the intermediate distillate have also been observed. 【0088】 Example 1 Table 2 shows the support and catalyst composition, as well as the properties of samples A, B, C, and D: [Table 2] 【0089】 Example 2 Catalyst (sample) A - Comparative Hydrocracking Catalyst A comparative hydrocracking catalyst was prepared according to the following procedure: 49.4 parts by weight of silica-alumina powder (obtained from Sasol), 22.6 parts by weight of pseudoboehmite-alumina powder (obtained from Sasol), 22.4 parts by weight of zeolite Y (Zeolyst, JGC, Tosoh), and 5.6 parts by weight of zeolite β (Clariant, Zeolyst, China Catalyst Group, BASF) were thoroughly mixed. Diluted aqueous HNO3 acid solution (2% by weight) was added to the mixed powder to form an extrudeable paste. The paste was extruded into 1 / 16-inch asymmetrical four-leaf clover shapes and dried overnight at 250°F (121°C). The dried extruded products were calcined at 1100°F (593°C) for 1 hour, purging excess dry air, and then cooled to room temperature. 【0090】 The impregnation of Ni and W was completed by using ammonium metatungstate and basic nickel carbonate hydrate in amounts of 3.8 wt% NiO and 32.0 wt% WO3, respectively, based on the bulk dry weight of the finished catalyst. The chelating agent citric acid (acid / Ni molar ratio of 0.79) was first mixed with DI water and then with basic nickel carbonate hydrate. Next, to decompose the carbonate, the nickel / acid solution was heated in a water bath to over 149°F (65°C), after which ammonium metatungstate was added to the solution. The total volume of the solution matched 103% of the water pore volume of the base extruded sample (initial immersion method). The metal solution was gradually added to the base extruded while rotating the extruded. After the addition of the solution was complete, the immersed extruded was aged for 2 hours. Next, the extruded was dried at 250°F (121°C) for 2 hours. The dried extruded material was calcined at 425°F (218°C) for 1 hour while purging excess dry air, and then cooled to room temperature. This catalyst was named Catalyst A, and its physical properties are summarized in Table 2 above. 【0091】 Example 3 Catalyst (sample) B - Second comparative hydrogen cracking catalyst A comparative hydrocracking catalyst was prepared according to the following procedure: 52.5 parts by weight of silica-alumina powder, 22.6 parts by weight of pseudoboehmite-alumina powder, 16.6 parts by weight of zeolite Y, and 8.3 parts by weight of zeolite β were thoroughly mixed. Diluted aqueous HNO3 acid solution (2% by weight) was added to the mixed powder to form an extrudeable paste. The paste was extruded into 1 / 16-inch asymmetrical four-leaf clover shapes and dried overnight at 250°F (121°C). The dried extruded products were calcined at 1100°F (593°C) for 1 hour, purging excess dry air, and then cooled to room temperature. 【0092】 The impregnation of Ni and W was completed by using ammonium metatungstate and basic nickel carbonate hydrate in amounts of 3.8 wt% NiO and 32.0 wt% WO3, respectively, based on the bulk dry weight of the finished catalyst. The chelating agent citric acid (acid / Ni molar ratio of 0.79) was first mixed with DI water and then with basic nickel carbonate hydrate. Next, to decompose the carbonate, the nickel / acid solution was heated in a water bath to over 149°F (65°C), after which ammonium metatungstate was added to the solution. The total volume of the solution matched 103% of the water pore volume of the base extruded sample (initial immersion method). The metal solution was gradually added to the base extruded while rotating the extruded. After the addition of the solution was complete, the immersed extruded was aged for 2 hours. Next, the extruded was dried at 250°F (121°C) for 2 hours. The dried extruded material was calcined at 425°F (218°C) for 1 hour while purging excess dry air, and then cooled to room temperature. This catalyst was named Catalyst B, and its physical properties are summarized in Table 2 above. 【0093】 Example 4 Novel hydrogen cracking catalyst containing catalyst (sample) C-ZSM-12 zeolite A hydrocracking catalyst was prepared according to the following procedure: 49.4 parts by weight of silica-alumina powder, 22.6 parts by weight of pseudoboehmite-alumina powder, 16.0 parts by weight of zeolite Y, 8.0 parts by weight of zeolite β, and 4.0 parts by weight of zeolite ZSM-12 were thoroughly mixed. Diluted aqueous solution of HNO3 acid (2% by weight) was added to the mixed powder to form an extrudeable paste. The paste was extruded into 1 / 16-inch asymmetrical four-leaf clover shapes and dried overnight at 250°F (121°C). The dried extruded products were calcined at 1100°F (593°C) for 1 hour, purging excess dry air, and then cooled to room temperature. 【0094】 The impregnation of Ni and W was completed by using ammonium metatungstate and basic nickel nitrate hydrate in amounts of 3.8 wt% NiO and 32.0 wt% WO3, respectively, based on the bulk dry weight of the finished catalyst. The chelating agent citric acid (acid / Ni molar ratio of 0.79) was first mixed with DI water and then with basic nickel carbonate hydrate. Next, to decompose the carbonate, the nickel / acid solution was heated to 149°F (65°C) in a water bath, and then ammonium metatungstate was added to the solution. The total volume of the solution matched 103% of the water pore volume of the base extruded sample (initial immersion method). The base solution was gradually added to the base extruded while rotating the extruded. After the addition of the solution was complete, the immersed extruded was aged for 5 hours. Next, the extruded material was dried at 150°F (66°C) for 1 hour, and then at 250°F (121°C) for 1 hour. The dried extruded material was calcined at 425°F (218°C) for 1 hour while purging excess dry air, and then cooled to room temperature. This catalyst was named Catalyst C, and its physical properties are summarized in Table 2 above. 【0095】 Example 5 Second novel hydrogen cracking catalyst containing catalyst (sample) D-ZSM-12 zeolite A novel hydrocracking catalyst was prepared according to the following procedure: 49.4 parts by weight of silica-alumina powder, 22.6 parts by weight of pseudoboehmite-alumina powder, 16.0 parts by weight of zeolite Y, and 12.0 parts by weight of zeolite ZSM-12 were thoroughly mixed. Diluted aqueous HNO3 acid solution (2% by weight) was added to the mixed powder to form an extrudeable paste. The paste was extruded into 1 / 16-inch asymmetrical four-leaf clover shapes and dried overnight at 250°F (121°C). The dried extruded products were calcined at 1100°F (593°C) for 1 hour, purging excess dry air, and then cooled to room temperature. 【0096】 The impregnation of Ni and W was completed by using ammonium metatungstate and basic nickel carbonate hydrate in amounts of 3.8 wt% NiO and 32.0 wt% WO3, respectively, based on the bulk dry weight of the finished catalyst. The chelating agent citric acid (acid / Ni molar ratio of 0.79) was first mixed with DI water and then with basic nickel carbonate hydrate. Next, to decompose the carbonate, the nickel / acid solution was heated in a water bath to over 149°F (65°C), after which ammonium metatungstate was added to the solution. The total volume of the solution matched 103% of the water pore volume of the base extruded sample (initial immersion method). The metal solution was gradually added to the base extruded while rotating the extruded. After the addition of the solution was complete, the immersed extruded was aged for 5 hours. Next, the extruded product was dried at 150°F (66°C) for 1 hour, and then at 250°F (121°C) for 1 hour. The dried extruded product was calcined at 425°F (218°C) for 1 hour while purging excess dry air, and then cooled to room temperature. This catalyst was named Catalyst D, and its physical properties are summarized in Table 2 above. 【0097】 [Table 3] 【0098】 Example 6 Various catalysts from Example 1 were used under similar conditions for the hydrocracking of VGO feedstocks shown in Table 3. All catalyst extrudes were shortened to 1-2 L / D and packed into 3 / 8-inch OD stainless steel reactors. A total catalyst volume of 16.0 mL was loaded into two reactors in bench-scale units (BSUs). 8.0 mL of ICR 511 was loaded into the first reactor as a hydrocracking pretreatment for nitrogenation, sulfuration, and dearomatization. ICR 511 was operated at temperatures of 710-725°F (373-385°C) to produce total liquid products (WLP) with nitrogen content ranging from 5-50 ppm. The 8 mL of hydrogenocrack catalyst prepared in Example 1 was loaded into the second reactor and operated at a temperature in the range of 710–780°F (373–416°F) to reach a hydrogenocrack conversion of 20%–90% by weight (<700°F or <371°F). 【0099】 The selected hydrocracking characteristics are shown in Table 4 below: [Table 4] 【0100】 As can be seen from the results in Table 4, samples C and D represent the catalysts used in this process, resulting in significant improvements in conversion of the middle distillate product (380-530°F, 193°C-277°F). Improvements in the light distillate (300-380°F) can also be observed. Figures 1 and 2 compare the low-temperature flow characteristics achieved when using samples B and C. Sample C shows a product with improved cloud point and pour point characteristics.

Claims

[Claim 1] A hydrocracking process comprising passing a hydrocarbon feed through a single-stage hydrocracking unit, wherein the feed is hydrocracking under hydrocracking conditions, and the catalyst in the hydrocracking unit comprises a substrate composed of alumina, amorphous silica-alumina (ASA) material, USY zeolite, ZSM-12, and β-zeolite, The amount of alumina is in the range of 5 to 40% by weight. The amount of ASA is in the range of 45-75% by weight. The amount of USY zeolite is in the range of 4 to 20% by weight. The amount of β-zeolite is in the range of 4 to 20% by weight. The amount of ZSM-12 is in the range of 2 to 20% by weight. The selectivity of the intermediate distillate (380–530°F (193–277°C)) is at least 28% by weight in an apparent conversion of 60% by weight (<700°F (<371°C)), The catalyst comprises metallic nickel (Ni) and tungsten (W) impregnated into the substrate. The catalyst comprises 2% to 10% by weight of nickel material and 8% to 40% by weight of tungsten material, based on the bulk dry weight of the hydrocracking catalyst. The process wherein the catalyst includes a modifier. [Claim 2] The process according to claim 1, wherein the supply includes VGO. [Claim 3] The modifier has the structure (1) to (4), 【Chemistry 1】 During the ceremony, (1) R １ , R ２ and R ３ are independently selected from the group consisting of hydrogen, hydroxyl, methyl, amine, and linear or branched, substituted or unsubstituted C １ -C ３ alkyl group, C １ -C ３ alkenyl group, C １ -C ３ hydroxyalkyl group, C １ -C ３ alkoxyalkyl group, C １ -C ３ aminoalkyl group, C １ -C ３ oxoalkyl group, C １ -C ３ carboxyalkyl group, C １ -C ３ aminocarboxyalkyl group, and C １ -C ３ hydroxycarboxyalkyl group, and are independently selected from the group consisting of: (2) R ４ ~R １０ C is a substituted or unsubstituted C, which is a linear or branched C molecule. ２ -C ３ Independently selected from the group consisting of carboxyalkyl groups, (3) Caution １１ C is a linear or branched, saturated and unsaturated, substituted or unsubstituted C １ -C ３ Alkyl alkyl group, C １ -C ３ Hydroxyalkyl groups, and C １ -C ３ Selected from the group consisting of oxoalkyl groups, The process according to claim 1, comprising a group of compounds represented by the structures (1) to (4) described above, and selected from their condensation forms. [Claim 4] The process according to claim 3, wherein the modifier comprises citric acid. [Claim 5] The catalyst in the hydrocracking unit is (a) To form an extrudeable mass containing the catalyst substrate, (b) Extruding the mass to form a shaped extruded product, (c) The shaped extruded product is fired to form a fired extruded product, (d) Prepare an impregnation solution containing at least one metal nitrate or metal carbonate, a solvent, a modifier and an ammonium-containing component, and adjust the pH of the impregnation solution to 1 to 5.5 (including both ends) with a hydroxide base, (e) bringing the calcined extruded product into contact with the impregnation solution to form an impregnated extruded product, (f) The process according to claim 1, wherein the impregnated extruded product is prepared by removing the impregnation solution solvent and drying it at a temperature sufficient to form a dry impregnated extruded product. [Claim 6] The process according to claim 5, wherein the impregnation solution contains nickel carbonate. [Claim 7] The modifier has the structure (1) to (4), 【Chemistry 1】 During the ceremony, (1) R １ , R ２ and R ３ This includes hydrogen, hydroxyl, methyl, amine, and linear or branched, substituted or unsubstituted C atoms. １ -C ３ Alkyl alkyl group, C １ -C ３ Alkenyl group, C １ -C ３ Hydroxyalkyl group, C １ -C ３ Alkoxyalkyl groups, C １ -C ３ Aminoalkyl group, C １ -C ３ Oxoalkyl group, C １ -C ３ Carboxyalkyl group, C １ -C ３ aminocarboxyalkyl groups, and C １ -C ３ Independently selected from the group consisting of hydroxycarboxyalkyl groups, (2) R ４ ~R １０ C is a substituted or unsubstituted C, which is a linear or branched C molecule. ２ -C ３ Independently selected from the group consisting of carboxyalkyl groups, (3) Caution １１ C is a linear or branched, saturated and unsaturated, substituted or unsubstituted C １ -C ３ Alkyl alkyl group, C １ -C ３ Hydroxyalkyl groups, and C １ -C ３ Selected from the group consisting of oxoalkyl groups, The process according to claim 5, comprising a group of compounds represented by the structures (1) to (4) described above, and selected from their condensation forms. [Claim 8] The process according to claim 7, wherein the modifier comprises citric acid. [Claim 9] A hydrocracking catalyst comprising alumina, amorphous silica-alumina (ASA), USY zeolite, β-zeolite, and ZSM-12 as substrates, The amount of alumina is in the range of 5 to 40% by weight. The amount of ASA is in the range of 45-75% by weight. The amount of USY zeolite is in the range of 4 to 20% by weight. The amount of β-zeolite is in the range of 4 to 20% by weight. The amount of ZSM-12 is in the range of 2 to 20% by weight. The catalyst comprises metallic nickel (Ni) and tungsten (W) impregnated into the substrate. The catalyst comprises 2% to 10% by weight of nickel material and 8% to 40% by weight of tungsten material, based on the bulk dry weight of the hydrocracking catalyst. A hydrocracking catalyst wherein the catalyst contains a reforming agent. [Claim 10] The modifier has the structure (1) to (4), 【Chemistry 1】 During the ceremony, (1) R １ , R ２ and R ３ This includes hydrogen, hydroxyl, methyl, amine, and linear or branched, substituted or unsubstituted C atoms. １ -C ３ Alkyl alkyl group, C １ -C ３ Alkenyl group, C １ -C ３ Hydroxyalkyl group, C １ -C ３ Alkoxyalkyl groups, C １ -C ３ Aminoalkyl group, C １ -C ３ Oxoalkyl group, C １ -C ３ Carboxyalkyl group, C １ -C ３ aminocarboxyalkyl groups, and C １ -C ３ Independently selected from the group consisting of hydroxycarboxyalkyl groups, (2) R ４ ~R １０ C is a substituted or unsubstituted C, which is a linear or branched C molecule. ２ -C ３ Independently selected from the group consisting of carboxyalkyl groups, (3) R １１ is a linear or branched, saturated and unsaturated, substituted or unsubstituted C １ -C ３ alkyl group, C １ -C ３ hydroxyalkyl group, and C １ -C ３ selected from the group consisting of oxoalkyl groups A hydrocracking catalyst process according to claim 9, comprising a group of compounds represented by the structures (1) to (4) described above, and selected from their condensation forms. [Claim 11] The hydrocracking catalyst according to claim 9, wherein the modifier contains citric acid.

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