Production of low sulfur marine fuel using a hydrogenation catalyst and method of making and using same

Abstract

The application discloses a hydrogenation catalyst for producing low-sulfur marine fuel and a preparation method and application thereof. The catalyst comprises a gallium-modified silicon-aluminum carrier and an active metal component. In the gallium-modified silicon-aluminum carrier, the mass content of gallium oxide is 2.0% to 5.0% based on the mass of the gallium-modified silicon-aluminum carrier, the mass content of silicon dioxide is 20.0% to 60.0%, and the mass content of aluminum oxide is 35.0% to 78.0%. The total acid content of the catalyst is 0.23 to 0.57 mmol / g, the B acid content is 0.03 to 0.07 mmol / g, and the L acid content is 0.2 to 0.5 mmol / g. The catalyst has the advantages of high active metal utilization rate, good wear resistance, high hydrogenation performance, high selective desulfurization activity, low aromatic hydrocarbon saturation activity and the like, and is suitable for being applied to a process for producing low-sulfur marine fuel from heavy and poor residual oil.

Description

Technical Field

[0001] This invention belongs to the field of catalyst preparation, and relates to a catalytic material and its preparation method, specifically to a hydrogenation catalyst for producing low-sulfur marine fuel, its preparation method, and its application. Background Technology

[0002] As global environmental problems intensify, countries around the world have successively introduced environmental regulations to limit the sulfur content of marine fuel oil (hereinafter referred to as marine fuel). The International Maritime Organization (IMO) requires that the upper limit of sulfur content in marine fuel be reduced to 0.5 wt% by January 1, 2020. After the implementation of the IMO's 2020 sulfur cap policy, it is estimated that low-sulfur heavy marine fuel will account for about 45% of total consumption in the short term and about 40% in the long term, leading to a supply shortage of low-sulfur marine fuel.

[0003] Currently, high-sulfur heavy marine fuel is mainly produced through blending. The blending components primarily originate from high-sulfur residue oil that is difficult to process in refineries, as well as non-ideal byproducts such as catalytic slurry and low-quality secondary processing distillates. The key to blending is ensuring that viscosity, stability, and the content of aluminum and silicon (catalyst powder in the catalytic slurry) meet quality requirements. However, directly producing low-sulfur marine fuel with a sulfur content below 0.5 wt% using current blending components is difficult; low-sulfur residue oil must be added for blending. Similarly, using large quantities of expensive low-sulfur straight-run residue oil to blend and produce heavy marine fuel would significantly increase production costs. Therefore, developing high-performance residue hydrotreating catalysts is an effective and economical means of producing low-sulfur marine fuel.

[0004] CN1458236A discloses a method for preparing a catalyst for the hydrodemetallization and desulfurization of heavy oil. This method uses two different forms of aluminum-containing materials: calcined alumina and aluminum hydroxide dry powder. Alkali metals and / or alkaline earth metals are used as additives. Part of the additive is premixed with the aluminum hydroxide dry powder, and part is loaded onto the catalyst using an impregnation method, resulting in a non-uniform distribution of the additive on the catalyst. The catalyst obtained by this method is not very suitable for producing low-sulfur marine fuel, and its activity and stability need further improvement.

[0005] CN114749193A discloses a hydrogenation catalyst for producing low-sulfur marine fuel and its preparation method. The catalyst comprises a silicon-aluminum material and a first metal and a second metal supported on the silicon-aluminum material; wherein the first metal is selected from at least one of Group IVB, Group VIB, and Group VIII metals; and the second metal is selected from at least one of Group VIB and Group VIII metals. The preparation method includes: adding an acidic aluminum source to a silicon source and then mixing it with a first metal salt solution to obtain a mixture A; contacting the mixture A with an alkaline aluminum source in the presence of water to obtain a slurry B; subjecting the slurry B to hydrothermal treatment to obtain a support precursor; mixing the support precursor, a molding agent, and a binder uniformly, molding, drying, and calcining to obtain a support; and mixing the support with a second metal salt solution, further drying, and calcining to obtain the catalyst. The catalyst is too acidic, with the ratio of Brønsted acid to Lewis acid reaching 0.3 to 0.8. While achieving desulfurization, this method often causes hydrocarbon cracking reactions, which not only increases processing costs but also greatly affects the properties of ship fuel. Summary of the Invention

[0006] To address the problems existing in the prior art, the purpose of this invention is to provide a hydrogenation catalyst for producing low-sulfur marine fuel, its preparation method, and its application. The catalyst of this invention has advantages such as high utilization rate of active metals, good wear resistance, high hydrogenation performance, especially high selective desulfurization activity, and low aromatic saturation activity, making it suitable for use in the production of low-sulfur marine fuel from heavy, low-quality residual oil.

[0007] The first aspect of the present invention provides a hydrogenation catalyst for producing low-sulfur marine fuel, comprising a gallium-modified silicon-aluminum support and an active metal component, wherein, based on the mass of the gallium-modified silicon-aluminum support, the mass content of gallium oxide is 2.0% to 5.0%, the mass content of silicon dioxide is 20.0% to 60.0%, and the mass content of aluminum oxide is 35.0% to 78.0%.

[0008] According to the present invention, the active metal comprises at least one metal component selected from Group VIII and at least one metal component selected from Group VIB; the Group VIII metal is preferably nickel and / or cobalt, and the Group VIB metal is preferably molybdenum and / or tungsten.

[0009] According to the present invention, based on the mass of the catalyst, the mass content of the support is 74.0% to 87.0%, the content of Group VIII metals (calculated as oxides) is 2.0% to 6.0%, and the content of Group VIB metals (calculated as oxides) is 10.0% to 20.0%.

[0010] According to the present invention, the catalyst also contains phosphorus, and the phosphorus content is 1.0% to 5.0% based on the mass of the catalyst and calculated as phosphorus pentoxide.

[0011] According to the present invention, the catalyst has the following properties: a specific surface area of ​​180–230 m². 2 / g, pore volume is 0.5~0.7mL / g, average pore size is 10.0~30.0nm, and mechanical strength is 120~190N / cm.

[0012] According to the present invention, the total acid content of the catalyst is 0.23-0.57 mmol / g, the Brønsted acid content is 0.03-0.07 mmol / g, and the Lewis acid content is 0.2-0.5 mmol / g.

[0013] A second aspect of the present invention provides a method for preparing the above-mentioned hydrogenation catalyst for producing low-sulfur marine fuel, comprising:

[0014] (1) Mix and stir the acidic aluminum salt aqueous solution, silicon source, and organic acid to obtain material I;

[0015] (2) Material I is subjected to a precipitation reaction with gallium-containing solution and alkaline aluminum salt aqueous solution in parallel flow to obtain material II;

[0016] (3) Material II is subjected to hydrothermal treatment with a nonionic surfactant to obtain gallium-modified silicon-aluminum material;

[0017] (4) The gallium-modified silicon-aluminum material, adhesive, extrusion aid and water obtained in step (3) are mixed and kneaded, dried and calcined to obtain a catalyst support;

[0018] (5) Load the active metal component onto the catalyst support obtained in step (4), and then dry and calcine it to obtain the catalyst.

[0019] According to the present invention, the acidic aluminum salt in step (1) is at least one of aluminum sulfate, aluminum chloride or aluminum nitrate, and the concentration of the acidic aluminum salt solution, calculated as Al2O3, is 20-100 g / 100 mL; the silicon source is one or more of water-soluble silicates, water glass, and silica sol, and the concentration of the silicon source, calculated as SiO2, is 30-70 g / 100 mL, and the weight ratio of the silicon source (calculated as SiO2) to the acidic aluminum source (calculated as Al2O3) is 1:1-7:1.

[0020] According to the present invention, the organic acid in step (1) is one or more selected from maleic acid, fumaric acid, adipic acid, tartaric acid, citric acid, oxalic acid, acetic acid, salicylic acid, and malic acid. The mass concentration of the organic acid is 7% to 16%. The amount of organic acid added makes the pH value of the material I 2 to 4, preferably 3 to 4.

[0021] According to the present invention, the gallium-containing solution in step (2) is a gallium nitrate solution with a concentration of 0.5–2.5 mol / L. The alkaline aluminum salt is at least one of sodium aluminate or potassium aluminate. The concentration of the alkaline aluminum salt solution, calculated as Al2O3, is 20–100 g / 100 mL. The ratio of the co-current flow rates of the gallium-containing solution, the material I, and the alkaline aluminum salt solution is 1:3–7:1–3. The reaction temperature in step (2) is 60–90 °C, the reaction time is 60–180 minutes, and the pH value is 8.0–9.7. The reaction is preferably carried out under stirring conditions, with a stirring rate of 100–500 rad / min, preferably 150–450 rad / min.

[0022] According to the present invention, the nonionic surfactant in step (3) is selected from one or more of polyethylene glycol, alkylolamide, and polyether; the alkylolamide is one or more of lauroyl diethanolamine and coconut oil fatty acid diethanolamide; the polyether is one or more of AEO-6 and AEO-9; the molecular weight of the polyethylene glycol is 200-1000, preferably 200-700; the amount of the nonionic surfactant added is 0.1%-5% of the mass of material II obtained in step (2) based on alumina, preferably 0.5%-3%. The concentration of the nonionic surfactant is 30-70 g / 100 mL.

[0023] According to the present invention, the conditions for the sealing hydrothermal treatment in step (3) are as follows: the hydrothermal treatment temperature is 80–130°C, the time is 3–18 hours, and the heating rate is 8–15°C / min. Preferably, the hydrothermal treatment adopts a two-stage hydrothermal treatment: the first stage hydrothermal treatment temperature is 80–110°C, the first stage hydrothermal treatment time is 1–9 hours, and the second stage hydrothermal treatment temperature is 100–130°C, the second stage hydrothermal treatment time is 1–9 hours, wherein the second stage hydrothermal treatment temperature is at least 15°C higher than the first stage hydrothermal treatment temperature, preferably at least 20°C higher. After the reaction, washing and drying can be performed. The drying conditions are: 100–170°C for 1–7 hours.

[0024] According to the present invention, the preparation process of the catalyst support in step (4) involves adding an extrusion aid, a binder, etc., to a gallium-modified silicon-aluminum material, kneading it into a plastic body, and then molding it. The molding can be carried out using conventional molding methods, such as extrusion molding, tablet molding, etc., with extrusion molding being preferred. The amount of extrusion aid added is 1.0 wt% to 4.0 wt% of the gallium-modified silicon-aluminum material; the amount of binder added is 1.0 wt% to 5.0 wt% of the gallium-modified silicon-aluminum material; and the amount of water added is 80.0 wt% to 100.0 wt% of the gallium-modified silicon-aluminum material. The extrusion aid is guar gum powder, and the binder is nitric acid.

[0025] According to the present invention, the drying temperature in step (4) is 120-160°C, the drying time is 2-6 hours, the calcination temperature is 550-800°C, and the calcination time is 4-6 hours.

[0026] According to the present invention, the method of loading the active metal component onto the catalyst support obtained in step (4) in step (5) is preferably an impregnation method. The active metal includes at least one metal component selected from Group VIII and at least one metal component selected from Group VIB. The Group VIII metal is preferably nickel and / or cobalt, and the Group VIB metal is preferably molybdenum and / or tungsten.

[0027] According to the present invention, the impregnation in step (5) adopts the spray impregnation method. During impregnation, the sample is impregnated with equal volume or supersaturated impregnation. Preferably, after impregnation, the sample is placed under closed conditions at 20-30°C for 6-12 hours before the drying step.

[0028] According to the present invention, the active metal in the impregnation solution used in step (5), calculated as metal oxides, comprises a Group VIB metal content of 150–450 g / L, preferably 300–400 g / L, and a Group VIII metal content of 10–120 g / L, preferably 40–60 g / L. Further, the impregnation solution also contains a phosphorus source; calculated as phosphorus, the phosphorus concentration is 20–80 g / L, preferably 40–60 g / L.

[0029] According to the present invention, in step (5), the drying conditions are constant temperature at 100-160°C for 1-8 hours; the calcination conditions are constant temperature at 450-650°C for 2-7 hours, preferably constant temperature at 480-600°C for 2-7 hours.

[0030] A third aspect of the present invention provides the application of the above-described catalyst or the catalyst obtained by the above-described preparation method in the hydrogenation of inferior residue oil to produce low-sulfur marine fuel.

[0031] Furthermore, in the above applications, the reaction conditions are: reaction pressure of 10–18 MPa, reaction temperature of 380–430 °C, and liquid hourly space velocity of 0.1–0.6 h⁻¹. -1 The hydrogen-to-oil volume ratio is 400–800.

[0032] Compared with the prior art, the present invention has the following advantages:

[0033] 1. The catalyst for producing low-sulfur marine fuel of this invention comprises a support and an active metal component, wherein the support includes a gallium-modified silicon-aluminum support; the total acid content of the catalyst is 0.23–0.57 mmol / g, the Brønsted acid content is 0.03–0.07 mmol / g, and the Lewis acid content is 0.2–0.5 mmol / g. The catalyst of this invention has suitable Brønsted acid and abundant Lewis acid content, exhibiting advantages such as high desulfurization rate and low aromatic saturation and cracking rate. It is suitable for the hydroconversion process of sulfides in asphaltene during the production of low-sulfur marine fuel, demonstrating high hydrodesulfurization activity and good stability.

[0034] 2. In the gallium-modified silicon-aluminum carrier preparation method provided by this invention, the addition of organic acid increases the absolute value of the Zeta potential of the system and strengthens the electrostatic repulsion between particles, which is beneficial to the dispersion and flowability of the slurry. Simultaneously, the acidified silica flocs adsorb onto the aluminum hydroxide colloid, providing nuclei for subsequent reactions and promoting the increase in the size of the prepared carrier precursor grains. This facilitates the formation of a carrier precursor with large pore volume and large pore size coated with organic chains. The formation of hydrogen bonds between the nonionic surfactant and the hydroxyl groups of the aluminum hydroxide hydrosol prevents the particles from adhering and agglomerating, causing the gel particles to oriented into ordered crystal precipitates or crystalline particles. Furthermore, the free silicon species can undergo ion exchange with the nonionic surfactant to form a complex, ultimately forming a mesoporous material with a stable structure. By replacing part of the framework Al with Ga, since Ga can enter the Si-O-Al framework structure like Al, the reduction of framework Al can be avoided from adversely affecting crystallinity while adjusting the acidity. This results in a silicon-aluminum material with controllable acidity. At the same time, the weak acid sites formed by framework Ga and the gallium present outside the framework can work synergistically with the strong Brønsted acid sites formed by Si-O-Al, which is beneficial for selective hydrodesulfurization and reduces the saturation of aromatics, so as to produce low-sulfur marine fuel with low hydrogen consumption and reduced costs.

[0035] 3. The catalyst of the present invention is applied to the process of producing low-sulfur marine fuel from heavy and inferior residual oil. It has the advantages of high utilization rate of active metal, good wear resistance, high hydrogenation performance, and especially high selective desulfurization activity, while having low aromatic saturation activity. Detailed Implementation

[0036] The technical solution of the present invention will be described in detail below with reference to the embodiments.

[0037] In this invention, the determination of total acidity, L-acid, or Brønsted acid is performed using infrared spectroscopy. The instrument used is a Nicot Fourier Transform Infrared Spectrometer-6700 (USA). The determination method is as follows: Weigh 20 mg of sample with a particle size less than 200 mesh, press it into a thin sheet with a diameter of 20 mm, and place it on the sample holder of the absorption cell. Place 200 mg of sample into the instrument's hanging cup, connect the absorption cell and adsorption tube, and perform vacuum treatment to achieve a vacuum degree of 4 × 10⁻⁶. -2At Pa, the temperature is raised to 500℃ and held for 1 hour to remove adsorbates from the sample surface. After cooling to room temperature, pyridine adsorption is allowed to reach saturation. The temperature is then raised to 160℃ and equilibrated for 1 hour to desorb the physically adsorbed pyridine, thus yielding the total acid content, Brønsted acid (B acid), and Lewis acid content. The acid content is expressed in mmol / g. In the infrared spectrum, the sample is located at 1450 cm⁻¹. -1 The nearby absorption peak is for L-acid, at 1540 cm⁻¹. -1 The nearby absorption peak indicates Brønsted acid.

[0038] In this invention, the specific surface area, pore volume, and average pore size were measured using an ASAP2420 fully automated physical adsorption instrument from Micron Instruments, Inc. The measurement method is as follows: the sample was treated at 300℃ and 0.1 MPa for 4 hours, with liquid N2 as the adsorbate at an adsorption temperature of -196℃. The sample was accurately weighed and then analyzed. The specific surface area was calculated using the BET method, and the pore volume and average pore size were calculated using the BJH method.

[0039] In this invention, the mechanical strength was measured using a ZQJ-Ⅲ type particle strength tester manufactured by Dalian Intelligent Testing Machine Factory.

[0040] In this invention, the catalyst composition was determined using spectrophotometry. The testing instrument was a Lambda 365 UV spectrophotometer.

[0041] In this invention, sulfur and nitrogen content are determined using a PHOTONLAB sulfur-nitrogen analyzer (USA). The method is as follows: Hydrocarbon samples are directly injected into a pyrolysis tube or sample boat. The sample is then fed to a high-temperature combustion tube by a sample injector. Nitrogen compounds in the sample are quantitatively converted to NO. The reaction products are carried by a carrier gas, and after passing through a dryer to remove moisture, they enter the reaction chamber. NO reacts with O3 gas from an ozone generator in the reaction chamber, converting into excited-state NO2. When the excited-state NO2 transitions to the ground state, it emits photons. The emitted light signal is detected by a photomultiplier tube at a specific wavelength, and its intensity is proportional to the total nitrogen content in the original sample. Therefore, the total nitrogen content in the sample can be determined by measuring the intensity of the chemiluminescence light. Under oxygen-rich conditions, sulfur is oxidized to SO2. The gas generated by sample combustion, after water removal, is irradiated with ultraviolet light. SO2 absorbs the energy of the ultraviolet light and transforms into excited-state SO2. When the excited-state SO2 returns to the stable state of SO2, it emits fluorescence, which is detected by a photomultiplier tube. The sulfur content of the sample is calculated from the obtained signal value.

[0042] In this invention, the aromatic fraction percentage is determined according to the Ministry of Transport standard JTJ 052—2000 "Test Procedures for Asphalt and Asphalt Mixtures in Highway Engineering" T0618 "Asphalt Chemical Component Test (Four-Component Method)" and the petrochemical industry standard NB / SH / T 0509—2010 "Determination of Petroleum Asphalt Components". Column chromatography is employed. First, asphaltene is separated using n-heptane. After filtration, soluble impurities in the asphaltene are separated by reflux with n-heptane. Then, the asphaltene is dissolved and purified by reflux with toluene. Next, the deasphalted components are concentrated and adsorbed onto an alumina column, and successively washed with n-heptane, toluene, and toluene-ethanol to obtain saturated fractions, aromatic fractions, and resins, respectively.

[0043] In this invention, the instrument for determining the percentage of carbon residue is the BT-17144 trace carbon residue analyzer. The determination method is to place the weighed sample into a sample tube and heat it to 500°C in an inert gas (nitrogen) atmosphere according to a specified temperature program. The volatile substances generated during the reaction are carried away by the nitrogen gas, and the carbonaceous residue is reported as a percentage of the original sample.

[0044] In this invention, unless otherwise specified, % refers to mass percentage.

[0045] Example 1

[0046] (1) Prepare an aluminum sulfate solution with a concentration of 50 g / 100 mL (based on Al2O3) and a silica sol solution with a concentration of 60 g / 100 mL (based on SiO2). The weight ratio of the silicon source (based on SiO2) to the acidic aluminum source (based on Al2O3) is 2.4:1. Add 8% citric acid to adjust the pH of the solution to 3 to obtain material I.

[0047] (2) Add 2.0L of clean water to the reactor and heat it to 60℃. Stir at 200rad / min. Control the flow rates of material I, 60g / 100mL sodium aluminate solution, and 2mol / L gallium nitrate solution to 50mL / min, 20mL / min, and 10mL / min, respectively. Continuously add them to the reactor. During the reaction, control the pH of the reaction to be 8, the reaction time to be 180min, and the reaction temperature to be 60℃.

[0048] (3) After the precipitation reaction was complete, the temperature was raised to 95℃ and the stirring rate was adjusted to 300 rad / min. A 55 g / 100 mL polyethylene glycol (molecular weight 600) solution was introduced into the reactor for hydrothermal treatment, with the nonionic surfactant added at 2.4 wt% of material II (calculated as alumina). After sealing, the temperature was raised to 100℃ at a rate of 15℃ / min and held for 3 hours, then raised to 120℃ at a rate of 10℃ / min and held for 6 hours. The resulting slurry was washed with 90℃ hot water until neutral, and dried at 120℃ for 3 hours to obtain gallium-modified silicon-aluminum material.

[0049] (4) Weigh 448g of gallium-modified silicon-aluminum material, add 12g of guar gum powder, 9g of nitric acid and 378g of water, mix and knead into shape, dry at 140℃ for 3 hours, and calcine at 650℃ for 4 hours to obtain catalyst support A.

[0050] (5) A 90 mL impregnation solution was prepared using 36 g of molybdenum trioxide, 9 g of basic nickel carbonate, and 16.2 g of phosphoric acid. The solution was then sprayed onto carrier A-0 to obtain A-1. A-1 was placed in a sealed container at 25 °C for 6 hours, dried at 120 °C for 4 hours, and finally calcined at 550 °C for 4 hours to obtain CA-1.

[0051] Example 2

[0052] (1) Prepare an aluminum sulfate solution with a concentration of 30 g / 100 mL (based on Al2O3) and a silica sol solution with a concentration of 60 g / 100 mL (based on SiO2). The weight ratio of the silicon source (based on SiO2) to the acidic aluminum source (based on Al2O3) is 4:1. Add 10% citric acid to adjust the pH of the solution to 4 to obtain material I.

[0053] (2) Add 2.0L of purified water to the reactor and heat it to 80℃. Stir at 250rad / min. Control the flow rates of material I, 80g / 100mL sodium aluminate solution, and 2.5mol / L gallium nitrate solution to 60mL / min, 11mL / min, and 10mL / min, respectively. Continuously add them to the reactor. During the reaction, control the reaction pH to 8.5, the reaction time to 90min, and the reaction temperature to 80℃.

[0054] (3) After the precipitation reaction was complete, the temperature was raised to 85℃ and the stirring rate was adjusted to 350 rad / min. A 60 g / 100 mL lauroyl diethanolamine solution was introduced into the reactor for hydrothermal treatment, with the nonionic surfactant added at 2.4 wt% of material II (calculated as alumina). After sealing, the temperature was raised to 90℃ at a rate of 10℃ / min and held for 4 hours, then raised to 130℃ at a rate of 15℃ / min and held for 4 hours. The resulting slurry was washed with 90℃ hot water until neutral, and dried at 130℃ for 4 hours to obtain gallium-modified aluminum-silicon material.

[0055] (4) Weigh 435g of gallium-modified silicon-aluminum material, add 12g of guar gum powder, 11.2g of nitric acid and 375g of water, mix and knead into shape, dry at 120℃ for 4 hours, and calcine at 620℃ for 6 hours to obtain catalyst support B.

[0056] (5) A 90 mL impregnation solution was prepared using 32 g of molybdenum trioxide, 7.8 g of basic nickel carbonate, and 14.2 g of phosphoric acid. The solution was then sprayed onto carrier B-0 to obtain B-1. B-1 was placed in a sealed container at 24 °C for 6 hours, dried at 120 °C for 4 hours, and finally calcined at 500 °C for 6 hours to obtain CB-1.

[0057] Example 3

[0058] (1) Prepare an aluminum sulfate solution with a concentration of 80 g / 100 mL (based on Al2O3) and a silica sol solution with a concentration of 40 g / 100 mL (based on SiO2). The weight ratio of the silicon source (based on SiO2) to the acidic aluminum source (based on Al2O3) is 1:1. Add 15% citric acid to adjust the pH of the solution to 3 to obtain material I.

[0059] (2) Add 2.0L of clean water to the reactor and heat it to 80℃. Stir at 200rad / min. Control the flow rates of material I, 75g / 100mL sodium aluminate solution, and 2mol / L gallium nitrate solution to 30mL / min, 15mL / min, and 10mL / min, respectively. Continuously add them to the reactor. During the reaction, control the reaction pH to 9, the reaction time to 120min, and the reaction temperature to 80℃.

[0060] (3) After the precipitation reaction was complete, the temperature was raised to 95℃ and the stirring rate was adjusted to 400 rad / min. A 45 g / 100 mL ALAEO-9 solution was introduced into the reactor for hydrothermal treatment, with the nonionic surfactant added at 2.6 wt% of material II (calculated as alumina). After sealing, the temperature was raised to 100℃ at a rate of 15℃ / min and held for 8 hours. Then, the temperature was raised to 130℃ at a rate of 10℃ / min and held for 8 hours. The slurry after the reaction was washed with hot water at 90℃ until neutral, and dried at 120℃ for 4 hours to obtain gallium-modified aluminum-silicon material.

[0061] (4) Weigh 446g of gallium-modified silicon-aluminum material, add 15g of guar gum powder, 9g of nitric acid and 363g of water, mix and knead into shape, dry at 120℃ for 5 hours, and calcine at 750℃ for 5 hours to obtain catalyst support C.

[0062] (5) A 90 mL impregnation solution was prepared using 36 g of molybdenum trioxide, 9 g of basic nickel carbonate, and 16.2 g of phosphoric acid. The solution was then sprayed onto the carrier C-0 to obtain C-1. C-1 was placed in a sealed container at 26 °C for 6 hours, dried at 120 °C for 4 hours, and finally calcined at 500 °C for 6 hours to obtain CC-1.

[0063] Example 4

[0064] (1) Prepare an aluminum sulfate solution with a concentration of 65 g / 100 mL (based on Al2O3) and a silica sol solution with a concentration of 70 g / 100 mL (based on SiO2). The weight ratio of the silicon source (based on SiO2) to the acidic aluminum source (based on Al2O3) is 2:1. Add 15% citric acid to adjust the pH of the solution to 3 to obtain material I.

[0065] (2) Add 2.0L of clean water to the reactor and heat it to 70℃. Stir at 300rad / min. Control the flow rates of material I, 90g / 100mL sodium aluminate solution, and 1.0mol / L gallium nitrate solution to 60mL / min, 25mL / min, and 10mL / min, respectively. Continuously add them to the reactor. During the reaction, control the pH to 9, the reaction time to 150min, and the reaction temperature to 70℃.

[0066] (3) After the precipitation reaction was complete, the temperature was raised to 95℃ and the stirring rate was adjusted to 350 rad / min. A 60 g / 100 mL polyethylene glycol (molecular weight 400) solution was introduced into the reactor for hydrothermal treatment, with the nonionic surfactant added at 2.5 wt% of material II (calculated as alumina). After sealing, the temperature was raised to 100℃ at a rate of 12℃ / min and held for 4 hours, then raised to 130℃ at a rate of 15℃ / min and held for 8 hours. The resulting slurry was washed with 90℃ hot water until neutral, and dried at 140℃ for 5 hours to obtain gallium-modified silicon-aluminum material.

[0067] (4) Weigh 435g of gallium-modified silicon-aluminum material, add 12g of guar gum powder, 11g of nitric acid and 375g of water, mix and knead into shape, dry at 130℃ for 5 hours, and calcine at 750℃ for 8 hours to obtain catalyst support D.

[0068] (5) A 90 mL impregnation solution was prepared using 36 g of molybdenum trioxide, 7.6 g of basic nickel carbonate, and 17.7 g of phosphoric acid. The solution was then sprayed onto carrier D-0 to obtain D-1. D-1 was placed in a sealed container at 25 °C for 6 hours, dried at 120 °C for 4 hours, and finally calcined at 480 °C for 6 hours to obtain CD-1.

[0069] Comparative Example 1

[0070] Compared with Example 1, the difference is that no organic acid is added in step (1) to adjust the pH value, but the rest is the same as Example 1.

[0071] The comparative hydrogenation catalyst DCA-1 was prepared.

[0072] Comparative Example 2

[0073] Compared with Example 1, the difference is that in step (3), no nonionic surfactant is added, and material II is subjected to hydrothermal treatment alone. Otherwise, it is the same as Example 1.

[0074] The comparative hydrogenation catalyst DCA-2 was prepared.

[0075] Comparative Example 3

[0076] Compared with Example 1, the difference is that gallium nitrate solution is not added in step (2).

[0077] The comparative hydrogenation catalyst DCA-3 was prepared.

[0078] Comparative Example 4

[0079] The feeding process follows the same procedure as in Example 1, but without the addition of gallium nitrate solution. The difference from Example 1 is that the catalyst preparation method in this example follows the steps below, while other steps are the same as in Example 1. The steps are as follows:

[0080] (1) Add the acidic aluminum source aluminum sulfate solution to the silicon source silica sol, and then mix it with the first metal salt nickel salt solution. Adjust the pH of the solution to 3 to obtain the mixture A;

[0081] (2) The mixture A and the alkaline aluminum source sodium aluminate are co-precipitated in the presence of water to obtain slurry B;

[0082] (3) The slurry B is subjected to hydrothermal treatment to obtain the carrier precursor; wherein the treatment temperature is 220℃, the treatment pressure is 0.3MPa, and the treatment time is 2h.

[0083] (4) After uniformly mixing the carrier precursor, molding agent and adhesive obtained in step (3), the carrier is shaped, dried at 120°C for 6 hours, and calcined at 650°C for 3 hours to obtain the carrier.

[0084] (5) The support was mixed with a second metal salt solution (containing molybdenum trioxide, basic nickel carbonate, and phosphoric acid), and then dried and calcined at 550°C for 4 hours to obtain the catalyst. The comparative hydrogenation catalyst DCA-4 was prepared.

[0085] Table 1. Composition of the catalysts obtained in each example.

[0086] Catalyst composition <![CDATA[MoO3,wt%]]> 12.9 12.5 12.6 12.8 NiO, wt% 4.8 5.0 4.6 4.7 <![CDATA[P2O5,wt%]]> 3.2 2.5 2.7 2.5 Carrier, wt% 79.1 80.0 80.1 80.0 Carrier composition <![CDATA[Al2O3,wt%]]> 64.9 64.1 64.8 65.2 <![CDATA[SiO2,wt%]]> 32.7 33.2 32.9 32.6 <![CDATA[Ga2O3,wt%]]> 2.4 2.7 2.3 2.2 nature <![CDATA[Specific surface area, m 2 / g]]> 198 205 211 202 <![CDATA[Pore volume, cm 3 / g]]> 0.56 0.54 0.57 0.55 Average pore size, nm 16.8 16.5 16.7 16.3 Mechanical strength, N / cm 147 154 167 149

[0087] Continued from Table 1

[0088]

[0089]

[0090] Table 2 Infrared acid properties of catalysts from each example and comparative example.

[0091]

[0092] Catalyst evaluation

[0093] The catalysts obtained in the examples and comparative examples were evaluated using the feed oils listed in Table 3. The reaction conditions are shown in Table 3. Samples of the production oil were taken and analyzed after 1000 hours of operation. The evaluation results are shown in Table 4.

[0094] Table 3. Properties of feedstock oil and reaction conditions

[0095]

[0096]

[0097] Table 4. Catalyst evaluation results in each example and comparative example.

[0098]

[0099] The specific embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combining the various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for preparing a low-sulfur marine fuel hydrogenation catalyst, characterized in that, The catalyst comprises a gallium-modified silicon-aluminum support and an active metal component. In the gallium-modified silicon-aluminum support, based on the mass of the gallium-modified silicon-aluminum support, the mass content of gallium oxide is 2.0%–5.0%, the mass content of silicon dioxide is 20.0%–60.0%, and the mass content of aluminum oxide is 35.0%–78.0%. The total acid content of the catalyst is 0.23~0.57 mmol / g, the Brønsted acid content is 0.03~0.07 mmol / g, and the Lewis acid content is 0.2~0.5 mmol / g; The catalyst has the following properties: specific surface area of ​​180~230 m². 2 / g, pore volume is 0.5~0.7mL / g, and average pore size is 10.0~30.0nm; The preparation method includes: (1) Mix and stir the acidic aluminum salt aqueous solution, silicon source, and organic acid to obtain material I; (2) Material I is subjected to a precipitation reaction with gallium-containing solution and alkaline aluminum salt aqueous solution in parallel flow to obtain material II; (3) Material II is subjected to hydrothermal treatment with a nonionic surfactant to obtain gallium-modified silicon-aluminum material; (4) The gallium-modified silicon-aluminum material, adhesive, extrusion aid and water obtained in step (3) are mixed and kneaded, dried and calcined to obtain the catalyst support; (5) The active metal component is loaded onto the catalyst support obtained in step (4), and then dried and calcined to obtain the catalyst. The active metal component is loaded onto the catalyst support by impregnation. The active metal component in the impregnation solution used in step (5) is calculated as metal oxide, wherein the content of Group VIB metal is 150~450 g / L and the content of Group VIII metal is 10~120 g / L. The impregnation solution also contains a phosphorus source. The concentration of phosphorus is 20~80 g / L. The active metal component includes at least one metal component selected from Group VIII and at least one metal component selected from Group VIB.

2. The preparation method according to claim 1, characterized in that, Based on the mass of the catalyst, the mass content of the support is 74% to 87%, the content of Group VIII metals (calculated as oxides) is 2% to 6%, and the content of Group VIB metals (calculated as oxides) is 10% to 20%.

3. The preparation method according to claim 1, characterized in that, The Group VIII metals are nickel and / or cobalt, and the Group VIB metals are molybdenum and / or tungsten.

4. The preparation method according to claim 1, characterized in that, The organic acid mentioned in step (1) is one or more of maleic acid, fumaric acid, adipic acid, tartaric acid, citric acid, oxalic acid, acetic acid, salicylic acid, and malic acid; And / or, the mass concentration of the organic acid is 7% to 16%; And / or, the amount of organic acid added makes the pH value of material I 2 to 4.

5. The preparation method according to claim 4, characterized in that, The amount of organic acid added in step (1) makes the pH value of material I 3~4.

6. The preparation method according to claim 1, characterized in that, The gallium-containing solution mentioned in step (2) is a gallium nitrate solution with a concentration of 0.5~2.5 mol / L; And / or, the concentration of the alkaline aluminum salt solution, calculated as Al2O3, is 20~100g / 100mL; And / or, the ratio of the co-flow velocities of the gallium-containing solution, the material I, and the alkaline aluminum salt solution is 1:3~7:1~3.

7. The preparation method according to claim 1 or 6, characterized in that, The reaction temperature in step (2) is 60~90℃, the reaction time is 60~180 minutes, and the pH value is 8.0~9.

7.

8. The preparation method according to claim 1, characterized in that, The nonionic surfactant mentioned in step (3) is selected from one or more of polyethylene glycol, alkylolamide, and polyether; And / or, the amount of the nonionic surfactant added is 0.1% to 5% of the mass of material II obtained in step (2) based on alumina.

9. The preparation method according to claim 8, characterized in that, The amount of nonionic surfactant added in step (3) is 0.5% to 3% of the mass of material II obtained in step (2) based on alumina.

10. The preparation method according to claim 1, characterized in that, The conditions for hydrothermal treatment in step (3) are as follows: the hydrothermal treatment temperature is 80~130℃ and the time is 3~18 hours.

11. The preparation method according to claim 1, characterized in that, The active metal component in the impregnation solution used in step (5) is calculated as metal oxide, wherein the content of Group VIB metals is 300~400g / L and the content of Group VIII metals is 40~60g / L; the impregnation solution also contains a phosphorus source; the concentration of phosphorus is 40~60g / L.

12. The application of a catalyst prepared by any one of claims 1 to 11 in the hydrogenation of inferior residual oil to produce low-sulfur marine fuel.

13. The application according to claim 12, characterized in that, The reaction conditions were: reaction pressure 10~18 MPa, reaction temperature 380~430℃, and liquid hourly space velocity 0.1~0.6 h⁻¹. -1 The hydrogen-to-oil volume ratio is 400-800.

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