Method for preparing marine fuel by integrating hydrogen production from methanol and heavy oil hydrogenation

Abstract

The application discloses a method for preparing marine fuel by integrating methanol hydrogen production and heavy oil hydrogenation, and belongs to the technical field of heavy oil hydrogenation upgrading. The method for preparing marine fuel by integrating methanol hydrogen production and heavy oil hydrogenation comprises the following steps: S1: methanol and water vapor enter a methanol reforming reactor to prepare hydrogen-rich gas; S2: heavy oil raw materials and the hydrogen-rich gas are preheated by a heavy oil preheater and then enter a heavy oil hydrogenation upgrading reactor to perform hydrogenation upgrading; and S3: upgraded oil after hydrogenation upgrading enters a quenching reactor and a product separator in sequence, and marine fuel is obtained. The process provided by the application uses a catalyst added with a cerium modifier, has high water resistance, can realize integrated and continuous production of methanol reforming hydrogen production, heavy oil catalytic hydrogenation desulfurization, denitrification, deoxygenation and other reactions, and is high in efficiency and energy saving.

Description

Technical Field

[0001] This invention belongs to the field of heavy oil hydrotreating technology, specifically relating to a method for the integrated production of marine fuel from methanol and heavy oil. Background Technology

[0002] Traditional marine fuel oil is primarily heavy oil, characterized by high viscosity, high density, and high content of heteroatomic compounds such as sulfur, nitrogen, oxygen, and metals. Physical blending methods are used to barely meet usage requirements. However, the International Maritime Organization (IMO) Convention on the Prevention of Pollution from Ships stipulates that, from January 1, 2020, all ships worldwide must use marine fuel oil with a sulfur content not exceeding 0.5%, a reduction of 86% from the previous 3.5%. 2020 also marked the beginning of the low-sulfur era for marine fuel oil. Simple physical blending methods, limited by sulfur content requirements and blending ratios, are no longer applicable, necessitating new low-sulfur marine fuel processing technologies to adapt to market developments.

[0003] Desulfurization technologies for heavy oil have been applied for a long time, including oxidative desulfurization, hydrodesulfurization, biological desulfurization, adsorption desulfurization, extraction desulfurization, and photocatalytic desulfurization. Hydrotreating technology for heavy oil is mature, flexible in operation, and currently the most economical and feasible method for producing low-sulfur marine fuel. Hydrotreating processes mainly include fixed-bed, suspended-bed, and slurry-bed hydrotreating technologies. In slurry-bed reactors, catalyst separation is difficult, and the high solids content at the bottom easily causes localized blockage of the gas distributor, leading to uneven hydrogen distribution and, in severe cases, gas-phase short circuits, affecting the continuous and stable operation of the reactor. Suspended-bed reactors suffer from severe catalyst wear, high equipment costs, and significant scale-up effects. Fixed-bed hydrotreating technology is relatively more flexible and simple to operate, with strong feedstock adaptability; however, this process suffers from high hydrogen consumption and severe catalyst carbon buildup, limiting its application.

[0004] To address these issues, researchers have conducted extensive and in-depth studies on reactor design and catalyst synthesis in heavy oil hydrotreating processes. One example is a slurry bed reactor with a slurry feed pipe in the lower middle section, its end opening vertically downwards to the reactor axis, and a slurry distributor at the bottom. A bottom material pipe is also located at the bottom of the reactor. This reactor design aims to suppress the deposition of solid particles and ensure uniform fluid distribution. However, the increased collisions between the slurry feed pipe and gas distributor and the catalyst solid particles in this slurry bed reactor lead to severe particle abrasion, easily clogging the gas distributor and affecting the stable operation of the reactor.

[0005] A method for preparing a heavy oil hydrodemetallization catalyst involves impregnating spherical carbon particles with an iron-containing solution and drying them. The dried carbon particles are then uniformly mixed with alumina sol and shaped into spheres. The shaped product is dried and calcined to obtain an iron-modified alumina support. The iron-modified alumina support is then subjected to a first and second hydrothermal treatment in an organic ammonium solution. After drying and calcining, the treated alumina support is obtained. Subsequently, active components such as nickel, molybdenum, and phosphorus are impregnated onto the surface of the support using an impregnation method. After drying and calcining, the heavy oil hydrodemetallization catalyst is obtained. However, this catalyst exhibits poor resistance to carbon deposition.

[0006] A method for preparing a heavy oil hydrodesulfurization catalyst involves first preparing a phosphorus-containing alumina sol, which is then uniformly mixed with spherical carbon particles. This mixture is then drop-formed into spheres in an oil-amine column, dried, and calcined to obtain a phosphorus-modified alumina precursor. This precursor is then hydrothermally treated with an organic amine, and dried to obtain a γ-Al₂O₃ and AlOOH mixed-phase support. One or more metals, such as Mo / W / Co / Ni, are then supported on the γ-Al₂O₃ and AlOOH mixed-phase support via impregnation. After high-temperature calcination, the hydrodesulfurization catalyst is obtained. This catalyst exhibits high hydrodesulfurization and demetallization activity; however, the catalyst prepared by this method shows poor resistance to carbon deposition and deactivation.

[0007] A heavy oil hydrotreating process coupling cracking and reforming hydrogen production is disclosed. This process combines cracking and reforming hydrogen production with fixed-bed hydrotreating to achieve continuous and efficient production of heavy oil through catalytic hydrogenation, catalytic desulfurization, denitrification, and deoxygenation. Replacing traditional water electrolysis with cracking or reforming hydrogen production allows for on-site hydrogen production and use. However, this coupled process suffers from significant heat loss and energy waste due to the need for condensation and gas-liquid separation of the hydrogen-rich mixture produced by cracking or reforming before preheating it before being introduced into the heavy oil hydrotreating reactor. Furthermore, the catalyst gradually deactivates and accumulates carbon over prolonged operation. Summary of the Invention

[0008] In view of the above-mentioned prior art, the present invention provides a method for the integrated production of marine fuel by methanol-to-hydrogen and heavy oil hydrogenation, realizing the integrated continuous production of methanol reforming for hydrogen production, heavy oil catalytic hydrodesulfurization, denitrification, and deoxygenation reactions.

[0009] To achieve the above objectives, the technical solution adopted by the present invention is: to provide a method for the integrated production of marine fuel from methanol and heavy oil hydrogenation, comprising the following steps:

[0010] S1: Methanol and water vapor enter the methanol reforming reactor to produce hydrogen-rich gas;

[0011] S2: Heavy oil feedstock and hydrogen-rich gas are preheated in a heavy oil preheater and then enter the heavy oil hydrotreating reactor for hydrotreating.

[0012] S3: The upgraded oil after hydrotreating enters the quench reactor and product separator in sequence to obtain marine fuel;

[0013] The heavy oil hydrotreating reactor is filled with a heavy oil hydrotreating catalyst, which includes a modifier, an active component of the hydrotreating catalyst, and a catalyst support. The modifier is CeO, the active component of the hydrotreating catalyst is at least one selected from Ni, Ni oxide, Mo, Mo oxide, Co, and Co oxide, and the catalyst support is at least one selected from Al2O3, TiO2, SiO2, and MgO. The mass ratio of the modifier, the active component of the hydrotreating catalyst, and the catalyst support is 0-10:1-30:60-99.

[0014] Based on the above technical solution, the present invention can be further improved as follows.

[0015] Furthermore, the ratio of methanol to water vapor is 1:1-5; the reaction temperature in the methanol reforming reactor is 200-400℃, the reaction pressure is 1-20MPa, and the liquid hourly space velocity is 0.005-1mol / min.

[0016] Furthermore, the interior of the methanol reforming reactor consists, from top to bottom, a methanol reforming protective agent bed composed of methanol reforming protective agent and a methanol reforming catalyst bed composed of methanol reforming catalyst.

[0017] Furthermore, the methanol reforming catalyst includes a reforming catalyst support and a reforming catalyst active component. The reforming catalyst support is at least one of Al2O3, TiO2, SiO2 and MgO. The reforming catalyst active component is at least one of Ni, Ni oxide, Mo, Mo oxide, Co, Co oxide, Zn, Zn oxide, Cu and Cu oxide. The active component accounts for 1-80% of the mass of the reforming catalyst.

[0018] Furthermore, the heavy oil hydrotreating catalyst is pretreated with a mixed gas containing H2S and hydrogen before use. The volume concentration of H2S in the mixed gas is 0.1-5%, the treatment temperature is 250-500℃, the treatment time is 1-20 h, and the space velocity is 1-10 h⁻¹. -1 .

[0019] Furthermore, the heavy oil feedstock is at least one of heavy crude oil, residual oil, shale oil, waste tire oil, bio-oil, and waste engine oil.

[0020] Furthermore, the volume ratio of hydrogen-rich gas to heavy oil feedstock is 100-1000:1, and it is preheated to a temperature of 250-500℃ in the heavy oil preheater (6).

[0021] Furthermore, the reaction temperature in the heavy oil hydrotreating reactor is 250-500℃, the pressure is 1-20MPa, and the liquid hourly space velocity is 0.1-10h. -1 .

[0022] Furthermore, the heavy oil hydrotreating catalyst is packed in the lower part of the heavy oil hydrotreating reactor to form a heavy oil hydrotreating catalyst bed, and there is also a heavy oil hydrotreating catalyst bed composed of heavy oil hydrotreating catalyst on the upper part.

[0023] Furthermore, the heavy oil hydrotreating catalyst is prepared by the following steps:

[0024] (1) Mix the modifier, active component of hydrogenation upgrading catalyst and hydrogenation upgrading catalyst support evenly, stir at 40-80℃ for 1-5h, and then dry at 100-150℃ for 5-48h to obtain catalyst precursor powder.

[0025] (2) The catalyst precursor powder is heated to 450-650℃ at a rate of 2-10℃ / min and calcined for 3-8h to obtain catalyst powder.

[0026] (3) Mix the catalyst powder with nitric acid evenly, extrude it into shape, and calcine it at a rate of 2-10℃ / min to 450-650℃ for 3-8 hours to obtain the product.

[0027] The beneficial effects of this invention are:

[0028] (1) The method of integrating methanol-to-hydrogen and heavy oil hydrogenation to prepare clean marine fuel can realize low-cost intelligent continuous production of low-sulfur marine fuel.

[0029] (2) The methanol steam reforming process can produce a mixed hydrogen-rich gas containing steam and CO2 without decarbonization and steam separation and purification. It can be directly fed into the heavy oil hydrotreating reactor, which can provide a hydrogen source for the heavy oil hydrotreating reaction, and at the same time provide a high-pressure environment and some heat for the system, greatly improving production efficiency.

[0030] (3) A two-stage bed is adopted. The first stage is filled with a protective agent and the second stage is filled with a catalyst. The first stage bed can carry out preliminary decarbonization and demetallization of the feed oil, effectively extending the service life of the main catalyst.

[0031] (4) The large amount of water vapor carried in the hydrogen-containing mixture produced by the methanol-water vapor reaction can pass evenly through the oil bed, dispersing the incompletely vaporized oil droplets uniformly, thereby increasing the contact area between hydrogen molecules and the catalyst; the unremoved water vapor can induce carbon gasification reactions and multi-carbon compound reforming reactions to eliminate the carbon deposits on the catalyst surface formed during the heavy oil hydrotreating process, thus extending the catalyst's service life (e.g., Figure 2 (as shown);

[0032] (5) The cerium-modified high water-resistant heavy oil hydrogenation catalyst can resist the high concentration of water vapor in the system and does not deactivate under long-term operation, which can better ensure the stable operation of the integrated process of methanol to hydrogen production and heavy oil hydrogenation to prepare marine fuel.

[0033] This invention provides a method for the integrated production of marine fuel from methanol-to-hydrogen and heavy oil hydrotreating. It utilizes a catalyst with high water resistance and a dual-bed reactor, integrating methanol reforming for hydrogen production and heavy oil hydrotreating for upgrading, achieving continuous and efficient production of clean and green marine fuel from heavy oil. The key feature of this invention is the integrated production of methanol-to-hydrogen and heavy oil hydrotreating. The CO2-rich reformed gas used in the process bypasses carbon separation and condensation dehydration processes, directly serving as the hydrogen source for heavy oil hydrotreating, replacing industrial high-purity hydrogen and effectively avoiding energy waste during temperature and pressure fluctuations. Simultaneously, the water vapor and CO2 contained in the hydrogen-rich reformed gas can eliminate carbon buildup on the catalyst surface during heavy oil hydrotreating through water vapor-induced carbon gasification and multi-carbon compound reforming reactions, extending catalyst lifespan (e.g., ...). Figure 2 (As shown). Furthermore, the cerium-modified catalyst in this invention exhibits significant resistance to water vapor deactivation, effectively matching the characteristics of the invented process. This ensures the integrated production of clean marine fuel from methanol and heavy oil, meeting the requirements for long-term operation, reducing costs, and improving efficiency, thus demonstrating broad application prospects. Attached Figure Description

[0034] Figure 1 A schematic diagram of a method for the integrated production of marine fuel from methanol and heavy oil hydrogenation; wherein, 1. Methanol steam inlet, 2. Methanol reforming reactor, 3. Methanol reforming protective agent bed, 4. Methanol reforming catalyst bed, 5. Heavy oil feedstock inlet, 6. Heavy oil preheater, 7. Heavy oil hydrogenation upgrading reactor, 8. Heavy oil hydrogenation upgrading protective agent bed, 9. Heavy oil hydrogenation upgrading catalyst bed, 10. Quenching reactor, 11. Product separator, 12. Product oil storage tank;

[0035] Figure 2 This is a diagram illustrating the interaction mechanism between steam, heavy oil, and catalyst in a heavy oil hydrotreating reactor.

[0036] Figure 3 SEM characterization of heavy oil hydrotreating catalyst before and after heavy crude oil hydrotreating reaction; where a and b are the catalysts before and after the reaction, respectively, which are 5% CoO-10% MoO3 / Al2O3; c and d are the cerium-modified catalysts before and after the reaction, respectively, which are 1% CeO-5% CoO-10% MoO3 / Al2O3.

[0037] Figure 4The effect of different molar ratios of methanol and water vapor on the catalytic hydrogenation and upgrading performance of catalysts 5% NiO-15% MoO3 / Al2O3 and cerium-modified catalysts 3% CeO-5% NiO-12% MoO3 / Al2O3 in the integrated process of methanol-to-hydrogen and shale oil hydrogenation for marine fuel production.

[0038] Figure 5 The catalytic hydrogenation life of catalysts 5% NiO-15% MoO3 / Al2O3 and cerium-modified catalysts 3% CeO-5% NiO-12% MoO3 / Al2O3 in the integrated process of methanol-to-hydrogen and shale oil hydrogenation for the production of marine fuel was tested. Detailed Implementation

[0039] The specific embodiments of the present invention will be described in detail below with reference to examples.

[0040] Example 1

[0041] A method for the integrated production of marine fuel from methanol and heavy oil hydrogenation:

[0042] Process flow as follows Figure 1 As shown, the reactor includes a methanol-to-hydrogen reactor 2, a heavy oil preheater 6, a heavy oil hydrotreating reactor 7, a quench reactor 10, a product separator 11, and a product oil storage tank 12. The methanol reforming reactor 2 consists, from top to bottom, a methanol reforming protective agent bed 3 composed of methanol reforming protective agent (Liaoning Haitai Technology Development Co., Ltd., product number HTP-100) and a methanol reforming catalyst bed 4 composed of methanol reforming catalyst. The heavy oil hydrotreating reactor 7 consists, from top to bottom, a heavy oil hydrotreating protective agent bed 8 composed of heavy oil hydrotreating protective agent (Liaoning Haitai Technology Development Co., Ltd., product numbers HTP-100, HTP-102B, and HTP-1, with a volume ratio of 1:1:1 during use) and a heavy oil hydrotreating catalyst bed 9 composed of heavy oil hydrotreating catalyst.

[0043] The reaction process of the integrated methanol-to-hydrogen and heavy oil hydrogenation process for producing clean marine fuel is as follows: Methanol and water vapor enter the methanol reactor 2 through the methanol-water vapor inlet 1. After passing through the methanol reforming protective agent bed 3 and the methanol reforming catalyst bed 4, the methanol is reformed to produce hydrogen-rich gas containing water vapor and CO2. This gas does not need to be dehydrated or decarbonized and can be directly used as the hydrogen source for the heavy oil hydrogenation and upgrading reaction. The heavy oil and hydrogen-rich gas are pumped together from the heavy oil feedstock inlet 5 into the heavy oil preheater 6 for preheating, and then pumped into the heavy oil hydrogenation and upgrading reactor 7. After passing through the heavy oil hydrogenation and upgrading protective agent bed 8 and the heavy oil hydrogenation and upgrading catalyst bed 9, the heavy oil and hydrogen-rich gas undergo desulfurization, denitrification, and deoxygenation reactions to achieve upgrading. The resulting upgraded oil enters the quench reactor 10 and the product separator 11 to separate and collect the upgraded oil. The upgraded oil is sent to the product oil storage tank 12, and the gaseous products can be returned to the heavy oil preheater 6 for recycling.

[0044] The reaction mechanism of water vapor with heavy oil and catalyst in heavy oil hydrotreating reactor 7 is as follows: Figure 2 As shown, the syngas reformed from methanol and water vapor carries water vapor, which can evenly distribute large oil droplets into small oil droplets when passing through the oil layer, increasing the oil-gas contact area. At the same time, the water vapor can undergo carbon gasification reaction and multi-carbon compound reforming reaction with the catalyst and heavy coke in the oil, thereby reducing the carbon deposition on the catalyst.

[0045] Example 2

[0046] 1. A heavy oil hydrotreating catalyst of 5% CoO-10% MoO3 / Al2O3, comprising the hydrotreating active component MoO3 and the hydrotreating catalyst support Al2O3, wherein CoO accounts for 5% of the total catalyst mass, MoO3 accounts for 10% of the total Al2O3 catalyst mass, and Al2O3 accounts for 85% of the total catalyst mass; the specific preparation steps are as follows:

[0047] S1: Mix the active component of the hydrogenation upgrading catalyst and the hydrogenation upgrading catalyst support in a certain proportion, heat and stir in a 50°C water bath for 3 hours, and dry in a forced-air drying oven at 120°C for 24 hours to obtain catalyst precursor powder.

[0048] S2: The catalyst precursor powder is placed in a muffle furnace and heated to 550°C at a heating rate of 5°C / min, and calcined for 3 hours to obtain the catalyst powder.

[0049] S3: Mix the catalyst powder with an appropriate amount of dilute nitric acid evenly, and extrude it into shape using an extruder; place the shaped wet catalyst back into a muffle furnace for calcination, and heat it to 550°C at a heating rate of 5°C / min for 3 hours to obtain the final product.

[0050] 2. The initial sulfur content of waste tire oil is approximately 11,000 ppm. The method for integrating methanol-to-hydrogen and waste tire oil hydrogenation to produce marine fuel is as follows:

[0051] S1: Methanol and water vapor are fed into methanol reforming reactor 2 at a molar ratio of 1:2. The methanol and water vapor are reformed to produce hydrogen-rich gas. This gas can be used directly as a hydrogen source for the hydrogenation and upgrading reaction of heavy oil without dehydration or decarbonization. The operating conditions for methanol reforming are: reaction temperature of 340℃, reaction pressure of 6MPa, liquid hourly space velocity of 0.005mol / min, and methanol reforming catalyst of 15% Zn-60% Cu / Al2O3 (customized by Liaoning Haitai Technology Development Co., Ltd.).

[0052] S2: The heavy oil hydrotreating catalyst is 5% CoO-10% MoO3 / Al2O3. Pretreatment is required before use under the following conditions: in-situ activation temperature of the hydrotreating catalyst is 300℃; the gas used is a mixture containing H2S and hydrogen, with an H2S concentration of 0.5%; treatment time is 5 hours; and space velocity is 1 hour. -1 .

[0053] S3: Waste tire oil and hydrogen-rich gas are pumped together into the heavy oil preheater 6 to preheat to 350℃, and then pumped into the heavy oil hydrotreating reactor 7. The waste tire oil and hydrogen source gas undergo desulfurization, denitrification, and deoxygenation reactions to achieve upgrading. The operating conditions for waste tire oil hydrotreating are: hydrotreating reaction temperature of 350℃, gas pressure of 6MPa, and liquid hourly space velocity of 0.5h. -1 The volume ratio of hydrogen-rich gas to waste tire oil is 600:1.

[0054] S4: The upgraded oil obtained after hydrogenation enters the quench reactor 10 and the product separator 11 to achieve product oil separation and collection. The upgraded oil is then fed into the product oil storage tank 12.

[0055] The parameters of the waste tire oil and the obtained upgraded oil are shown in Table 1. The upgraded oil has a hydrodesulfurization efficiency of 89%, a denitrification efficiency of 75%, a product oil yield of 98%, and a sulfur content as low as 1200ppm, which meets the national standards for marine fuel oil.

[0056] Table 1 Parameters of Waste Tire Oil and Upgraded Oil

[0057]

[0058] Example 3

[0059] 1. A heavy oil hydrotreating catalyst of 1% CeO-5% CoO-10% MoO3 / Al2O3, comprising a modifier CeO, hydrotreating active components CoO and MoO3, and a hydrotreating catalyst support Al2O3, wherein CeO accounts for 1% of the catalyst mass, CoO accounts for 5% of the catalyst mass, MoO3 accounts for 10% of the catalyst mass, and Al2O3 accounts for 84% of the catalyst mass; the specific preparation steps are as follows:

[0060] S1: Mix the modifier, active component of hydrogenation upgrading catalyst and hydrogenation upgrading catalyst support in proportion, heat and stir in a 40℃ water bath for 5 hours, and dry in a forced-air drying oven at 150℃ for 5 hours to obtain catalyst precursor powder.

[0061] S2: The catalyst precursor powder is placed in a muffle furnace and heated to 450°C at a heating rate of 2°C / min, and calcined for 3 hours to obtain the catalyst powder.

[0062] S3: Mix the catalyst powder with an appropriate amount of dilute nitric acid evenly, and extrude it into various shapes using an extruder; place the shaped wet catalyst back into a muffle furnace for calcination, and heat it to 450°C at a heating rate of 2°C / min for 3 hours to obtain the final product.

[0063] The heavy oil hydrotreating catalyst 5% CoO-10% MoO3 / Al2O3, comprising the hydrotreating active components CoO and MoO3, and the hydrotreating catalyst support Al2O3, wherein CoO accounts for 5% of the total catalyst mass, MoO3 accounts for 10% of the total catalyst mass, and Al2O3 accounts for 85% of the total catalyst mass, is prepared by following the same steps described above.

[0064] 2. The initial sulfur content of heavy crude oil is approximately 20,000 ppm. The method for integrating methanol-to-hydrogen and heavy crude oil hydrogenation to produce marine fuel is as follows:

[0065] S1: Methanol and water vapor are fed into methanol reforming reactor 2 at a molar ratio of 1:3. The methanol and water vapor are reformed to produce hydrogen-rich gas. This gas can be used directly as a hydrogen source for the hydrogenation and upgrading reaction of heavy oil without dehydration or decarbonization. The operating conditions for methanol reforming are: reaction temperature of 360℃, reaction pressure of 10MPa, liquid hourly space velocity of 0.007mol / min, and methanol reforming catalyst of 15% Zn-60% Cu / Al2O3 (customized by Liaoning Haitai Technology Development Co., Ltd.).

[0066] S2: The heavy oil hydrotreating catalyst is 1% CeO-5% CoO-10% MoO3 / Al2O3 or 5% CoO-10% MoO3 / Al2O3. Pretreatment is required before use under the following conditions: in-situ activation temperature of the hydrotreating catalyst is 340℃; the gas used is a mixture containing H2S and hydrogen, with an H2S concentration of 0.8%; treatment time is 6 hours; and space velocity is 1 hour. -1 .

[0067] S3: Heavy crude oil and hydrogen-rich gas are pumped together into the heavy oil preheater 6 to preheat to 400℃, and then pumped into the heavy oil hydrotreating reactor 7. The heavy crude oil and hydrogen source gas undergo desulfurization, denitrification, and deoxygenation reactions to achieve upgrading. The operating conditions for heavy crude oil hydrotreating are: hydrotreating reaction temperature of 400℃, gas pressure of 10MPa, and liquid hourly space velocity of 4h. -1 The volume ratio of hydrogen-rich gas to heavy crude oil is 800:1.

[0068] S4: The hydrogenated upgraded oil enters the quench reactor 10 and the product separator 11 to achieve product oil separation and collection, and the upgraded oil is sent to the product oil storage tank 12.

[0069] The desulfurization efficiency of the upgraded oil obtained after hydrogenation of heavy crude oil reached 75%, the denitrification efficiency reached 68%, and the oil yield was 98%.

[0070] The heavy oil hydrotreating catalysts before and after the reaction (5% CoO-10% MoO3 / Al2O3 and 1% CeO-5% CoO-10% MoO3 / Al2O3) were characterized by SEM, and the results are as follows: Figure 3 As shown, the active components of the catalyst modified with CeO are more evenly distributed, and the appearance morphology after the reaction is less affected by water vapor. No obvious water erosion or pore collapse is observed. Furthermore, the active component particles are more evenly distributed and smaller in size, indicating that the addition of cerium is more compatible with the integrated process of methanol-to-hydrogen and heavy crude oil hydrogenation to produce clean marine fuel.

[0071] Example 4

[0072] 1. A heavy oil hydrotreating catalyst comprising 3% CeO-7% CoO-10% MoO3 / Al2O3-MgO, including a modifier CeO, hydrotreating active components CoO and MoO3, and a hydrotreating catalyst support Al2O3 and MgO, wherein CeO accounts for 3% of the total catalyst mass, CoO accounts for 7% of the total catalyst mass, MoO3 accounts for 10% of the total catalyst mass, Al2O3 accounts for 30% of the total catalyst mass, and MgO accounts for 50% of the total catalyst mass; the specific preparation steps are as follows:

[0073] S1: Mix the modifier, the active component of the upgrading catalyst and the upgrading catalyst support in proportion, heat and stir in an 80℃ water bath for 1 hour, and dry in a forced-air drying oven at 100℃ for 48 hours to obtain catalyst precursor powder.

[0074] S2: The catalyst precursor powder is placed in a muffle furnace and heated to 650°C at a heating rate of 10°C / min, and calcined for 5 hours to obtain the catalyst powder.

[0075] S3: Mix the catalyst powder with an appropriate amount of dilute nitric acid evenly, and extrude it into various shapes using an extruder; place the shaped wet catalyst back into a muffle furnace for calcination, and heat it to 650°C at a heating rate of 10°C / min for 5 hours to obtain the final product.

[0076] 2. The initial sulfur content of waste engine oil is approximately 2000 ppm. The method for integrating methanol-to-hydrogen and waste engine oil hydrogenation to produce marine fuel is as follows:

[0077] S1: Methanol and water vapor are fed into methanol reforming reactor 2 at a molar ratio of 1:3. The methanol and water vapor are reformed to produce hydrogen-rich gas. This gas can be used directly as a hydrogen source for the hydrogenation and upgrading reaction of heavy oil without dehydration or decarbonization. The operating conditions for methanol reforming are: reaction temperature of 320℃, reaction pressure of 8MPa, liquid hourly space velocity of 0.04mol / min, and methanol reforming catalyst of 5%Co-5%Mo-50%Cu / TiO2 (customized by Liaoning Haitai Technology Development Co., Ltd.).

[0078] S2: The heavy oil hydrotreating catalyst is 3% CeO-7% CoO-10% MoO3 / Al2O3-MgO. Pretreatment is required before use under the following conditions: in-situ activation temperature of the hydrotreating catalyst is 360℃; the gas used is a mixture containing H2S and hydrogen, with an H2S concentration of 10%; the treatment time is 6 hours; and the space velocity is 1 hour. -1 .

[0079] S3: Waste engine oil and hydrogen-rich gas are pumped together into the heavy oil preheater 6 to preheat to 350℃, and then pumped into the heavy oil hydrotreating reactor 7. The waste engine oil and hydrogen source gas undergo desulfurization, denitrification, and deoxygenation reactions to achieve upgrading. The operating conditions for waste engine oil hydrotreating are: hydrotreating reaction temperature of 350℃, gas pressure of 6MPa, and liquid hourly space velocity of 0.5h. -1 The volume ratio of hydrogen-rich gas to waste engine oil is 600:1.

[0080] S4: The hydrogenated upgraded oil enters the quench reactor 10 and the product separator 11 to achieve product oil separation and collection. The upgraded oil is fed into the product oil storage tank 12, and the gaseous products are recycled after being pressurized and treated.

[0081] The upgraded oil obtained after hydrogenation of waste engine oil has a desulfurization efficiency of 95%, a denitrification efficiency of 85%, an oil-to-oil yield of 99%, and a sulfur content reduced to 100 ppm, which meets the standards for use of marine fuel oil in near-port areas of my country.

[0082] Example 5

[0083] 1. A heavy oil hydrotreating catalyst of 3% CeO-5% NiO-12% MoO3 / Al2O3, comprising a modifier CeO, hydrotreating active components NiO and MoO3, and a hydrotreating catalyst support Al2O3, wherein CeO accounts for 3% of the total catalyst mass, NiO accounts for 5% of the total catalyst mass, MoO3 accounts for 12% of the total catalyst mass, and Al2O3 accounts for 80% of the total catalyst mass; the specific preparation steps are as follows:

[0084] S1: Mix the modifier, the active component of the upgrading catalyst and the upgrading catalyst support in proportion, heat and stir in a 50°C water bath for 3 hours, and dry in a forced-air drying oven at 120°C for 24 hours to obtain catalyst precursor powder.

[0085] S2: The catalyst precursor powder is placed in a muffle furnace and heated to 450°C at a heating rate of 5°C / min, and calcined for 8 hours to obtain the catalyst powder.

[0086] S3: Mix the catalyst powder with an appropriate amount of dilute nitric acid evenly, and extrude it into various shapes using an extruder; place the shaped wet catalyst back into a muffle furnace for calcination, and heat it to 450°C at a heating rate of 5°C / min for 8 hours to obtain the final product.

[0087] The heavy oil hydrotreating catalyst is composed of 5% NiO-15% MoO3 / Al2O3, including the hydrotreating active components Ni and MoO3, and the hydrotreating catalyst support Al2O3. Ni accounts for 5% of the total mass of the catalyst, MoO3 accounts for 15% of the total mass of the catalyst, and Al2O3 accounts for 80% of the total mass of the catalyst. It is prepared by following the same steps as described above.

[0088] 2. The initial sulfur content of shale oil is approximately 13,500 ppm. The method for integrating methanol-to-hydrogen and shale oil hydrogenation to produce marine fuel is as follows:

[0089] S1: Methanol and water vapor are fed into methanol reforming reactor 2 at molar ratios of 1:1, 1:1.5, 1:2.0, 1:2.5, and 1:3. The methanol and water vapor are reformed to produce hydrogen-rich gas. This gas can be used directly as a hydrogen source for the hydrogenation and upgrading reaction of heavy oil without dehydration or decarbonization. The operating conditions for methanol reforming are: reaction temperature of 320℃, reaction pressure of 4MPa, liquid hourly space velocity of 0.04mol / min, and methanol reforming catalyst of 10% Zn-65% Cu / Al2O3 (customized by Liaoning Haitai Technology Development Co., Ltd.).

[0090] S2: The heavy oil hydrotreating catalyst is 5% NiO-15% MoO3 / Al2O3 or 3% CeO-5% NiO-12% MoO3 / Al2O3. Pretreatment is required before use under the following conditions: in-situ activation temperature of the hydrotreating catalyst is 360℃; the gas used is a mixture containing H2S and hydrogen, with an H2S concentration of 0.5%; treatment time is 6 hours; and space velocity is 0.5 h⁻¹. -1 .

[0091] S3: Shale oil and hydrogen-rich gas are pumped together into heavy oil preheater 6 to preheat to 380℃, and then pumped into heavy oil hydrotreating reactor 7. Shale oil and hydrogen source gas undergo desulfurization, denitrification, and deoxygenation reactions to achieve upgrading. The shale oil hydrotreating operation conditions are: hydrotreating reaction temperature of 380℃, gas pressure of 4MPa, and liquid hourly space velocity of 4h. -1 The volume ratio of hydrogen-rich gas to shale oil is 600:1.

[0092] S4: The hydrogenated upgraded oil enters the quench reactor 10 and the product separator 11 to achieve product oil separation and collection. The upgraded oil is fed into the product oil storage tank 12, and the gaseous products are recycled after being pressurized and treated.

[0093] like Figure 4 As shown, under different molar ratios of methanol to water vapor, the hydrodesulfurization performance of catalyst 3% CeO-5%NiO-12%MoO3 / Al2O3 is consistently superior to that of catalyst 5% NiO-15%MoO3 / Al2O3. Furthermore, at a water-to-methanol molar ratio of 1.5:1, the oil treated with catalyst 3% CeO-5% NiO-12% MoO3 / Al2O3 achieves a desulfurization efficiency of 70%, a denitrification efficiency of 63%, and an oil yield of 99%.

[0094] The catalyst, consisting of 3% CeO-5% NiO-12% MoO3 / Al2O3, exhibits stable performance under long-term stable operation (within 120 hours), maintaining the sulfur content in the product oil at approximately 4000 ppm. Figure 5 As shown, the product oil meets the national standard requirements for marine fuel oil. In the initial stage of the catalytic hydrotreating reaction, the unmodified catalyst also produces oil that meets the national standard requirements, but its processing capacity decreases later, possibly due to its weaker water resistance. This indicates that the cerium-modified catalyst has higher water resistance and the potential to be compatible with the long-term stable operation of this integrated process.

[0095] Although specific embodiments of the present invention have been described in detail with reference to examples, they should not be construed as limiting the scope of protection of this patent. Various modifications and variations that can be made by those skilled in the art without inventive effort within the scope described in the claims are still within the scope of protection of this patent.

Claims

1. A method for the integrated production of marine fuel from methanol and heavy oil hydrogenation, characterized in that, Includes the following steps: S1: Methanol and water vapor enter the methanol reforming reactor (2) to produce a hydrogen-rich gas containing water vapor and CO2. This hydrogen-rich gas does not require dehydration or decarbonization. S2: The heavy oil feedstock and the hydrogen-rich gas are preheated by the heavy oil preheater (6) and then enter the heavy oil hydrotreating reactor (7) for hydrotreating. S3: The upgraded oil after hydrogenation enters the quench reactor (10) and product separator (11) in sequence to obtain marine fuel; The heavy oil hydrotreating reactor (7) is filled with a heavy oil hydrotreating catalyst, which includes a modifier, an active component of the hydrotreating catalyst, and a support for the hydrotreating catalyst. The modifier is CeO, the active component of the hydrotreating catalyst is at least one of Ni, Ni oxide, Mo, Mo oxide, Co, and Co oxide, and the support for the hydrotreating catalyst is at least one of Al2O3, TiO2, SiO2, and MgO. The mass ratio of the modifier, the active component of the hydrotreating catalyst, and the support for the hydrotreating catalyst is 1-10:1-30:60-99. The heavy oil hydrotreating catalyst is prepared by the following steps: (1) Mix the modifier, the active component of the hydrogenation upgrading catalyst and the hydrogenation upgrading catalyst support evenly, stir at 40-80 °C for 1-5 h, and then dry at 100-150 °C for 5-48 h to obtain catalyst precursor powder. (2) The catalyst precursor powder is heated to 450-650 ℃ at a rate of 2-10 ℃ / min and calcined for 3-8 h to obtain catalyst powder; (3) Mix the catalyst powder with nitric acid evenly, extrude it into shape, and calcine it at a rate of 2-10 ℃ / min to 450-650 ℃ for 3-8 h to obtain the product; The heavy oil hydrotreating catalyst is packed in the lower part of the heavy oil hydrotreating reactor (7) to form a heavy oil hydrotreating catalyst bed (9), and there is also a heavy oil hydrotreating protective agent bed (8) composed of heavy oil hydrotreating protective agent on the upper part.

2. The method for integrated methanol-to-hydrogen and heavy oil hydrogenation for marine fuel production according to claim 1, characterized in that: The molar ratio of methanol to water vapor is 1:1-5; the reaction temperature in the methanol reforming reactor (2) is 200-400℃, the reaction pressure is 1-20 MPa, and the liquid hourly space velocity is 0.005-1 mol / min.

3. The method for integrated methanol-to-hydrogen and heavy oil hydrogenation for the production of marine fuel according to claim 1 or 2, characterized in that: The methanol reforming reactor (2) consists of, from top to bottom, a methanol reforming protective agent bed (3) composed of methanol reforming protective agent and a methanol reforming catalyst bed (4) composed of methanol reforming catalyst.

4. The method for integrated methanol-to-hydrogen and heavy oil hydrogenation for the production of marine fuel according to claim 3, characterized in that: The methanol reforming catalyst comprises a reforming catalyst support and a reforming catalyst active component. The reforming catalyst support is at least one of Al2O3, TiO2, SiO2, and MgO. The reforming catalyst active component is at least one of Ni, Ni oxide, Mo, Mo oxide, Co, Co oxide, Zn, Zn oxide, Cu, and Cu oxide. The active component constitutes 1-80% of the mass of the methanol reforming catalyst.

5. The method for integrated methanol-to-hydrogen and heavy oil hydrogenation for the production of marine fuel according to claim 1, characterized in that: The heavy oil hydrotreating catalyst is pretreated with a mixed gas containing H2S and hydrogen before use. The volume concentration of H2S in the mixed gas is 0.1-5%, the pretreatment temperature is 250-500 °C, the pretreatment time is 1-20 h, and the space velocity is 1-10 h⁻¹. -1 .

6. The method for integrated methanol-to-hydrogen and heavy oil hydrogenation for the production of marine fuel according to claim 1, characterized in that: The heavy oil feedstock is at least one of heavy crude oil, residual oil, shale oil, waste tire oil, bio-oil, and waste engine oil.

7. The method for integrated methanol-to-hydrogen and heavy oil hydrogenation for the production of marine fuel according to claim 1, characterized in that: The volume ratio of the hydrogen-rich gas to the heavy oil feedstock is 100-1000:1, and the feedstock is preheated to a temperature of 250-500 ℃ in the heavy oil preheater (6).

8. The method for integrated methanol-to-hydrogen and heavy oil hydrogenation for the production of marine fuel according to claim 1, characterized in that: The reaction temperature in the heavy oil hydrotreating reactor (7) is 250-500 ℃, the pressure is 1-20 MPa, and the liquid hourly space velocity is 0.1-10 h⁻¹. -1 .

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