Method for preparing marine fuel through integration of methanol hydrogen production and heavy oil hydrogenation

Abstract

The invention discloses a method for preparing marine fuel through integration of methanol hydrogen production and heavy oil hydrogenation, and belongs to the technical field of heavy oil hydrogenation quality improvement. The invention relates to a method for integrally preparing marine fuel by methanol hydrogen production and heavy oil hydrogenation. The method comprises the following steps: S1, methanol and water vapor enter a methanol reforming reactor to prepare hydrogen-rich gas; s2, the heavy oil raw material and the hydrogen-rich gas are preheated by a heavy oil preheater and then enter a heavy oil hydrogenation upgrading reactor for hydrogenation upgrading; s3, the upgraded oil subjected to hydrogenation upgrading sequentially enters a quenching reactor and a product separator, and the marine fuel is obtained. The process provided by the invention uses the catalyst added with the cerium modifier, has high water resistance, can realize integrated continuous production of hydrogen production by methanol reforming, heavy oil catalytic hydrodesulfurization, denitrification, deoxidation and other reactions, and is efficient and energy-saving.

Description

Technical Field

[0001] The invention belongs to the technical field of heavy oil hydrogenation and quality upgrading, and specifically relates to a method for preparing marine fuel by integrating methanol hydrogenation and heavy oil hydrogenation. Background Art

[0002] Traditional marine fuel oil is mainly heavy oil with high viscosity, high density, high content of heteroatom compounds such as sulfur, nitrogen, oxygen, and metals, and can barely meet the use requirements through physical blending. The International Maritime Organization (IMO) "International Convention for the Prevention of Pollution from Ships" stipulates that from January 1, 2020, ships around the world must use marine fuel oil with a sulfur content of no more than 0.5%, a decrease of 86% from the original 3.5%. 2020 also marks the arrival of the first year of low-sulfur marine fuel oil. Simple physical blending methods are limited by sulfur content requirements and blending ratios, and are no longer applicable. New low-sulfur marine fuel processing technology is urgently needed to adapt to market development.

[0003] Heavy oil desulfurization technology has long been used, including oxidative desulfurization, hydrodesulfurization, biological desulfurization, adsorption desulfurization, extractive desulfurization and photocatalytic desulfurization. Heavy oil hydro-upgrading technology is mature and flexible in operation. It is currently the most economical and feasible method for producing low-sulfur marine fuel. Hydro-upgrading processes mainly include fixed bed, suspended bed and slurry bed hydro-upgrading technologies. The catalyst in the slurry bed reactor is difficult to separate, and the high solid content at the bottom can easily cause local blockage of the gas distributor, resulting in uneven hydrogen distribution. In severe cases, gas phase short circuit occurs, affecting the continuous and stable operation of the reactor. The suspended bed catalyst is severely worn, the cost of the reaction equipment is high, and the amplification effect is obvious. Fixed bed hydro-upgrading technology is relatively more flexible and simple to operate, and has strong raw material adaptability. However, the process has problems such as high hydrogen consumption and serious catalyst carbon deposition, which limits the application of the process.

[0004] To solve the above problems, researchers have conducted extensive and in-depth research on reactor design and catalyst synthesis in the heavy oil hydrogenation and upgrading process. For example, there is a slurry bed reactor with a slurry feed pipe in the middle and lower part, and the end is vertically opened downward at the axis of the reactor, and a slurry distributor is provided at the bottom, and a bottom material pipe is provided at the bottom of the reactor. The reactor design is intended to suppress the deposition of solid particles and make the fluid evenly distributed. However, the collision between the slurry feed pipe and gas distributor of the slurry bed reactor and the solid particles of the catalyst is intensified, resulting in severe wear of the particles, which is easy to block the gas distributor and affect the stable operation of the reactor.

[0005] A preparation method for a heavy oil hydrodemetallization catalyst comprises the following steps: impregnating spherical carbon particles with an iron-containing solution and drying the spherical carbon particles; uniformly mixing the dried carbon particles with an aluminum sol and forming them into spheres; drying and calcining the formed products to obtain an iron-modified alumina carrier; placing the iron-modified alumina carrier into an organic ammonium solution for a first hydrothermal treatment and a second hydrothermal treatment; drying and calcining the product to obtain a treated alumina carrier. Subsequently, active components such as nickel, molybdenum, and phosphorus are impregnated onto the carrier surface by an impregnation method; and drying and calcining to obtain a heavy oil hydrodemetallization catalyst. However, the catalyst has poor carbon deposition resistance.

[0006] A preparation method of a heavy oil hydrodesulfurization catalyst comprises the following steps: first preparing phosphorus-containing alumina sol, mixing it evenly with spherical carbon particles, dropping it into an oleylamine column to form a ball, and drying and calcining it to obtain a phosphorus-modified alumina precursor; then subjecting the precursor to hydrothermal treatment with an organic amine, and drying it to obtain a γ-Al 2 O 3 and AlOOH mixed phase support; Preparation of γ-Al by impregnation method 2 O 3 One or more metals such as Mo / W / Co / Ni supported on a mixed phase carrier of AlOOH are calcined at high temperature to obtain a hydrodesulfurization catalyst. The catalyst has high hydrodesulfurization and demetallization activity, but the catalyst prepared by this method has poor resistance to carbon deposition and deactivation.

[0007] A heavy oil hydrogenation and upgrading process that couples cracking and reforming to produce hydrogen, using a cracking and reforming hydrogen production and fixed bed hydrogenation and upgrading coupling process to achieve continuous and efficient production of heavy oil catalytic hydrogenation, catalytic desulfurization, denitrogenation, and deoxygenation. Using cracking or reforming to produce hydrogen instead of the traditional water electrolysis hydrogen production process can achieve the immediate production and use of hydrogen. However, in this coupling process, since the hydrogen-rich mixed gas prepared by cracking or reforming needs to be condensed for gas-liquid separation, and then preheated and passed into the heavy oil hydrogenation reactor, a large amount of heat loss and energy waste is caused, and the catalyst will gradually become carbonized and deactivated after long-term operation. Summary of the invention

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

[0009] In order to achieve the above object, the technical solution adopted by the present invention is: to provide a method for preparing marine fuel by integrating methanol hydrogen production 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: The heavy oil feedstock and hydrogen-rich gas are preheated in a heavy oil preheater and then enter a heavy oil hydrogenation reactor for hydrogenation and upgrading;

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

[0013] The heavy oil hydro-upgrading reactor is filled with a heavy oil hydro-upgrading catalyst, which includes a modifier, an active component of the hydro-upgrading catalyst and a carrier of the hydro-upgrading catalyst, wherein the modifier is CeO, the active component of the hydro-upgrading catalyst is at least one of Ni, Ni oxide, Mo, Mo oxide, Co and Co oxide, and the carrier of the hydro-upgrading catalyst is Al 2 O 3 、TiO 2 、SiO 2 and MgO; the mass ratio of the modifier, the active component of the hydro-upgrading catalyst and the carrier of the hydro-upgrading catalyst is 0-10:1-30:60-99.

[0014] Based on the above technical solution, the present invention can also be 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°C, the reaction pressure is 1-20MPa, and the liquid space velocity is 0.005-1mol / min.

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

[0017] Further, the methanol reforming catalyst comprises a reforming catalyst carrier and a reforming catalyst active component, wherein the reforming catalyst carrier is Al 2 O 3 、TiO 2 、SiO 2 and MgO, the active components of the reforming catalyst are at least one of Ni, Ni oxide, Mo, Mo oxide, Co, Co oxide, Zn, Zn oxide, Cu and Cu oxide, and the active components of the reforming catalyst account for 1-80% of the mass of the reforming catalyst.

[0018] Furthermore, the heavy oil hydro-upgrading catalyst is treated with a H-containing 2 The mixed gas of S and hydrogen is pretreated, and the H 2 The volume concentration of S is 0.1-5%, the treatment temperature is 250-500℃, the treatment time is 1-20h, and the space velocity is 1-10h -1 .

[0019] Furthermore, the heavy oil raw material 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 the hydrogen-rich gas to the heavy oil feedstock is 100-1000:1, and the hydrogen-rich gas is preheated to a temperature of 250-500°C in the heavy oil preheater (6).

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

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

[0023] Further, the heavy oil hydrogenation upgrading catalyst is prepared by the following steps:

[0024] (1) uniformly mixing the modifier, the active component of the hydrogenation upgrading catalyst and the hydrogenation upgrading catalyst carrier, stirring at 40-80° C. for 1-5 h, and then drying at 100-150° C. for 5-48 h to obtain a catalyst precursor powder;

[0025] (2) heating the catalyst precursor powder to 450-650° C. at a rate of 2-10° C. / min and calcining for 3-8 hours to obtain a catalyst powder;

[0026] (3) The catalyst powder is mixed evenly with nitric acid, extruded into a mold, heated to 450-650° C. at a rate of 2-10° C. / min, and calcined for 3-8 hours to obtain the catalyst.

[0027] The beneficial effects of the present invention are:

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

[0029] (2) Methanol steam reforming to produce steam, CO 2 The mixed hydrogen-rich gas can be directly introduced into the heavy oil hydrogenation and upgrading reactor without the need for decarbonization and water vapor separation and purification, which can provide a hydrogen source for the heavy oil hydrogenation and upgrading reaction, and also provide a high-pressure environment and partial heat for the system, greatly improving production efficiency;

[0030] (3) A two-stage bed is used, with the first stage filled with protective agent and the second stage filled with catalyst. The first stage bed can be used for the initial decarbonization and demetallization of the crude oil, effectively extending the service life of the main catalyst;

[0031] (4) The large amount of water vapor entrained in the hydrogen-containing mixed gas produced by the methanol-water vapor reaction can evenly pass through the oil bed and disperse the oil droplets that have not been completely vaporized, thereby increasing the contact area between the hydrogen molecules and the catalyst; the unremoved water vapor can induce carbon gasification reaction and multi-carbon compound reforming reaction to eliminate the carbon accumulation on the catalyst surface formed during the heavy oil hydrogenation and upgrading process, thereby extending the service life of the catalyst (such as Figure 2 shown);

[0032] (5) The cerium-modified highly water-resistant heavy oil hydrogenation catalyst can withstand the high concentration of water vapor in the system and will not deactivate during long-term operation. It can better ensure the stable operation of the process of integrated methanol hydrogenation and heavy oil hydrogenation to prepare marine fuel.

[0033] The method for preparing marine fuel by integrating methanol hydrogen production and heavy oil hydrogenation provided by the present invention uses a catalyst with high water resistance and a double-bed reactor to integrate methanol reforming hydrogen production and heavy oil hydrogenation and upgrading reactions, thereby realizing continuous and efficient heavy oil hydrogenation and upgrading to produce clean and green marine fuel. The present invention is characterized by the integrated integration of methanol hydrogen production and heavy oil hydrogenation and upgrading, and the CO2-containing 2 The hydrogen-rich reformed gas is used directly as the hydrogen source for heavy oil hydrogenation without carbon separation and condensation and water removal, replacing industrial high-purity hydrogen and effectively avoiding energy waste during the temperature and pressure rise and fall process. 2 In the process of heavy oil hydrogenation and upgrading, the carbon accumulation on the catalyst surface formed in the process of heavy oil hydrogenation and upgrading can be eliminated through the carbon gasification reaction induced by water vapor and the reforming reaction of multi-carbon compounds, thereby extending the service life of the catalyst (such as Figure 2 In addition, the cerium-modified catalyst in the present invention has significant resistance to water vapor deactivation, effectively matches the characteristics of the invention process, ensures the process and long-term operation requirements of the integrated preparation of clean marine fuel by methanol hydrogenation and heavy oil hydrogenation, reduces costs, improves efficiency, and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1Schematic diagram of a method for preparing marine fuel by integrating methanol hydrogen production and heavy oil hydrogenation; wherein, 1, methanol water vapor 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 and upgrading reactor, 8, heavy oil hydrogenation and upgrading protective agent bed, 9, heavy oil hydrogenation and upgrading catalyst bed, 10, quenching reactor, 11, product separator, 12, product oil storage tank;

[0035] Figure 2 This is a diagram showing the mechanism of action of water vapor on heavy oil and catalyst in a heavy oil hydrogenation and upgrading reactor;

[0036] Figure 3 The SEM characterization of the heavy oil hydro-upgrading catalyst before and after the heavy crude oil hydro-upgrading reaction; a and b are the catalyst 5% CoO-10% MoO before and after the reaction, respectively. 3 / Al 2 O 3 , c and d are the cerium-modified catalyst 1% CeO-5% CoO-10% MoO before and after reaction, respectively. 3 / Al 2 O 3 ;

[0037] Figure 4 The different molar ratios of methanol to water vapor on the catalyst 5% NiO-15% MoO 3 / Al 2 O 3 3% CeO-5% NiO-12% MoO with cerium modified catalyst 3 / Al 2 O 3 The influence of catalytic hydrogenation on the quality improvement performance in the process of integrated methanol hydrogenation and shale oil hydrogenation to prepare marine fuel;

[0038] Figure 5 Catalyst 5% NiO-15% MoO 3 / Al 2 O 3 3% CeO-5% NiO-12% MoO with cerium modified catalyst 3 / Al 2 O 3 Testing of the catalytic hydrogenation life in the process of integrated methanol to hydrogen production and shale oil hydrogenation to prepare marine fuel. DETAILED DESCRIPTION

[0039] The specific implementation modes of the present invention are described in detail below with reference to the embodiments.

[0040] Example 1

[0041] Method for preparing marine fuel by integrating methanol hydrogen production and heavy oil hydrogenation:

[0042] Process flow such as Figure 1 As shown, it includes a methanol hydrogen production reactor 2, a heavy oil preheater 6, a heavy oil hydro-upgrading reactor 7, a quenching reactor 10, a product separator 11 and a product oil storage tank 12; wherein, the interior of the methanol reforming reactor 2 is composed of a methanol reforming protective agent bed 3 composed of a methanol reforming protective agent (Liaoning Haitai Technology Development Co., Ltd., item number HTP-100) and a methanol reforming catalyst bed 4 composed of a methanol reforming catalyst from top to bottom; the interior of the heavy oil hydro-upgrading reactor 7 is composed of a heavy oil hydro-upgrading protective agent bed 8 composed of a heavy oil hydro-upgrading protective agent (Liaoning Haitai Technology Development Co., Ltd., item number HTP-100, HTP-102B, HTP-1, the volume ratio of the three when used is 1:1:1) and a heavy oil hydro-upgrading catalyst bed 9 composed of a heavy oil hydro-upgrading catalyst from top to bottom.

[0043] The reaction process of the methanol hydrogen production and heavy oil hydrogenation integrated clean marine fuel production process is as follows: methanol and water vapor enter the methanol reactor 2 through the methanol water vapor inlet 1, pass through the methanol reforming protective agent bed 3 and the methanol reforming catalyst bed 4, and methanol is reformed to produce water vapor, CO 2 The hydrogen-rich gas is directly used as a hydrogen source for the heavy oil hydrogenation and upgrading reaction without dehydration and decarbonization. The heavy oil and the hydrogen-rich gas are pumped into the heavy oil preheater 6 from the heavy oil feedstock inlet 5 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 the hydrogen-rich gas undergo desulfurization, denitrogenation, deoxygenation and other reactions to achieve upgrading. The upgraded oil obtained enters the quenching reactor 10 and the product separator 11 to separate and collect the upgraded oil. The upgraded oil is input into the product oil storage tank 12, and the gas product can be returned to the heavy oil preheater 6 for recycling.

[0044] The mechanism of water vapor reacting with heavy oil and catalyst in the heavy oil hydrogenation reactor 7 is as follows: Figure 2 As shown, the synthesis gas produced by methanol steam reforming carries water vapor, which can evenly distribute large oil droplets into small oil droplets when passing through the oil layer, thereby increasing the oil-gas contact surface; at the same time, water vapor can react with the catalyst and heavy coke in the oil to undergo carbon gasification and multi-carbon compound reforming reactions, thereby reducing carbon deposition on the catalyst.

[0045] Example 2

[0046] 1. A heavy oil hydrogenation catalyst 5% CoO-10% MoO 3 / Al 2 O 3, including the hydrogenation active component MoO 3 , Hydrogenation Upgrading Catalyst Support Al 2 O 3 , CoO is 5% of the total mass of the catalyst, MoO 3 For Al 2 O 3 10% of the total mass of the catalyst, Al 2 O 3 It accounts for 85% of the total mass of the catalyst; the specific preparation steps are as follows:

[0047] S1: The active components of the hydrogenation upgrading catalyst and the hydrogenation upgrading catalyst carrier are mixed in proportion, heated and stirred in a 50°C water bath for 3 hours, and dried in a forced air drying oven at 120°C for 24 hours to obtain a catalyst precursor powder;

[0048] S2: placing the catalyst precursor powder in a muffle furnace and heating it to 550°C at a heating rate of 5°C / min, and calcining it for 3 hours to obtain a catalyst powder;

[0049] S3: Evenly mix the catalyst powder with an appropriate amount of dilute nitric acid, and extrude it into a strip through an extruder; the formed wet catalyst is placed in a muffle furnace for calcination again, and the temperature is increased to 550°C at a heating rate of 5°C / min, and calcined for 3h to obtain the catalyst.

[0050] 2. The initial sulfur content of waste tire oil is about 11000ppm. The method of preparing marine fuel by integrating methanol hydrogen production and waste tire oil hydrogenation is as follows:

[0051] S1: Methanol and water vapor enter the methanol reforming reactor 2 at a molar ratio of 1:2, and methanol water vapor reforming produces hydrogen-rich gas; the gas is directly used as a hydrogen source for heavy oil hydrogenation and upgrading reaction without dehydration and decarbonization; the operating conditions of methanol reforming are: reaction temperature of 340°C, reaction pressure of 6MPa, liquid space velocity of 0.005mol / min, and methanol reforming catalyst of 15% Zn-60% Cu / Al 2 O 3 (Customized by Liaoning Hitech Technology Development Co., Ltd.).

[0052] S2: Heavy oil hydro-upgrading catalyst is 5% CoO-10% MoO 3 / Al 2 O 3 , pre-treated before use, the conditions are: the in-situ activation temperature of the hydrogenation catalyst is 300 °C, the gas used is H 2 A mixture of S and hydrogen, where H 2 The concentration of S is 0.5%, the treatment time is 5h, and the space velocity is 1h -1 .

[0053] S3: The waste tire oil and hydrogen-rich gas are pumped into the heavy oil preheater 6 to be preheated to 350°C, and then pumped into the heavy oil hydrogenation reactor 7, where the waste tire oil and the hydrogen source gas undergo desulfurization, denitrification, deoxygenation and other reactions to achieve quality improvement; the operating conditions for hydrogenation of waste tire oil are: the hydrogenation reaction temperature is 350°C, the gas pressure is 6MPa, and the liquid space velocity is 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 separate and collect the product oil, and the upgraded oil is input into the product oil storage tank 12.

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

[0056] Table 1 Parameters of waste tire oil and upgraded oil

[0057]

[0058] Example 3

[0059] 1. A heavy oil hydrogenation catalyst 1% CeO-5% CoO-10% MoO 3 / Al 2 O 3 , including modifier CeO, hydrogenation active components CoO and MoO 3 , Hydrogenation Upgrading Catalyst Support Al 2 O 3 , CeO is 1% of the catalyst mass, CoO is 5% of the catalyst mass, MoO 3 10% of the catalyst mass, Al 2 O 3 The catalyst mass is 84%. The specific preparation steps are as follows:

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

[0061] S2: placing the catalyst precursor powder in a muffle furnace and heating it to 450°C at a heating rate of 2°C / min, and calcining it for 3 hours to obtain a catalyst powder;

[0062] S3: Evenly mix the catalyst powder with an appropriate amount of dilute nitric acid, and extrude it into various shapes through an extruder; the formed wet catalyst is placed in a muffle furnace for calcination again, and the temperature is increased to 450°C at a heating rate of 2°C / min, and calcined for 3h to obtain the catalyst.

[0063] Heavy oil hydro-upgrading catalyst 5% CoO-10% MoO 3 / Al 2 O 3 , including the hydrogenation active components CoO and MoO 3 , Hydrogenation Upgrading Catalyst Support Al 2 O 3 , CoO is 5% of the total mass of the catalyst, MoO 3 10% of the total mass of the catalyst, Al 2 O 3 It accounts for 85% of the total mass of the catalyst and is prepared by the same steps as above.

[0064] 2. The initial sulfur content of heavy crude oil is about 20,000 ppm. The method for preparing marine fuel by integrating methanol hydrogen production and heavy crude oil hydrogenation is as follows:

[0065] S1: Methanol and water vapor enter the methanol reforming reactor 2 at a molar ratio of 1:3, and methanol water vapor reforming produces hydrogen-rich gas; the gas is directly used as a hydrogen source for heavy oil hydrogenation and upgrading reaction without dehydration and decarbonization; the operating conditions of methanol reforming are: reaction temperature of 360°C, reaction pressure of 10MPa, liquid space velocity of 0.007mol / min, and methanol reforming catalyst of 15% Zn-60% Cu / Al 2 O 3 (Customized by Liaoning Hitech Technology Development Co., Ltd.).

[0066] S2: Heavy oil hydro-upgrading catalyst is 1% CeO-5% CoO-10% MoO 3 / Al 2 O 3 Or 5%CoO-10%MoO 3 / Al 2 O 3 , pre-treated before use, the conditions are: the in-situ activation temperature of the hydrogenation catalyst is 340 °C, the gas used is H 2 A mixture of S and hydrogen, where H 2 The concentration of S is 0.8%, the treatment time is 6h, and the space velocity is 1h -1 .

[0067] S3: Pump the heavy crude oil and hydrogen-rich gas into the heavy oil preheater 6 to be preheated to 400°C, and then pump them into the heavy oil hydrogenation reactor 7, where the heavy crude oil and the hydrogen source gas undergo desulfurization, denitrification, deoxygenation and other reactions to achieve quality improvement; the heavy crude oil hydrogenation operation conditions are: the hydrogenation reaction temperature is 400°C, the gas pressure is 10MPa, and the liquid space velocity is 4h -1 , the volume ratio of hydrogen-rich gas to heavy crude oil is 800:1.

[0068] S4: the upgraded oil after hydrogenation enters the quench reactor 10 and the product separator 11 to separate and collect the product oil, and the upgraded oil is input into the product oil storage tank 12.

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

[0070] 5% CoO-10% MoO catalyst for heavy oil hydrogenation before and after reaction 3 / Al 2 O 3 With 1% CeO-5% CoO-10% MoO 3 / Al 2 O 3 SEM characterization was performed and the results were as follows Figure 3 As shown in the figure, the active components of the catalyst modified with CeO are more evenly distributed, and the appearance after the reaction is less affected by water vapor. There is no obvious moisture erosion, pore collapse and other phenomena. The active component particles are more evenly distributed and have smaller particle size, indicating that the addition of cerium is more suitable for 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 hydrogenation catalyst 3% CeO-7% CoO-10% MoO 3 / Al 2 O 3 -MgO, including modifier CeO, hydrogenation active components CoO and MoO 3 , Hydrogenation Upgrading Catalyst Support Al 2 O 3 MgO, CeO accounted for 3% of the total mass of the catalyst, CoO accounted for 7% of the total mass of the catalyst, and MoO 3 10% of the total mass of the catalyst, Al 2 O 3 The catalyst mass is 30%, and MgO is 50% of the total mass of the catalyst. The specific preparation steps are as follows:

[0073] S1: Mix the modifier, the active component of the upgraded catalyst and the upgraded catalyst carrier in proportion, heat and stir in a water bath at 80°C for 1 hour, and dry in a forced air drying oven at 100°C for 48 hours to obtain a catalyst precursor powder;

[0074] S2: placing the catalyst precursor powder in a muffle furnace and heating it to 650°C at a heating rate of 10°C / min, and calcining it for 5 hours to obtain a catalyst powder;

[0075] S3: Evenly mix the catalyst powder with an appropriate amount of dilute nitric acid, and extrude it into various shapes through an extruder; the formed wet catalyst is placed in a muffle furnace for calcination again, and the temperature is increased to 650°C at a heating rate of 10°C / min, and calcined for 5h to obtain the catalyst.

[0076] 2. The initial sulfur content of waste oil is about 2000ppm. The method of preparing marine fuel by integrating methanol hydrogen production and waste oil hydrogenation is as follows:

[0077] S1: Methanol and water vapor enter the methanol reforming reactor 2 at a molar ratio of 1:3, and methanol water vapor reforming produces hydrogen-rich gas; the gas is directly used as a hydrogen source for heavy oil hydrogenation and upgrading reaction without dehydration and decarbonization; the operating conditions of methanol reforming are: reaction temperature of 320°C, reaction pressure of 8MPa, liquid space velocity of 0.04mol / min, and methanol reforming catalyst of 5%Co-5%Mo-50%Cu / TiO 2 (Customized by Liaoning Hitech Technology Development Co., Ltd.).

[0078] S2: Heavy oil hydro-upgrading catalyst is 3%CeO-7%CoO-10%MoO 3 / Al 2 O 3 -MgO was pretreated before use under the following conditions: the in-situ activation temperature of the hydrogenation catalyst was 360 °C, and the gas used was H 2 A mixture of S and hydrogen, where H 2 The concentration of S is 10%, the treatment time is 6h, and the space velocity is 1h -1 .

[0079] S3: The waste oil and hydrogen-rich gas are pumped into the heavy oil preheater 6 to be preheated to 350°C, and then pumped into the heavy oil hydrogenation reactor 7, where the waste oil and the hydrogen source gas undergo desulfurization, denitrification, deoxygenation and other reactions to achieve quality improvement; the operating conditions for the waste oil hydrogenation are: the hydrogenation reaction temperature is 350°C, the gas pressure is 6MPa, and the liquid space velocity is 0.5h -1 , the volume ratio of hydrogen-rich gas to waste oil is 600:1.

[0080] S4: The upgraded oil after hydrogenation enters the quench reactor 10 and the product separator 11 to separate and collect the product oil. The upgraded oil is input into the product oil storage tank 12, and the gas product is recycled after being pressurized and processed.

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

[0082] Example 5

[0083] 1. A heavy oil hydrogenation catalyst 3% CeO-5% NiO-12% MoO 3 / Al 2 O 3 , including modifier CeO, hydrogenation active components NiO and MoO 3 , Hydrogenation Upgrading Catalyst Support Al 2 O 3 , CeO is 3% of the total mass of the catalyst, NiO is 5% of the total mass of the catalyst, MoO 3 12% of the total mass of the catalyst, Al 2 O 3 The catalyst accounts for 80% of the total mass. The specific preparation steps are as follows:

[0084] S1: Mix the modifier, the active component of the upgraded catalyst and the upgraded catalyst carrier 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 a catalyst precursor powder;

[0085] S2: placing the catalyst precursor powder in a muffle furnace and heating it to 450°C at a heating rate of 5°C / min, and calcining it for 8 hours to obtain a catalyst powder;

[0086] S3: Evenly mix the catalyst powder with an appropriate amount of dilute nitric acid, and extrude it into various shapes through an extruder; the formed wet catalyst is placed in a muffle furnace for calcination again, and the temperature is increased to 450°C at a heating rate of 5°C / min, and calcined for 8h to obtain the catalyst.

[0087] Heavy oil hydro-upgrading catalyst 5% NiO-15% MoO 3 / Al 2 O 3 , including hydrogenation active components Ni and MoO 3 , Hydrogenation Upgrading Catalyst Support Al 2 O 3 , Ni is 5% of the total mass of the catalyst, MoO 3 15% of the total mass of the catalyst, Al 2 O 3It accounts for 80% of the total mass of the catalyst; it is prepared by the same steps as above.

[0088] 2. The initial sulfur content of shale oil is about 13500ppm. The method of preparing marine fuel by integrating methanol hydrogen production and shale oil hydrogenation is as follows:

[0089] S1: Methanol and water vapor enter the methanol reforming reactor 2 at a molar ratio of 1:1, 1:1.5, 1:2.0, 1:2.5 and 1:3, and methanol water vapor reforming produces hydrogen-rich gas; the gas is directly used as a hydrogen source for heavy oil hydrogenation and upgrading reaction without dehydration and decarbonization; the operating conditions of methanol reforming are: reaction temperature of 320°C, reaction pressure of 4MPa, liquid space velocity of 0.04mol / min, methanol reforming catalyst of 10% Zn-65%Cu / Al 2 O 3 (Customized by Liaoning Hitech Technology Development Co., Ltd.).

[0090] S2: Heavy oil hydro-upgrading catalyst is 5% NiO-15% MoO 3 / Al 2 O 3 or 3% CeO-5% NiO-12% MoO 3 / Al 2 O 3 , pre-treated before use, the conditions are: the in-situ activation temperature of the hydrogenation catalyst is 360 ° C, the gas used is H 2 A mixture of S and hydrogen, where H 2 The concentration of S is 0.5%, the treatment time is 6h, and the space velocity is 0.5h -1 .

[0091] S3: The shale oil and hydrogen-rich gas are pumped into the heavy oil preheater 6 to be preheated to 380°C, and then pumped into the heavy oil hydrogenation reactor 7, where the shale oil and the hydrogen source gas undergo desulfurization, denitrification, deoxygenation and other reactions to achieve quality improvement; the operating conditions for shale oil hydrogenation are: the hydrogenation reaction temperature is 380°C, the gas pressure is 4MPa, and the liquid space velocity is 4h -1 , the volume ratio of hydrogen-rich gas to shale oil is 600:1.

[0092] S4: The upgraded oil after hydrogenation enters the quench reactor 10 and the product separator 11 to separate and collect the product oil. The upgraded oil is input into the product oil storage tank 12, and the gas product is recycled after being pressurized and processed.

[0093] like Figure 4 As shown in the figure, under the conditions of different molar ratios of methanol to water vapor, the catalyst 3% CeO-5% NiO-12% MoO 3 / Al 2 O 3The HDS performance is consistently better than that of the catalyst 5% NiO-15% MoO 3 / Al 2 O 3 When the water-to-alcohol molar ratio is 1.5:1, the catalyst is 3% CeO-5% NiO-12% MoO 3 / Al 2 O 3 The treated oil has a desulfurization efficiency of 70%, a denitrification efficiency of 63%, and an oil yield of 99%.

[0094] Catalyst 3% CeO-5% NiO-12% MoO 3 / Al 2 O 3 Under long-term stable operation conditions (within 120 hours), the performance is stable and the sulfur content in the product oil is maintained at around 4000ppm. Figure 5 As shown, it meets the index requirements of national standard marine fuel oil. In the early stage of catalytic hydrogenation and upgrading reaction, the product oil treated by the unmodified catalyst can also meet the national standard requirements, but the treatment capacity decreased in the later stage, probably due to its weak water resistance. This shows that the cerium-modified catalyst has high water resistance and has the application potential to match the long-term stable operation of the integrated process.

[0095] Although the specific implementation of the present invention is described in detail in conjunction with the embodiments, it should not be understood as limiting the scope of protection of this patent. Within the scope described in the claims, various modifications and variations that can be made by those skilled in the art without creative work still fall within the scope of protection of this patent.

Claims

1. A method for preparing marine fuel by integrating methanol hydrogen production and heavy oil hydrogenation, characterized in that: The following steps are involved: S1: Methanol and water vapor enter the methanol reforming reactor (2) to produce hydrogen-rich gas; S2: The heavy oil feedstock and the hydrogen-rich gas are preheated in a heavy oil preheater (6) and then enter a heavy oil hydrogenation reactor (7) for hydrogenation and upgrading; S3: the upgraded oil after hydrogenation enters the quenching reactor (10) and the product separator (11) in sequence to obtain marine fuel; The heavy oil hydro-upgrading reactor (7) is filled with a heavy oil hydro-upgrading catalyst, which comprises a modifier, an active component of the hydro-upgrading catalyst and a carrier of the hydro-upgrading catalyst, wherein the modifier is CeO, the active component of the hydro-upgrading catalyst is at least one of Ni, Ni oxide, Mo, Mo oxide, Co and Co oxide, and the carrier of the hydro-upgrading catalyst is at least one of Al2O3, TiO2, SiO2 and MgO; and the mass ratio of the modifier, the active component of the hydro-upgrading catalyst and the carrier of the hydro-upgrading catalyst is 0-10:1-30:60-99.

2. The method for preparing marine fuel by integrating methanol hydrogen production and heavy oil hydrogenation 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°C, the reaction pressure is 1-20MPa, and the liquid space velocity is 0.005-1mol / min.

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

4. The method for preparing marine fuel by integrating methanol hydrogen production and heavy oil hydrogenation according to claim 3, characterized in that: The methanol reforming catalyst includes a reforming catalyst carrier and a reforming catalyst active component, the reforming catalyst carrier 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, and the reforming catalyst active component accounts for 1-80% of the mass of the reforming catalyst.

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

6. The method for preparing marine fuel by integrating methanol hydrogen production and heavy oil hydrogenation according to claim 1, characterized in that: The heavy oil raw material 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 preparing marine fuel by integrating methanol hydrogen production and heavy oil hydrogenation 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 heavy oil feedstock is preheated to a temperature of 250-500°C in the heavy oil preheater (6).

8. The method for preparing marine fuel by integrating methanol hydrogen production and heavy oil hydrogenation according to claim 1, characterized in that: The reaction temperature in the heavy oil hydrogenation reactor (7) is 250-500°C, the pressure is 1-20MPa, and the liquid space velocity is 0.1-10h -1 .

9. The method for preparing marine fuel by integrating methanol hydrogen production and heavy oil hydrogenation according to claim 1, characterized in that: The heavy oil hydro-upgrading catalyst is loaded in the lower part of the heavy oil hydro-upgrading reactor (7) to form a heavy oil hydro-upgrading catalyst bed (9), and a heavy oil hydro-upgrading protective agent bed (8) composed of a heavy oil hydro-upgrading protective agent is also provided on the upper part.

10. The method for preparing marine fuel by integrating methanol hydrogen production and heavy oil hydrogenation according to claim 1, characterized in that: The heavy oil hydrogenation upgrading catalyst is prepared by the following steps: (1) mixing the modifier, the active component of the hydrogenation upgrading catalyst and the hydrogenation upgrading catalyst carrier uniformly, stirring at 40-80° C. for 1-5 h, and then drying at 100-150° C. for 5-48 h to obtain a catalyst precursor powder; (2) heating the catalyst precursor powder to 450-650° C. at a rate of 2-10° C. / min and calcining for 3-8 hours to obtain a catalyst powder; (3) The catalyst powder is mixed evenly with nitric acid, extruded into a mold, heated to 450-650° C. at a rate of 2-10° C. / min, and calcined for 3-8 hours to obtain the catalyst.

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