Low-sulfur heavy marine fuel oil and its preparation method

Abstract

This invention relates to the field of marine fuel oil technology, and discloses a low-sulfur heavy marine fuel oil and its preparation method. The preparation method includes: subjecting inferior residue oil I to a mild catalytic cracking reaction, then separating the obtained mild catalytic cracking reaction products to obtain catalytic cracked heavy oil; subjecting the catalytic cracked heavy oil to a hydrodesulfurization reaction, then separating the obtained hydrodesulfurization reaction products to obtain hydrotreated heavy oil; and mixing the hydrotreated heavy oil with oilseed components to obtain low-sulfur heavy marine fuel oil. This preparation method combines hydrotreating of catalytic cracked heavy oil with catalytic cracking, and mixes the obtained hydrotreated heavy oil with oilseed components, enabling the maximum production of low-sulfur marine fuel oil from inferior residue oil, expanding the source of marine fuel oil. Furthermore, the low-sulfur heavy marine fuel oil has a low sulfur content and a low kinematic viscosity at 50°C, and all indicators meet the RMG180 or RMG380 product standards.

Description

Technical Field

[0001] This invention relates to the field of marine fuel oil technology, specifically to low-sulfur heavy marine fuel oil and its preparation method. Background Technology

[0002] As global environmental problems intensify, relevant environmental regulations are becoming increasingly stringent. The International Maritime Organization (IMO) mandated that, from March 1, 2020, the sulfur content limit for marine fuel oil (referred to as marine fuel) be reduced to 0.5 g / kg. Faced with the trend towards low-sulfur marine fuel oil, low-sulfur heavy marine fuel oil will be the primary solution. However, considering existing production capacity, there is still a significant shortage of low-sulfur heavy marine fuel oil.

[0003] It is difficult to directly produce residual marine fuel oil with a sulfur content of less than 0.5% using existing blending components; low-sulfur residue oil must be used for blending. However, using large quantities of expensive low-sulfur straight-run residue oil to produce heavy marine fuel oil will significantly increase the production cost of heavy marine fuel oil.

[0004] To produce low-sulfur marine fuel, most refineries currently remove sulfur from residue oil through hydrotreating to obtain the blending components for low-sulfur marine fuel. However, because residue hydrotreating units are high-pressure hydrotreating units, their investment is large and operating costs are high, resulting in high production costs for low-sulfur marine fuel.

[0005] After hydrotreating, high-sulfur residual oil can be used to produce low-sulfur marine fuel or blending components for low-sulfur marine fuel. For example, CN112300833A discloses a method for producing low-sulfur residual marine fuel. This method involves sequentially loading a hydrotreating protective catalyst, a hydrodemetallization catalyst, and a hydrodemetallization desulfurization protective agent along the stream flow direction in a residual oil hydrotreating unit. This method exhibits good hydrotreating activity and better reaction stability, enabling long-term production of high-quality low-sulfur marine fuel.

[0006] Catalytic slurry oil is rich in polycyclic aromatic hydrocarbons, with high carbon content and low hydrogen content. After desolidification and desulfurization pretreatment, it can be used as a blending component for low-sulfur marine fuel. For example, CN111088068A discloses a method for producing low-sulfur marine fuel oil. In this method, catalytic slurry oil is mixed with a first additive, and after mixing, it is subjected to sedimentation separation to obtain a first material and residue. The first material enters a hydrotreating unit, where a hydrotreating reaction is carried out under the action of a hydrotreating catalyst and hydrogen. The liquid effluent obtained from the reaction enters a clarification unit, and the clarified oil obtained after separation is further subjected to solid-liquid separation to obtain purified slurry oil. The purified slurry oil is mixed with the hydrotreating tail oil of high-sulfur feedstock to obtain low-sulfur marine fuel oil.

[0007] For example, CN101531923A discloses a method for combined catalytic cracking and hydrotreating of inferior feedstock oil. The inferior feedstock oil is hydrotreated, and the resulting hydrotreated residue is then subjected to catalytic cracking to obtain propylene, gasoline, catalytic cracked heavy oil, and other products. The catalytic cracked heavy oil enters the hydrotreating unit, and the hydrotreated catalytic cracked heavy oil is recycled to the catalytic cracking unit for further reaction to obtain the target products propylene and gasoline. This method employs moderate catalytic cracking technology, which can reduce the yield of coke and dry gas during catalytic cracking. Furthermore, this method generates some unconverted catalytic cracked heavy oil. Catalytic cracked heavy oil is also rich in polycyclic aromatic hydrocarbons, but compared to catalytic slurry oil, it has lower viscosity and lower sulfur content, making it easier to remove solids and allowing it to be used as a blending component for low-sulfur marine fuel without desulfurization.

[0008] Most existing technologies achieve desulfurization of residual oil through residual oil hydrotreating units to obtain the main blending components for low-sulfur heavy marine fuel. However, residual oil hydrotreating units have high pressure, large investment, and high operating costs, which increases the production cost of low-sulfur heavy marine fuel. Moreover, most residual oil hydrotreating units are currently matched with downstream catalytic cracking units, resulting in a waste of the processing capacity of the catalytic cracking unit after the production of low-sulfur marine fuel.

[0009] Therefore, it is necessary to develop new catalytic cracking and hydrodesulfurization (MFP) technologies for marine fuel oil, which can produce low-sulfur heavy marine fuel oil from MFP fuel oil components (hydrogenated FGO) and various low-cost components such as residual oil and asphalt, with the aim of producing standard-compliant low-sulfur heavy marine fuel oil at the lowest cost. Summary of the Invention

[0010] The purpose of this invention is to overcome the problems of insufficient production capacity and high production cost of low-sulfur marine fuel oil in the existing technology.

[0011] To achieve the above objectives, the first aspect of the present invention provides a method for preparing low-sulfur heavy marine fuel oil, the method comprising:

[0012] (1) In the presence of a catalytic cracking catalyst, inferior residue oil I is subjected to a moderate catalytic cracking reaction to obtain a moderate catalytic cracking reaction product; wherein, in the inferior residue oil I, the mass content of sulfur element is 0.6%-3.0%, and the density of the inferior residue oil I at 20°C is not greater than 0.97 g / cm³. 3 ;

[0013] (2) The mild catalytic cracking reaction products are separated to obtain catalytic cracked gasoline, catalytic cracked diesel and catalytic cracked heavy oil;

[0014] (3) In the presence of a selective hydrodesulfurization catalyst, the catalytic cracking heavy oil is subjected to a hydrodesulfurization reaction to obtain the hydrodesulfurization reaction product;

[0015] (4) Separate the hydrodesulfurization reaction products to obtain the hydrotreated heavy oil;

[0016] (5) The hydrotreated heavy oil is mixed with the oilseed components to obtain the low-sulfur heavy marine fuel oil; wherein the density of the oilseed components at 20°C is greater than 0.97 g / cm³. 3 Furthermore, the sulfur content is 0.6-0.8% by mass; or, the density of the oil component at 20°C is not greater than 0.97 g / cm³. 3 Furthermore, the mass content of sulfur is less than 0.6%.

[0017] The second aspect of the present invention provides a low-sulfur heavy marine fuel oil prepared by the preparation method described in the first aspect.

[0018] The low-sulfur heavy marine fuel oil prepared by the method provided by this invention contains hydrogenated FGO components (hydrogenated heavy oil) and various marine fuel components (oil components). This low-sulfur heavy marine fuel oil has a low sulfur content (less than 0.49 wt%) and a low kinematic viscosity at 50°C. All indicators meet the RMG180 or RMG380 product standards. The preparation method provided by this invention has a simple preparation process, expands the source of marine fuel oil, and has the potential to increase the production capacity of low-sulfur marine fuel oil. Detailed Implementation

[0019] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0020] The first aspect of this invention provides a method for preparing low-sulfur heavy marine fuel oil, the method comprising:

[0021] (1) In the presence of a catalytic cracking catalyst, inferior residue oil I is subjected to a moderate catalytic cracking reaction to obtain a moderate catalytic cracking reaction product; wherein, in the inferior residue oil I, the mass content of sulfur element is 0.6%-3.0%, and the density of the inferior residue oil I at 20°C is not greater than 0.97 g / cm³. 3 ;

[0022] (2) The mild catalytic cracking reaction products are separated to obtain catalytic cracked gasoline, catalytic cracked diesel and catalytic cracked heavy oil;

[0023] (3) In the presence of a selective hydrodesulfurization catalyst, the catalytic cracking heavy oil is subjected to a hydrodesulfurization reaction to obtain the hydrodesulfurization reaction product;

[0024] (4) Separate the hydrodesulfurization reaction products to obtain the hydrotreated heavy oil;

[0025] (5) The hydrotreated heavy oil is mixed with the oilseed components to obtain the low-sulfur heavy marine fuel oil; wherein the density of the oilseed components at 20°C is greater than 0.97 g / cm³. 3 Furthermore, the sulfur content is 0.6-0.8% by mass; or, the density of the oil component at 20°C is not greater than 0.97 g / cm³. 3 Furthermore, the mass content of sulfur is less than 0.6%.

[0026] The inventors of this invention discovered during their research that a technology for producing low-sulfur heavy marine fuel oil from MFP fuel oil components (hydrogenated FGO) with various low-cost components such as residual oil and asphalt can produce standard-compliant low-sulfur heavy marine fuel oil while reducing production costs. Simultaneously, the relationship between the multiple components of marine fuel oil and their compatibility and stability is crucial. By assisting refineries in controlling the relative proportions of the multiple components of low-sulfur marine fuel, the compatibility and stability of the marine fuel product can be guaranteed to meet standards. Furthermore, the use of hydrogenated FGO to blend and prepare marine fuel oil can significantly expand marine fuel oil production capacity, and there have been no related reports to date.

[0027] The preparation method provided by this invention combines catalytic cracking heavy oil hydrotreating with catalytic cracking, enabling the maximum production of low-sulfur marine fuel oil and light oil products from inferior residue oil, thereby reducing production costs. This preparation method fully utilizes the conversion function of the catalytic cracking unit and the desulfurization function of the catalytic cracking heavy oil hydrotreating unit. The process is simple and reasonable, improving the utilization efficiency of petroleum resources. The hydrodesulfurization reaction is preferably carried out in the catalytic cracking heavy oil hydrotreating unit, employing a selective hydrodesulfurization process to reduce hydrogen consumption. It avoids the need to construct a high-pressure residue hydrotreating unit, saving investment and operating costs, and is also more suitable for producing low-sulfur heavy marine fuel oil with even lower sulfur content.

[0028] According to some embodiments of the present invention, in step (5), the density of the oil component at 20°C is greater than 0.97 g / cm³. 3 The sulfur content is 0.6-0.8% by mass; preferably, the density of the oil component at 20°C is 0.975-0.99 g / cm³. 3 Furthermore, the mass content of sulfur is 0.62-0.7%.

[0029] According to some embodiments of the present invention, in step (5), the density of the oil component at 20°C is not greater than 0.97 g / cm³. 3 Furthermore, the sulfur content is less than 0.6% by mass; preferably, the density of the oil component at 20°C is 0.93-0.97 g / cm³. 3Furthermore, the mass content of sulfur is 0.5-0.59%.

[0030] According to some embodiments of the present invention, preferably, in step (5), the mass ratio of the hydrotreated heavy oil to the oil component is 1:(1-1000), more preferably 1:(1-200), and even more preferably 1:(1.5-20). Adopting the above preferred embodiments is beneficial for further reducing the sulfur content in low-sulfur heavy marine fuel oil.

[0031] According to some embodiments of the present invention, preferably, in step (5), the oil component is selected from at least one of hydrogenated residue, vacuum residue, heavy aromatics, desolidified oil slurry, catalytic diesel, hydrogenated diesel, ethylene tar, hydrogenated wax oil, atmospheric residue and deoiled bitumen, and more preferably at least one of vacuum residue, hydrogenated diesel, catalytic diesel and desolidified oil slurry.

[0032] According to some embodiments of the present invention, preferably, in step (5), the mixing conditions are at least: temperature of 20-100°C, time of 20-40 min, and rotation speed of 50-500 rpm.

[0033] According to some embodiments of the present invention, in step (1), the mass content of sulfur in the inferior residue oil I is 0.6%-3.0%, and the density of the inferior residue oil I at 20°C is not greater than 0.97 g / cm³. 3 ;

[0034] In a preferred embodiment, the kinematic viscosity of the inferior residual oil I at 100°C is 50 mmHg. 2 / s-5000mm 2 / s, residual carbon content is 5%-50%, nitrogen content is 0.05%-2.0%, asphaltene content is 0.1%-10.0%, nickel content is 2ppm-200ppm, and vanadium content is 2ppm-200ppm.

[0035] According to some embodiments of the present invention, preferably, in step (1), the conditions for the moderate catalytic cracking reaction are at least satisfied as follows: volume hourly space velocity is 25 h⁻¹. -1 -100h -1 The reaction temperature is 450℃-600℃.

[0036] According to some embodiments of the present invention, preferably, the catalytic cracking catalyst is at least one of zeolite, inorganic oxide and clay.

[0037] According to some embodiments of the present invention, preferably, the catalytic cracking catalyst is a waste equilibrium catalyst with a cracking activity of not less than 45. The cracking activity can be measured by the method specified in NB / SH / T 0952-2017.

[0038] According to a particularly preferred embodiment of the present invention, step (1) further includes: introducing inferior residue oil I into a mild catalytic cracking unit in the presence of a catalytic cracking catalyst to carry out a mild catalytic cracking reaction, thereby obtaining mild catalytic cracking reaction products.

[0039] According to some embodiments of the present invention, preferably, the preparation method may further include: preheating the inferior residue oil I before introducing it into the mild catalytic cracking unit to obtain preheated inferior residue oil I; and then introducing the preheated inferior residue oil I into the mild catalytic cracking unit to carry out the mild catalytic cracking reaction.

[0040] This invention does not impose any special requirements on the specific conditions of the preheating treatment. Those skilled in the art can perform the preheating operation in conjunction with known preheating operations in the art. There are also no special requirements on the temperature of the material after preheating, which those skilled in the art can determine based on their known knowledge.

[0041] For example, the mild catalytic cracking device of the present invention may include a first reaction zone and a second reaction zone arranged sequentially along the liquid phase flow direction. The mild catalytic cracking device does not specifically contain two reaction zones. The main point is that in the mild catalytic cracking device, as the mild catalytic cracking reaction proceeds, the catalytic cracking activity of the catalytic cracking catalyst continuously decreases. As the catalytic cracking activity of the catalytic cracking catalyst continuously decreases, the mass content of the catalytic cracked heavy oil continuously increases, thereby achieving the effect of mild catalytic cracking.

[0042] Preferably, the preheated inferior residue oil I described in this invention is introduced into the mild catalytic cracking unit under the lifting action of steam to react with the catalytic cracking catalyst contained therein. Through this contact, a macromolecular cracking reaction is carried out to remove at least one impurity from the inferior residue oil I, including metals, sulfur, and nitrogen.

[0043] Preferably, in this invention, after the preheated inferior residue oil I undergoes the macromolecular cracking reaction, the resulting reaction stream is further subjected to cracking, hydrogen transfer, and isomerization reactions.

[0044] According to some embodiments of the present invention, preferably, in step (2), the separation conditions are controlled such that the cutting point between the catalytic cracked diesel and the catalytic cracked heavy oil is 260°C-380°C.

[0045] According to some embodiments of the present invention, preferably, in step (2), the separation can also yield dry gas and / or liquefied gas.

[0046] According to a particularly preferred embodiment of the present invention, in step (2), the separation conditions are controlled to obtain dry gas, propylene, propane, C4 hydrocarbons, the catalytic cracked gasoline, the catalytic cracked diesel, and the catalytic cracked heavy oil.

[0047] According to some embodiments of the present invention, preferably, in step (3), the conditions of the hydrodesulfurization reaction are such that the mass content of sulfur in the obtained hydrodesulfurization reaction product is 0.001%-0.5%, the mass content of silicon is 0ppm-50ppm, the mass content of aluminum is 0ppm-50ppm, and the density of the hydrodesulfurization reaction product at 20°C is 0.85 g / cm³. 3 -0.95g / cm 3 The kinematic viscosity at 50°C is 2 mm. 2 / s-200mm 2 / s.

[0048] According to some embodiments of the present invention, preferably, the conditions for the hydrodesulfurization reaction are at least: a reaction temperature of 330℃-430℃, a reaction pressure of 0.5MPa-8.0MPa, and a volume hourly space velocity of 0.1h. -1 -5.0h -1 The hydrogen-to-oil volume ratio is 200-2000:1;

[0049] According to some embodiments of the present invention, preferably, in step (3), the selective hydrodesulfurization catalyst contains a support and an active metal component supported on the support, wherein the active metal element in the active metal component is a combination of at least one group VIB metal element and at least one group VIII metal element; the support is selected from at least one of alumina, silica and amorphous silica-alumina.

[0050] In a preferred embodiment, the content of the active metal component, calculated as oxide, in the selective hydrodesulfurization catalyst is 0.05-0.30% by weight, based on the total weight of the selective hydrodesulfurization catalyst, and the content of the support is 0.70-0.95% by weight.

[0051] According to some embodiments of the present invention, preferably, in the selective hydrodesulfurization catalyst, the active metal elements are molybdenum and cobalt, and the support is alumina.

[0052] According to a particularly preferred embodiment of the present invention, in the selective hydrodesulfurization catalyst, the active metal elements are molybdenum and cobalt, the support is alumina, and based on the total weight of the selective hydrodesulfurization catalyst, the content of molybdenum as oxide is 0.05-0.20% by weight, the content of cobalt as oxide is 0.05-0.20% by weight, and the content of alumina as support is 0.60-0.90% by weight.

[0053] According to some embodiments of the present invention, preferably, in step (3), the selective hydrodesulfurization catalyst is in the shape of a gear with a central hole or a butterfly extrusion strip.

[0054] According to some embodiments of the present invention, preferably, in the hydrodesulfurization reaction, a hydroprotective catalyst and a hydrotransition catalyst are sequentially loaded upstream of the selective hydrodesulfurization catalyst. That is, preferably, in the hydrodesulfurization reaction, the catalytic cracking heavy oil is sequentially contacted with the hydroprotective catalyst, the hydrotransition catalyst, and the selective hydrodesulfurization catalyst.

[0055] According to a preferred embodiment of the present invention, in the hydrodesulfurization reaction, the loading volume ratio of the hydroprotective catalyst, the hydrotransition catalyst, and the selective hydrodesulfurization catalyst is 0.05-0.10:0.05-0.40:1.

[0056] This invention does not impose any particular requirements on the specific types of the hydrogenation protection catalyst and the hydrogenation transition catalyst. Those skilled in the art can use various hydrogenation protection catalysts and hydrogenation transition catalysts known in the art in this invention. The specific types of hydrogenation protection catalysts and hydrogenation transition catalysts listed in the embodiments of this invention should not be construed as limitations on this invention.

[0057] According to some embodiments of the present invention, preferably, in step (3), the desulfurization selectivity of the selective hydrodesulfurization catalyst is higher than 90%, and the desulfurization selectivity = (sulfur content in inferior residue oil I - sulfur content in hydrodesulfurization reaction product) * (hydrogen content in hydrodesulfurization reaction product - hydrogen content in inferior residue oil I) / sulfur content in inferior residue oil I * 100%; more preferably, the desulfurization selectivity of the selective hydrodesulfurization catalyst is higher than 95%.

[0058] According to some embodiments of the present invention, preferably, in step (3), the method further includes: before carrying out the hydrodesulfurization reaction, filtering the catalytic cracking heavy oil to obtain pretreated catalytic cracking heavy oil with a solid content of less than 100 ppm, and then carrying out the hydrodesulfurization reaction on the pretreated catalytic cracking heavy oil.

[0059] According to some embodiments of the present invention, there are no special requirements for the equipment and processes used in the filtration process, and any existing filtration technology can be used. For better filtration results, the filtration process preferably employs a flexible deconsolidation technique.

[0060] According to some embodiments of the present invention, preferably, the hydrodesulfurization reaction is carried out in a catalytic cracking heavy oil hydrotreating unit.

[0061] According to a particularly preferred embodiment of the present invention, step (3) includes: introducing the catalytic cracking heavy oil into the catalytic cracking heavy oil hydrotreating unit in the presence of a selective hydrodesulfurization catalyst to carry out a hydrodesulfurization reaction, thereby obtaining the hydrodesulfurization reaction product.

[0062] In a preferred embodiment, the catalytic cracking heavy oil hydrotreating unit adopts a pressure-switching operation mode. During the first 6 months of unit operation, the first reaction pressure of the unit is 3MPa-6MPa to improve the selectivity of hydrodesulfurization. After 6 months of unit operation, as catalyst coking increases and hydrodesulfurization selectivity improves, the second reaction pressure of the unit is adjusted to 6MPa-8MPa to reduce the catalyst coking rate and further extend the unit's operating cycle.

[0063] In a further preferred embodiment, the second reaction pressure is higher than the first reaction pressure.

[0064] According to some embodiments of the present invention, preferably, in step (4), the density of the hydrotreated heavy oil at 20°C is 0.955-0.97 g / cm³. 3 The kinematic viscosity at 50℃ is 6-9 mm. 2 / s; the hydrogenated heavy oil contains 0.02-0.07% sulfur by mass and 25-50 ppm silicon and aluminum by mass.

[0065] According to some embodiments of the present invention, preferably, in step (4), the separated products further include hydrogenated gasoline and / or hydrogenated diesel.

[0066] According to some embodiments of the present invention, preferably, the separation conditions are controlled such that the cutting point between the hydrogenated gasoline and the hydrogenated heavy oil is 160°C-210°C.

[0067] According to some embodiments of the present invention, preferably, the separation conditions are controlled such that the final boiling point of the hydrotreated heavy oil is 240°C-380°C.

[0068] According to some embodiments of the present invention, preferably, in step (4), the method can also obtain gas by controlling the separation conditions.

[0069] The second aspect of the present invention provides a low-sulfur heavy marine fuel oil prepared by the preparation method described in the first aspect.

[0070] According to a particularly preferred embodiment of the present invention, the preparation method includes:

[0071] S1: In the presence of a catalytic cracking catalyst, inferior residue oil I is preheated to obtain preheated inferior residue oil I. The preheated inferior residue oil I is then introduced into a moderate catalytic cracking unit for moderate catalytic cracking reaction to obtain moderate catalytic cracking reaction products. Specifically, the inferior residue oil I contains 0.6%-3.0% sulfur by mass, and its density at 20°C is greater than 0.97 g / cm³. 3 ;

[0072] S2: Separate the products of the moderate catalytic cracking reaction to obtain dry gas, liquefied petroleum gas, catalytic cracked gasoline, catalytic cracked diesel, and catalytic cracked heavy oil;

[0073] S3: The catalytic cracking heavy oil is filtered to obtain pretreated catalytic cracking heavy oil with a solid content of less than 100 ppm; in the presence of a hydroprotective catalyst, a hydrotransition catalyst, and a selective hydrodesulfurization catalyst, the pretreated catalytic cracking heavy oil is introduced into a catalytic cracking heavy oil hydrotreating unit for hydrodesulfurization reaction to obtain hydrodesulfurization reaction products; wherein the loading volume ratio of the hydroprotective catalyst, the hydrotransition catalyst, and the selective hydrodesulfurization catalyst is 0.05-0.10:0.05-0.40:1;

[0074] S4: Separate the hydrodesulfurization reaction products to obtain gas, hydrotreated gasoline, hydrotreated diesel and hydrotreated heavy oil respectively;

[0075] S5: The hydrotreated heavy oil is mixed with the oilseed components to obtain the low-sulfur heavy marine fuel oil; wherein the density of the oilseed components at 20°C is greater than 0.97 g / cm³. 3 Furthermore, the sulfur content is 0.6-0.8% by mass; or, the density of the oil component at 20°C is not greater than 0.97 g / cm³. 3 The sulfur content is less than 0.6% by mass; the oil component is selected from at least one of vacuum residue, hydrotreated diesel, catalytic diesel and desolidified slurry; the mass ratio of the hydrotreated heavy oil to the oil component is 1:(1-1000); the mixing conditions at least meet the following requirements: temperature 20-100℃, time 20-40min, and rotation speed 50-500rpm.

[0076] The present invention will be described in detail below through examples. Unless otherwise specified, all raw materials used in the following examples and comparative examples are commercially available.

[0077] The oil components used were all from Sinopec Qingdao Petrochemical Co., Ltd., and their main properties are shown in Table 1.

[0078] The inferior residue oil raw materials used were residue oil A and residue oil B, and their main properties are shown in Table 2.

[0079] The catalysts with the following grades RG-202, RDM-33B and RFS-100 are all produced by Changling Catalyst Plant of Sinopec Catalyst Branch, and their main properties are shown in Table 3.

[0080] The catalytic cracking catalyst used is MLC-500, which is produced by Sinopec Catalyst Changling Branch.

[0081] Table 1

[0082]

[0083]

[0084] Table 2

[0085] Inferior residue oil feedstock number Residue Oil A Residue oil B <![CDATA[Density (20 °C), kg / m 3 > 936 960 <![CDATA[Kinematic viscosity (100 °C), millimeters 2 / second]]> 3500 5000 Carbon residue, weight % 6.0 9.0 Nitrogen, by weight 0.32 0.36 Sulfur, by weight 0.78 0.80 <![CDATA[Asphaltenes (C7 insolubles), wt%]]> 1.2 6.5 Metal content, ppm Nickel content, ppm 13.5 26 Vanadium content, ppm 5.3 77

[0086] Table 3

[0087] Catalyst grade RG-202 RDM-33B RFS-100 category Hydrogenation Protectant Hydrogenation transition agent Selective hydrodesulfurization agent shape Gear type with a hole in the middle Butterfly Extrusion Butterfly Extrusion Active metals Ni-Mo Co-Mo Co-Mo Physical properties <![CDATA[Specific surface area, m 2 / g]]> ≮100 ≮160 ≮165 Pore ​​volume, ml / g ≮0.60 ≮0.50 ≮0.45

[0088] The following examples illustrate the low-sulfur heavy marine fuel oil and its preparation method provided by the present invention.

[0089] Example 1

[0090] S1: In the presence of a catalytic cracking catalyst, inferior residue oil I is preheated to obtain preheated inferior residue oil I; under the lifting action of steam, the preheated inferior residue oil I is introduced into a moderate catalytic cracking unit via pipeline to carry out a moderate catalytic cracking reaction to obtain moderate catalytic cracking reaction products.

[0091] Among them, inferior residual oil I is residual oil A;

[0092] S2: Separate the products of the moderate catalytic cracking reaction to obtain dry gas, liquefied petroleum gas, catalytic cracked gasoline, catalytic cracked diesel, and catalytic cracked heavy oil; wherein:

[0093] The conditions for the moderate catalytic cracking reaction in the moderate catalytic cracking unit are: a volume hourly space velocity (VHSV) of 30 h⁻¹. -1 The reaction temperature is 520℃; the initial boiling point of catalytic cracking heavy oil is 280℃.

[0094] S3: Catalytic cracking heavy oil is introduced into a filtration unit for filtration treatment. After filtering out solid particles, filtered catalytic cracking heavy oil (i.e., pretreated catalytic cracking heavy oil) with properties as shown in Table 4 is obtained. In the presence of a hydrotreating protective catalyst, a hydrotreating transition catalyst, and a selective hydrodesulfurization catalyst, the filtered catalytic cracking heavy oil is introduced into a catalytic cracking heavy oil hydrotreating unit for hydrodesulfurization reaction to obtain hydrodesulfurization reaction products; wherein:

[0095] The loading volume ratio of the hydrogenation protection catalyst, the hydrogenation transition catalyst, and the selective hydrodesulfurization catalyst is 6:10:100; the conditions for the catalytic cracking hydrodesulfurization reaction are shown in Table 4.

[0096] S4: Separate the products of the hydrodesulfurization reaction to obtain gas, hydrotreated gasoline, hydrotreated diesel, and hydrotreated heavy oil; wherein:

[0097] Hydrogenated gasoline has a boiling range of 30℃-170℃, and the initial boiling point of hydrogenated heavy oil is 170℃; other properties of hydrogenated heavy oil are listed in Table 4.

[0098] S5: In a 2L stirred tank, hydrotreated heavy oil (350g) is mixed with the oil components to obtain low-sulfur heavy marine fuel oil, denoted as S1; wherein:

[0099] The oilseed component is vacuum residue; the mass ratio of hydrotreated heavy oil to the oilseed component is 1:1.857.

[0100] The mixing conditions were: temperature 80℃, time 30min, and rotation speed 200rpm.

[0101] Example 2

[0102] The method of Example 1 was followed, except that the amount of hydrotreated heavy oil used was 300g, the mass ratio of hydrotreated heavy oil to oil components was 1:2.333, and the rest was the same as in Example 1, resulting in low-sulfur heavy marine fuel oil, denoted as S2.

[0103] Example 3

[0104] The method of Example 2 is the same, except that the oil components are vacuum residue (600g) and hydrotreated diesel (100g), and the vacuum residue and hydrotreated diesel are added in sequence during the mixing process. The rest is the same as in Example 2, and a low-sulfur heavy marine fuel oil is obtained, which is denoted as S3.

[0105] Example 4

[0106] The method of Example 2 is followed, except that the amount of hydrotreated heavy oil is 100g, and the mass ratio of hydrotreated heavy oil to oil components is 1:9; the oil components are vacuum residue (600g), catalytic diesel (100g) and hydrotreated diesel (200g), and during the mixing process, vacuum residue, catalytic diesel and hydrotreated diesel are added in sequence, and the rest is the same as in Example 2, to obtain low sulfur heavy marine fuel oil, denoted as S4.

[0107] Example 5

[0108] The method of Example 4 is the same, except that the oil components are vacuum residue (600g), desolidified slurry (100g) and hydrotreated diesel (200g). During the mixing process, vacuum residue, desolidified slurry and hydrotreated diesel are added in sequence. The rest is the same as in Example 4. Low sulfur heavy marine fuel oil is obtained and is denoted as S5.

[0109] Example 6

[0110] The method of Example 1 is the same, except that the inferior residue oil I used is residue oil B, and the process parameters are different. Specifically, the main operating conditions and main product properties of the catalytic cracking heavy oil hydrotreating unit are shown in Table 4; the rest are the same as in Example 1, and low-sulfur heavy marine fuel oil is obtained, denoted as S6.

[0111] Comparative Example 1

[0112] In a 2L stirred tank, catalytic diesel oil (350g) was mixed with vacuum residue to obtain low-sulfur heavy marine fuel oil, denoted as D1.

[0113] The mass ratio of catalytic diesel to vacuum residue was 1:1.857; the mixing conditions were the same as in Example 1.

[0114] The specific property parameters of the low-sulfur heavy marine fuel oils prepared in the examples and comparative examples are shown in Table 5.

[0115] Table 4

[0116] Examples 1-5 Example 6 Inferior residue oil feedstock number Residue Oil A Residue oil B Properties of filtered catalytic cracking heavy oil <![CDATA[Density (20 °C), kg / m 3 > 960 975 Sulfur content, % by weight 0.53 0.42 <![CDATA[Viscosity at 50°C, mm 2 / s]]> 55.5 9.6 Si+Al, ppm 30 80 Operating conditions of catalytic cracking heavy oil hydrotreating unit Hydrogen partial pressure, MPa 4.8 4.8 Overall average temperature of the reactor bed, °C 370 380 <![CDATA[Space velocity, h -1 > 1.0 1.0 Hydrogen-to-oil volume ratio, v / v 600 800 Properties of Hydrogenated Heavy Oil <![CDATA[Density (20 °C), kg / m 3 > 960 965 Sulfur content, % by weight 0.040 0.050 <![CDATA[Viscosity at 50°C, mm 2 / s]]> 8.1 8.1 Si+Al, ppm 50 50

[0117] Table 5

[0118]

[0119] The results above show that the low-sulfur heavy marine fuel oil prepared by the method provided by this invention contains hydrotreated heavy oil (hydrotreated FGO) components and various marine fuel components. It has a low sulfur content (below 0.49 wt%) and a low kinematic viscosity at 50°C. All indicators of this low-sulfur heavy marine fuel oil meet the RMG180 or RMG380 product standards. The preparation method provided by this invention has a simple process, expands the sources of marine fuel oil, and has the potential to increase the production capacity of low-sulfur marine fuel oil.

[0120] The preferred 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 combinations of 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 low-sulfur heavy marine fuel oil, characterized in that, The preparation method includes: (1) In the presence of a catalytic cracking catalyst, inferior residue oil I is subjected to a moderate catalytic cracking reaction to obtain a moderate catalytic cracking reaction product; wherein, in the inferior residue oil I, the mass content of sulfur element is 0.78%-3.0%, and the density of the inferior residue oil I at 20°C is not greater than 0.97 g / cm³. 3 The kinematic viscosity of the inferior residual oil I at 100°C is 3500 mmHg. 2 / s-5000mm 2 / s, residual carbon content is 6%-50%, nitrogen content is 0.32%-2.0%, asphaltene content is 1.2%-10.0%, nickel content is 13.5ppm-200ppm, and vanadium content is 5.3ppm-200ppm; (2) The mild catalytic cracking reaction products are separated to obtain catalytic cracked gasoline, catalytic cracked diesel and catalytic cracked heavy oil; (3) In the presence of a selective hydrodesulfurization catalyst, the catalytic cracking heavy oil is subjected to a hydrodesulfurization reaction to obtain the hydrodesulfurization reaction product; (4) Separate the hydrodesulfurization reaction products to obtain hydrotreated heavy oil and hydrotreated gasoline; control the separation conditions so that the cutting point between the hydrotreated gasoline and the hydrotreated heavy oil is 160℃-210℃; control the separation conditions so that the final boiling point of the hydrotreated heavy oil is 240℃-380℃. (5) The hydrotreated heavy oil is mixed with the oilseed components to obtain the low-sulfur heavy marine fuel oil; wherein the density of the oilseed components at 20°C is 0.93-0.97 g / cm³. 3 The sulfur content is 0.5-0.59% by mass; the oil components are selected from at least two of vacuum residue, hydrotreated diesel, catalytic diesel, and desolidified slurry oil; the density of the hydrotreated heavy oil at 20°C is 0.955-0.97 g / cm³. 3 The kinematic viscosity at 50℃ is 6-9 mm. 2 / s; the hydrogenated heavy oil contains 0.02-0.07% sulfur by mass and 25-50 ppm silicon and aluminum by mass.

2. The preparation method according to claim 1, wherein, In step (5), the mass ratio of the hydrotreated heavy oil to the oil component is 1:(1-1000). And / or, the mixing conditions shall at least satisfy: temperature of 20-100℃, time of 20-40min, and rotation speed of 50-500rpm.

3. The preparation method according to claim 2, wherein, The mass ratio of the hydrogenated heavy oil to the oil component is 1:(1-200).

4. The preparation method according to claim 2, wherein, The mass ratio of the hydrogenated heavy oil to the oil component is 1:(1.5-20).

5. The preparation method according to claim 1, wherein, In step (1), the conditions for the moderate catalytic cracking reaction must at least satisfy: a volume hourly space velocity (VHSV) of 25 h⁻¹. -1 -100h -1 The reaction temperature is 450℃-600℃; And / or, the catalytic cracking catalyst is at least one of zeolite, inorganic oxide and clay; And / or, the catalytic cracking catalyst is a waste equilibrium catalyst with a cracking activity of not less than 45.

6. The preparation method according to any one of claims 1-3, wherein, In step (2), the separation conditions are controlled such that the cutting point between the catalytic cracked diesel and the catalytic cracked heavy oil is 260℃-380℃.

7. The preparation method according to any one of claims 1-3, wherein, In step (3), the conditions for the hydrodesulfurization reaction must at least meet the following requirements: reaction temperature of 330℃-430℃, reaction pressure of 0.5MPa-8.0MPa, and volume hourly space velocity of 0.1h. -1 -5.0h -1 The hydrogen-to-oil volume ratio is 200-2000:

1.

8. The preparation method according to any one of claims 1-3, wherein, In step (3), the selective hydrodesulfurization catalyst contains a support and an active metal component supported on the support. The active metal element in the active metal component is a combination of at least one group VIB metal element and at least one group VIII metal element. The support is selected from at least one of alumina, silica and amorphous silica-alumina.

9. The preparation method according to claim 8, wherein, In the selective hydrodesulfurization catalyst, the active metal elements are molybdenum and cobalt, and the support is alumina.

10. The preparation method according to any one of claims 1-3, wherein, In step (3), the selective hydrodesulfurization catalyst has a desulfurization selectivity of more than 90%, and the desulfurization selectivity = (sulfur content in inferior residue oil I - sulfur content in hydrodesulfurization reaction product) * (hydrogen content in hydrodesulfurization reaction product - hydrogen content in inferior residue oil I) / sulfur content in inferior residue oil I * 100%.

11. The preparation method according to claim 10, wherein, The selective hydrodesulfurization catalyst has a desulfurization selectivity of over 95%.

12. The preparation method according to any one of claims 1-3, wherein, In step (3), the method further includes: before carrying out the hydrodesulfurization reaction, filtering the catalytic cracking heavy oil to obtain pretreated catalytic cracking heavy oil with a solid content of less than 100 ppm, and then carrying out the hydrodesulfurization reaction on the pretreated catalytic cracking heavy oil.

13. The preparation method according to claim 12, wherein, The filtration process employs a flexible desolidification technique.

14. Low-sulfur heavy marine fuel oil prepared by the preparation method according to any one of claims 1-13.

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