Marine fuel oil and preparation method thereof

Abstract

The invention relates to the technical field of marine fuel oil, in particular to a method for preparing marine fuel oil from high-viscosity, high-acid-value and high-ash asphalt, which comprises the following steps: firstly, carrying out thermal cracking reaction on the high-viscosity, high-acid-value and high-ash asphalt serving as a raw material by adopting a thermal cracking process to obtain thermal cracked asphalt, and secondly, carrying out blending by adopting a blending process to obtain the marine fuel oil. The preparation method comprises the following steps: uniformly mixing a required amount of thermal cracking asphalt with a light component to obtain blended asphalt, and finally, uniformly mixing the required amount of thermal cracking asphalt with the light component by adopting a blending process to obtain the blended asphalt. According to the preparation method for preparing the residue type marine fuel oil from the high-viscosity high-acid-value high-ash-content asphalt, the prepared marine fuel oil not only improves the proportion of the cracked asphalt in the marine fuel oil, but also improves the economical efficiency of the marine fuel oil on the basis of meeting the product technical requirements of the'marine fuel oil '(GB17411-2015).

Description

Technical Field

[0001] The invention relates to the technical field of marine fuel oil, in particular to marine fuel oil and a preparation method thereof. Background Art

[0002] At present, marine fuel oil refers to the fuel oil used for ship engines to provide them with kinetic energy and electrical energy. There are two types of marine fuel oil: distillate marine fuel oil, which is suitable for medium and high-speed diesel engines; and residual marine fuel oil, which is suitable for low-speed diesel engines. Ship pollutant emissions have become the main source of air pollution in ports and seas around the world.

[0003] There are three main production processes for low-sulfur marine fuel oil: one is to use low-sulfur crude oil through distillation-blending process; the second is to use low-sulfur residual oil and high-sulfur heavy fuel oil for mixing and blending production; the third is to use residual oil processing equipment (mainly fixed bed asphalt hydrogenation or boiling bed asphalt hydrocracking) to reduce the sulfur content in high-sulfur residual oil for the production of low-sulfur marine fuel oil. This route is the current mainstream production technology route. It can be seen that the high and low sulfur content of crude oil determines the production technology of low-sulfur marine fuel oil. At present, the focus of marine fuel oil product research is the technical research on the preparation of low-sulfur marine fuel oil from high-sulfur crude oil.

[0004] In the product standard "Marine Fuel Oil" GB17411-2015, the technical requirements for residual marine fuel oil indicators, in addition to sulfur content, also limit the viscosity, acid value, ash content and other indicators of marine fuel oil. Acidic compounds in fuel oil can cause corrosion and damage to marine internal combustion engines, and ash in fuel oil will be deposited on pipe walls, boiler heating surfaces and other equipment, reducing the efficiency of heat transfer. Therefore, the marine fuel oil product standard stipulates that the technical requirements for acid value and ash content are not more than 2.5mg KOH / g and not more than 0.10%, respectively.

[0005] The heavy oil from Xinjiang Oilfield undergoes vacuum distillation and solvent deasphalting to obtain an asphalt with a sulfur content of less than 0.35%, which is a high-quality raw material for producing low-sulfur residual marine fuel oil. However, the acid value of the asphalt is greater than 6.8 mg KOH / Kg, the ash content is greater than 0.30%, and the viscosity at 50°C is greater than 3.5×10 5 mm 2 / s. If the asphalt is directly used to prepare marine fuel oil, the amount of asphalt in the marine fuel oil will be less than 30%, and the amount of light components added will be large, resulting in poor economic efficiency of marine fuel oil. Therefore, it is necessary to reduce the acidity and ash content of high-viscosity, high-acidity and high-ash asphalt, increase the amount of asphalt in marine fuel oil, and improve the economy of fuel oil.

[0006] Organic acids in asphalt are the main factors affecting the acid value of asphalt. Organic acids mainly exist in the form of cyclohexane acid in asphalt. Reducing the acid value of asphalt is mainly achieved by reducing the content of cyclohexane acid. According to the different properties of raw materials, there are three main process technologies for removing cyclohexane acid from raw materials: high temperature decomposition, hydrodeacidification and chemical neutralization. Among them, hydrodeacidification and chemical neutralization deacidification have the problems of complex process flow and high cost.

[0007] The Chinese patent document with publication number CN113322098A discloses a method for reducing the acid value of high-acid crude oil and marine fuel oil. The method uses high-acid crude oil as raw material, and adopts flash-viscosity reduction-vacuum distillation to obtain low-acid asphalt. The acid value of low-acid asphalt can be reduced to 3.0 mg KOH / g to 3.5 mg KOH / g. Subsequently, the low-acid asphalt can be further blended with light components to obtain RMG380, RMG500, RMG700 and other brands of low-sulfur residual marine fuel oil, with an acid value of no more than 2.5 mg KOH / g, which meets the national mandatory implementation standard GB17411-2015. However, the raw material used in the invention has a low viscosity, and does not involve asphalt ash pretreatment, and cannot reduce the ash content of asphalt.

[0008] The ash content of petroleum products is mainly caused by a small amount of inorganic salts and metal organic compounds. If the ash content of petroleum products is to be reduced, the metal content in the raw materials needs to be removed. Chemical demetallization, crude oil electro-desalting and asphalt hydrodemetallization processes are usually used. Among them, the chemical demetallization technology combined with electro-desalting equipment has become a research hotspot because of its low cost, industrialization and easy operation.

[0009] The Chinese patent document with publication number CN102399580A discloses a method for demetallizing hydrocarbon oil. The viscosity of these raw materials is relatively small, while for high-viscosity raw materials, especially those with a viscosity greater than 3.5×10 5 mm 2 There is no public report on the demetallization of vacuum residue or asphalt with a capacity of 1 / 2 s.

[0010] Therefore, the current method for preparing marine fuel oil not only does not involve the technical field of preparing marine fuel oil with high-viscosity, high-acid value and high-ash asphalt, but also the weight percentage of asphalt in marine fuel oil is less than 30%, and the amount of light components added is large, resulting in poor economic efficiency in preparing marine fuel oil. Summary of the invention

[0011] The present invention provides a marine fuel oil and a preparation method thereof, which overcomes the deficiencies of the above-mentioned prior art and can effectively solve the problems of low asphalt content, high light component content and poor economic performance existing in marine fuel oil.

[0012] One of the technical solutions of the present invention is achieved through the following measures: a marine fuel oil is prepared according to the following steps: the first step is to use high-viscosity, high-acid value and high-ash asphalt as raw material, adopt a thermal cracking process, and obtain cracked asphalt through thermal cracking reaction; the second step is to adopt a blending process to evenly mix the required amount of cracked asphalt and light components to obtain blended asphalt; the third step is to chemically demetallize the blended asphalt to obtain marine fuel oil.

[0013] The following is a further optimization and / or improvement of one of the above-mentioned technical solutions: In the first step above, the needle penetration of high viscosity, high acid value and high ash asphalt at 25°C ranges from 10 dmm to 300 dmm, and the viscosity at 50°C is not less than 2.5×10 5 mm 2 / s, the acid value is not less than 6.8mg KOH / g, the ash content is not less than 0.3%, and the thermal cracking reaction temperature is 370℃ to 460℃, and the reaction time is 20min to 90min.

[0014] The above-mentioned thermal cracking reaction temperature is 390° C. to 440° C., and the reaction time is 30 min to 60 min.

[0015] In the above second step, the light component is one or more of catalytic wax oil, catalytic diesel, coker wax oil, and coker diesel, and the weight percentage of cracked asphalt in the blended asphalt is 40% to 80%, and the weight percentage of light components in the blended asphalt is 20% to 60%.

[0016] In the third step above, the specific process of chemical demetallization treatment is: firstly, the required amount of blended asphalt, demetallization agent, demulsifier and water are evenly mixed by shearing, and then the oil and water are separated by electrical desalting, and the metal-containing water in the blended asphalt is removed to obtain marine fuel oil.

[0017] The above-mentioned shear temperature is 80°C to 100°C, the shear time is 20min to 60min, the electro-desalting temperature is 110°C to 140°C, the electro-desalting electric field is 500v / cm to 1200v / cm, the electro-desalting time is 10min to 60min, the demetallizing agent is one or more of acetic acid, propionic acid, butyric acid, acetic anhydride, and acetic-propionic anhydride, and the metal in the metal-containing water in the blended asphalt is calcium, wherein the molar amount of the demetallizing agent is 0.6 to 2.2 times the molar amount of calcium in the blended asphalt.

[0018] The molar amount of the above-mentioned demetallizing agent is 0.8 to 2.0 times the molar amount of calcium in the blended asphalt.

[0019] The weight ratio of the above-mentioned demulsifier to the blended asphalt is 50μg / g to 150μg / g, wherein the weight percentage of water to the blended asphalt is 4% to 12%.

[0020] The weight ratio of the above-mentioned demulsifier to the blended asphalt is 70μg / g to 130μg / g, wherein the weight percentage of water to the blended asphalt is 6% to 10%.

[0021] The second technical solution of the present invention is achieved through the following measures: a method for preparing marine fuel oil, which is carried out according to the following steps: the first step is to use high-viscosity, high-acid value and high-ash asphalt as raw material, adopt a thermal cracking process, and obtain cracked asphalt through thermal cracking reaction; the second step is to adopt a blending process to evenly mix the required amount of cracked asphalt and light components to obtain blended asphalt; the third step is to chemically demetallize the blended asphalt to obtain marine fuel oil.

[0022] The present invention provides a method for preparing residual marine fuel oil by utilizing high-viscosity, high-acid value, and high-ash asphalt. The prepared marine fuel oil not only meets the product technical requirements of Marine Fuel Oil (GB17411-2015), but also increases the proportion of cracked asphalt in marine fuel oil and improves the economy of marine high fuel oil. DETAILED DESCRIPTION

[0023] The present invention is not limited by the following embodiments, and specific implementation methods can be determined according to the technical scheme of the present invention and actual conditions. Unless otherwise specified, the various chemical reagents and chemicals mentioned in the present invention are all known and commonly used chemical reagents and chemicals in the prior art; the percentages in the present invention are all mass percentages unless otherwise specified.

[0024] The present invention will be further described below in conjunction with embodiments: Example 1: The marine fuel oil is prepared according to the following steps: the first step is to use high-viscosity, high-acid value and high-ash asphalt as raw material, adopt a thermal cracking process, and obtain cracked asphalt through thermal cracking reaction; the second step is to adopt a blending process to evenly mix the required amount of thermal cracked asphalt and light components to obtain blended asphalt; the third step is to chemically demetallize the blended asphalt to obtain marine fuel oil.

[0025] Example 2: As an optimization of the above example, in the first step, the needle penetration of the high viscosity, high acid value and high ash asphalt at 25°C ranges from 10 dmm to 300 dmm, and the viscosity at 50°C is not less than 2.5×10 5 mm 2 / s, the acid value is not less than 6.8mg KOH / g, the ash content is not less than 0.3%, and the thermal cracking reaction temperature is 370℃ to 460℃, and the reaction time is 20min to 90min.

[0026] Example 3: As an optimization of the above example, the thermal cracking reaction temperature is 390°C to 440°C, and the reaction time is 30min to 60min.

[0027] Example 4: As an optimization of the above example, in the second step, the light component is one or more of catalytic wax oil, catalytic diesel, coking wax oil, and coking diesel, and the weight percentage of cracked asphalt in the blended asphalt is 40% to 80%, and the weight percentage of light components in the blended asphalt is 20% to 60%.

[0028] Example 5: As an optimization of the above example, in the third step, the specific process of chemical demetallization treatment is: first, the required amount of blended asphalt, demetallization agent, demulsifier and water are shear-mixed evenly, and then oil-water separation is performed through electrical desalting, and after removing the metal-containing water in the blended asphalt, marine fuel oil is obtained.

[0029] Example 6: As an optimization of the above example, the shear temperature is 80°C to 100°C, the shear time is 20min to 60min, the electro-desalting temperature is 110°C to 140°C, the electro-desalting electric field is 500v / cm to 1200v / cm, the electro-desalting time is 10min to 60min, the demetallizing agent is one or more of acetic acid, propionic acid, butyric acid, acetic anhydride, and acetic-propionic anhydride, and the metal in the metal-containing water in the blended asphalt is calcium, wherein the molar amount of the demetallizing agent is 0.6 to 2.2 times the molar amount of calcium in the blended asphalt.

[0030] The demulsifier used in the present invention is a commercially available demulsifier known in the art.

[0031] Example 7: As an optimization of the above example, the molar amount of the demetallizing agent is 0.8 to 2.0 times the molar amount of calcium in the blended asphalt.

[0032] Example 8: As an optimization of the above example, the weight ratio of demulsifier to blended asphalt is 50 μg / g to 150 μg / g, wherein the weight percentage of water to blended asphalt is 4% to 12%.

[0033] Example 9: As an optimization of the above example, the weight ratio of demulsifier to blended asphalt is 70 μg / g to 130 μg / g, wherein the weight percentage of water to blended asphalt is 6% to 10%.

[0034] Example 10: The method for preparing the marine fuel oil is carried out according to the following steps: the first step is to use high-viscosity, high-acid value and high-ash asphalt as raw material, adopt a thermal cracking process, and obtain cracked asphalt through thermal cracking reaction; the second step is to adopt a blending process to evenly mix the required amount of thermal cracked asphalt and light components to obtain blended asphalt; the third step is to chemically demetallize the blended asphalt to obtain marine fuel oil.

[0035] Example 11: The marine fuel oil is prepared according to the following method: In the first step, high viscosity, high acid value and high ash asphalt is used as raw material, and its needle penetration at 25°C is 35 dmm and its viscosity at 50°C is 1.07×10 7 mm 2 / s, acid value is 7.10mg KOH / g, ash content is 0.37%, calcium content is 1315ug / g, thermal cracking process is used for thermal cracking reaction, thermal cracking reaction temperature is 440℃, reaction time is 30min, and cracked asphalt is obtained through thermal cracking reaction; secondly, a blending process is used to stir and mix the cracked asphalt with a content of 44% and coking wax oil with a content of 56% to obtain blended asphalt; thirdly, the blended asphalt is subjected to chemical demetallization treatment to obtain marine fuel oil, and the specific process of chemical demetallization treatment is as follows: firstly, the obtained blended asphalt, demetallizing agent, demulsifier and water are uniformly mixed by shearing, wherein the demetallizing agent is acetic acid, and the demetallizing agent is acetic acid. The amount of the metal agent is 1.8 times the molar amount of calcium in the blended asphalt, the demulsifier model is KR40, the amount of the demulsifier is 120μg / g of the weight of the blended asphalt, and the amount of water injected is 10% of the weight of the blended asphalt; secondly, at a temperature of 95°C, the obtained blended asphalt, the demetallizing agent, the demulsifier and water are mixed on a shear emulsifier for 20 minutes, and then placed in an electric desalting device for oil-water separation, the electric desalting temperature is 140°C, the electric desalting electric field is 1000v / cm, and the electric desalting time is 20min. Under this condition, the metal in the blended asphalt is removed, and finally marine fuel oil is obtained, and its viscosity at 50°C is 352mm 2 / s, acid value is 2.19mg KOH / g, ash content is 0.034%. In this embodiment, high viscosity, high acid value and high ash asphalt are used to prepare marine fuel oil. The final marine fuel oil product meets the product technical requirements of "Marine Fuel Oil" GB17411-2015 in terms of 50°C viscosity, acid value and ash content, and the amount of light components added is less than 70%, which improves the economy of marine high fuel oil.

[0036] Example 12: The marine fuel oil is prepared according to the following method: In the first step, high viscosity, high acid value and high ash asphalt is used as raw material, and its needle penetration at 25°C is 10 dmm and its viscosity at 50°C is 1.5×10 7 mm 2 / s, acid value is 7.13mg KOH / g, ash content is 0.38%, calcium content is 1320ug / g, thermal cracking process is used for thermal cracking reaction, thermal cracking reaction temperature is 440℃, reaction time is 30min, and cracked asphalt is obtained through thermal cracking reaction; secondly, a blending process is used to stir and mix the cracked asphalt with a content of 40% and 60% catalytic diesel to obtain blended asphalt; thirdly, the blended asphalt is subjected to chemical demetallization treatment to obtain marine fuel oil, and the specific process of chemical demetallization treatment is as follows: firstly, the obtained blended asphalt, demetallizing agent, demulsifier and water are uniformly mixed by shearing, wherein the demetallizing agent is acetic acid and acetic anhydride, The amount of the metal agent is 2.0 times the molar amount of calcium in the blended asphalt, the demulsifier model is KR40, the amount of the demulsifier is 130μg / g of the weight of the blended asphalt, and the amount of water injected is 10% of the weight of the blended asphalt; secondly, at a temperature of 100°C, the obtained blended asphalt, the demetallizing agent, the demulsifier and water are mixed on a shear emulsifier for 20 minutes, and then placed in an electric desalting device for oil-water separation, the electric desalting temperature is 140°C, the electric desalting electric field is 1200v / cm, and the electric desalting time is 10min. Under this condition, the metal in the blended asphalt is removed, and finally marine fuel oil is obtained, and its viscosity at 50°C is 113mm 2 / s, acid value is 1.72mg KOH / g, and ash content is 0.042%. In this embodiment, high-viscosity, high-acid value, and high-ash asphalt are used to prepare marine fuel oil. The final marine fuel oil product meets the product technical requirements of "Marine Fuel Oil" GB17411-2015 at 50°C in terms of viscosity, acid value, and ash content, and the amount of light components added is less than 70%, thereby improving the economy of marine high fuel oil.

[0037] Example 13: The marine fuel oil is prepared according to the following method: In the first step, high viscosity, high acid value and high ash asphalt is used as raw material, and its needle penetration at 25°C is 60 dmm and its viscosity at 50°C is 8.9×10 6 mm 2 / s, acid value is 7.07mg KOH / g, ash content is 0.37%, calcium content is 1282ug / g, thermal cracking process is used for thermal cracking reaction, thermal cracking reaction temperature is 430℃, reaction time is 30min, and cracked asphalt is obtained through thermal cracking reaction; secondly, a blending process is used to stir and mix the cracked asphalt with a content of 47% and coking diesel with a content of 53% to obtain blended asphalt; thirdly, the blended asphalt is subjected to chemical demetallization treatment to obtain marine fuel oil, and the specific process of chemical demetallization treatment is as follows: firstly, the obtained blended asphalt, demetallizing agent, demulsifier and water are uniformly mixed by shearing, wherein the demetallizing agent is acetic acid, acetic anhydride and ethylene propylene anhydride, the amount of demetallizing agent is 1.8 times the molar amount of calcium in the blended asphalt, the model of the demulsifier is KR40, the amount of the demulsifier is 120μg / g of the weight of the blended asphalt, and the amount of water injected is 10% of the weight of the blended asphalt; secondly, at a temperature of 95°C, the obtained blended asphalt, demetallizing agent, demulsifier and water are mixed on a shear emulsifier for 30 minutes, and then placed in an electric desalting device for oil-water separation, the electric desalting temperature is 130°C, the electric desalting electric field is 1000v / cm, and the electric desalting time is 20min. Under this condition, the metal in the blended asphalt is removed, and finally marine fuel oil is obtained, and its viscosity at 50°C is 266mm 2 / s, acid value is 2.23mg KOH / g, and ash content is 0.039%. In this embodiment, high-viscosity, high-acid value, and high-ash asphalt are used to prepare marine fuel oil. The final marine fuel oil product meets the product technical requirements of "Marine Fuel Oil" GB17411-2015 at 50°C in terms of viscosity, acid value, and ash content, and the amount of light components added is less than 70%, thereby improving the economy of marine high fuel oil.

[0038] Example 14: The marine fuel oil, in the first step, uses high viscosity, high acid value, high ash asphalt as raw material, with a needle penetration of 85 dmm at 25°C and a viscosity of 8.2×10 6 mm 2 / s, acid value is 7.05mg KOH / g, ash content is 0.36%, calcium content is 1265ug / g, thermal cracking process is used for thermal cracking reaction, thermal cracking reaction temperature is 430℃, reaction time is 40min, and cracked asphalt is obtained through thermal cracking reaction; secondly, a blending process is used to stir and mix the cracked asphalt with a content of 51% and 49% catalytic wax oil to obtain blended asphalt; thirdly, the blended asphalt is subjected to chemical demetallization treatment to obtain marine fuel oil, and the specific process of chemical demetallization treatment is as follows: firstly, the obtained blended asphalt, demetallizing agent, demulsifier and water are uniformly mixed by shearing, wherein the demetallizing agent is acetic acid and propionic acid, The amount of the demetallizer is 1.6 times the molar amount of calcium in the blended asphalt, the model of the demulsifier is KR40, the amount of the demulsifier is 110 μg / g of the weight of the blended asphalt, and the amount of water injected is 9% of the weight of the blended asphalt; secondly, at a temperature of 90°C, the obtained blended asphalt, the demetallizer, the demulsifier and water are mixed on a shear emulsifier for 30 minutes, and then placed in an electric desalting device for oil-water separation, the electric desalting temperature is 130°C, the electric desalting electric field is 800v / cm, and the electric desalting time is 30min. Under this condition, the metal in the blended asphalt is removed, and finally marine fuel oil is obtained, and its viscosity at 50°C is 295mm 2 / s, acid value is 2.11mg KOH / g, and ash content is 0.047%. In this embodiment, high-viscosity, high-acid value, and high-ash asphalt are used to prepare marine fuel oil. The final marine fuel oil product meets the product technical requirements of "Marine Fuel Oil" GB17411-2015 at 50°C in terms of viscosity, acid value, and ash content, and the amount of light components added is less than 70%, thereby improving the economy of marine high fuel oil.

[0039] Example 15: The marine fuel oil is prepared according to the following method: In the first step, high viscosity, high acid value and high ash asphalt is used as raw material, and its needle penetration at 25°C is 110 dmm and its viscosity at 50°C is 6.5×10 6 mm 2 / s, acid value is 7.02mg KOH / g, ash content is 0.36%, calcium content is 1236ug / g, thermal cracking process is used for thermal cracking reaction, thermal cracking reaction temperature is 420℃, reaction time is 40min, and cracked asphalt is obtained through thermal cracking reaction; secondly, a blending process is used to stir and mix cracked asphalt with a content of 55%, 45% catalytic diesel and catalytic wax oil to obtain blended asphalt; thirdly, the blended asphalt is subjected to chemical demetallization treatment to obtain marine fuel oil. The specific process of chemical demetallization treatment is as follows: firstly, the obtained blended asphalt, demetallizing agent, demulsifier and water are uniformly mixed by shearing, wherein the demetallizing agent is acetic acid and propionic acid and acetic anhydride, the amount of the demetallizing agent is 1.6 times the molar amount of calcium in the blended asphalt, the model of the demulsifier is LH-12, the amount of the demulsifier is 110μg / g of the weight of the blended asphalt, and the amount of water injected is 9% of the weight of the blended asphalt; secondly, at a temperature of 90°C, the obtained blended asphalt, the demetallizing agent, the demulsifier and water are mixed on a shear emulsifier for 30 minutes, and then placed in an electric desalting device for oil-water separation, the electric desalting temperature is 130°C, the electric desalting electric field is 800v / cm, and the electric desalting time is 30min. Under this condition, the metal in the blended asphalt is removed, and finally marine fuel oil is obtained, and its viscosity at 50°C is 325mm 2 / s, acid value is 2.35mg KOH / g, and ash content is 0.038%. In this embodiment, high-viscosity, high-acid value, and high-ash asphalt are used to prepare marine fuel oil. The final marine fuel oil product meets the product technical requirements of "Marine Fuel Oil" GB17411-2015 in terms of 50°C viscosity, acid value, and ash content, and the amount of light components added is less than 70%, which improves the economy of marine high fuel oil.

[0040] Example 16: The marine fuel oil is prepared according to the following method: In the first step, high viscosity, high acid value and high ash asphalt is used as raw material, and its needle penetration at 25°C is 135 dmm and its viscosity at 50°C is 2.8×10 6 mm 2 / s, acid value is 6.99mg KOH / g, ash content is 0.35%, calcium content is 1218ug / g, thermal cracking process is used for thermal cracking reaction, thermal cracking reaction temperature is 440℃, reaction time is 30min, and cracked asphalt is obtained through thermal cracking reaction; secondly, a blending process is used to stir and mix cracked asphalt with a content of 58%, 42% coking diesel and coking wax oil to obtain blended asphalt; thirdly, the blended asphalt is subjected to chemical demetallization treatment to obtain marine fuel oil, and the specific process of chemical demetallization treatment is as follows: firstly, the obtained blended asphalt, demetallizing agent, demulsifier and water are uniformly mixed by shearing, wherein the demetallizing agent is acetic acid, propionic acid and The amount of acetic anhydride, the amount of demetallizing agent is 1.5 times the molar amount of calcium in the blended asphalt, the model of the demulsifier is LH-12, the amount of the demulsifier is 100μg / g of the weight of the blended asphalt, and the amount of water injected is 8% of the weight of the blended asphalt; secondly, at a temperature of 90°C, the obtained blended asphalt, demetallizing agent, demulsifier and water are mixed on a shear emulsifier for 40 minutes, and then placed in an electric desalting device for oil-water separation, the electric desalting temperature is 130°C, the electric desalting electric field is 800v / cm, and the electric desalting time is 30min. Under this condition, the metal in the blended asphalt is removed, and finally marine fuel oil is obtained, and its viscosity at 50°C is 344mm 2 / s, acid value is 2.16mg KOH / g, and ash content is 0.023%. In this embodiment, high-viscosity, high-acid value, and high-ash asphalt are used to prepare marine fuel oil. The final marine fuel oil product meets the product technical requirements of "Marine Fuel Oil" GB17411-2015 at 50°C in terms of viscosity, acid value, and ash content, and the amount of light components added is less than 70%, thereby improving the economy of marine high fuel oil.

[0041] Example 17: The marine fuel oil is prepared according to the following method: In the first step, high viscosity, high acid value and high ash asphalt is used as raw material, and its needle penetration at 25°C is 160 dmm and its viscosity at 50°C is 9.2×10 5 mm 2 / s, acid value is 6.96mg KOH / g, ash content is 0.34%, calcium content is 1183ug / g, thermal cracking process is used for thermal cracking reaction, thermal cracking reaction temperature is 410℃, reaction time is 50min, and cracking asphalt is obtained through thermal cracking reaction; secondly, a blending process is used to stir and mix cracking asphalt with a content of 62%, 38% catalytic diesel, catalytic wax oil and coking wax oil to obtain blending asphalt; thirdly, the blending asphalt is subjected to chemical demetallization treatment to obtain marine fuel oil, and the specific process of chemical demetallization treatment is as follows: firstly, the obtained blending asphalt, demetallizing agent, demulsifier and water are uniformly mixed by shearing, wherein the demetallizing agent is ethyl Acid and butyric acid, the amount of demetallizing agent is 1.5 times the molar amount of calcium in the blended asphalt, the demulsifier model is LH-12, the amount of demulsifier is 100μg / g of the weight of the blended asphalt, and the water injection amount is 8% of the weight of the blended asphalt; secondly, at a temperature of 90°C, the obtained blended asphalt, demetallizing agent, demulsifier and water are mixed on a shear emulsifier for 40 minutes, and then placed in an electric desalting device for oil-water separation, the electric desalting temperature is 120°C, the electric desalting electric field is 800v / cm, and the electric desalting time is 30min. Under this condition, the metal in the blended asphalt is removed, and finally marine fuel oil is obtained, and its viscosity at 50°C is 342mm 2 / s, acid value is 2.32mg KOH / g, and ash content is 0.045%. In this embodiment, high-viscosity, high-acid value, and high-ash asphalt are used to prepare marine fuel oil. The final marine fuel oil product meets the product technical requirements of "Marine Fuel Oil" GB17411-2015 at 50°C in terms of viscosity, acid value, and ash content, and the amount of light components added is less than 70%, thereby improving the economy of marine high fuel oil.

[0042] Example 18: The marine fuel oil is prepared according to the following method: In the first step, high viscosity, high acid value and high ash asphalt is used as raw material, and its needle penetration at 25°C is 185 dmm and its viscosity at 50°C is 7.6×10 5 mm 2 / s, acid value is 6.93mg KOH / g, ash content is 0.34%, calcium content is 1167ug / g, thermal cracking process is used for thermal cracking reaction, thermal cracking reaction temperature is 410℃, reaction time is 50min, and cracking asphalt is obtained through thermal cracking reaction; secondly, a blending process is used to stir and mix 65% cracking asphalt, 35% catalytic diesel, catalytic wax oil and coking diesel to obtain blending asphalt; thirdly, the blending asphalt is subjected to chemical demetallization treatment to obtain marine fuel oil, and the specific process of chemical demetallization treatment is as follows: firstly, the obtained blending asphalt, demetallizing agent, demulsifier and water are shear-mixed uniformly, wherein the demetallizing agent is acetic acid , butyric acid and acetic anhydride, the amount of demetallizing agent is 1.2 times the molar amount of calcium in blended asphalt, the model of demulsifier is LH-12, the amount of demulsifier is 90μg / g of the weight of blended asphalt, and the amount of water injection is 8% of the weight of blended asphalt; secondly, at a temperature of 85°C, the obtained blended asphalt, demetallizing agent, demulsifier and water are mixed on a shear emulsifier for 40 minutes, and then placed in an electric desalting device for oil-water separation, the electric desalting temperature is 120°C, the electric desalting electric field is 600v / cm, and the electric desalting time is 40min. Under this condition, the metal in the blended asphalt is removed, and finally marine fuel oil is obtained, and its viscosity at 50°C is 262mm 2 / s, acid value is 1.70mg KOH / g, and ash content is 0.012%. In this embodiment, high-viscosity, high-acid value, and high-ash asphalt are used to prepare marine fuel oil. The final marine fuel oil product meets the product technical requirements of "Marine Fuel Oil" GB17411-2015 at 50°C in terms of viscosity, acid value, and ash content, and the amount of light components added is less than 70%, thereby improving the economy of marine high fuel oil.

[0043] Example 19: The marine fuel oil is prepared according to the following method: In the first step, high viscosity, high acid value and high ash asphalt is used as raw material, and its needle penetration at 25°C is 210 dmm and its viscosity at 50°C is 5.5×10 5 mm 2 / s, acid value is 6.91mg KOH / g, ash content is 0.33%, calcium content is 1134ug / g, thermal cracking process is used for thermal cracking reaction, thermal cracking reaction temperature is 400℃, reaction time is 50min, and cracking asphalt is obtained through thermal cracking reaction; secondly, a blending process is used to stir and mix 70% cracking asphalt, 30% coking wax oil, coking diesel and catalytic diesel to obtain blending asphalt; thirdly, the blending asphalt is subjected to chemical demetallization treatment to obtain marine fuel oil, and the specific process of chemical demetallization treatment is as follows: firstly, the obtained blending asphalt, demetallizing agent, demulsifier and water are uniformly mixed by shearing, wherein the demetallizing agent is acetic acid, butane Acid, acetic anhydride and acetic anhydride, the amount of demetallizing agent is 1.2 times the molar amount of calcium in the blended asphalt, the demulsifier model is LH-14, the amount of demulsifier is 90μg / g of the weight of the blended asphalt, and the water injection amount is 7% of the weight of the blended asphalt; secondly, at a temperature of 85°C, the obtained blended asphalt, demetallizing agent, demulsifier and water are mixed on a shear emulsifier for 50 minutes, and then placed in an electric desalting device for oil-water separation, the electric desalting temperature is 120°C, the electric desalting electric field is 600v / cm, and the electric desalting time is 40min. Under this condition, the metal in the blended asphalt is removed, and finally marine fuel oil is obtained, and its viscosity at 50°C is 189mm 2 / s, acid value is 1.43mg KOH / g, and ash content is 0.057%. In this embodiment, high-viscosity, high-acid value, and high-ash asphalt are used to prepare marine fuel oil. The final marine fuel oil product meets the product technical requirements of "Marine Fuel Oil" GB17411-2015 at 50°C in terms of viscosity, acid value, and ash content, and the amount of light components added is less than 70%, thereby improving the economy of marine high fuel oil.

[0044] Example 20: The marine fuel oil is prepared according to the following method: In the first step, high viscosity, high acid value and high ash asphalt is used as raw material, and its needle penetration at 25°C is 235 dmm and its viscosity at 50°C is 4.2×10 5 mm 2 / s, acid value is 6.88mg KOH / g, ash content is 0.33%, calcium content is 1119ug / g, thermal cracking process is used for thermal cracking reaction, thermal cracking reaction temperature is 400℃, reaction time is 50min, and cracking asphalt is obtained through thermal cracking reaction; secondly, a blending process is used to stir and mix cracking asphalt with a content of 73%, coking wax oil, coking diesel and catalytic wax oil with a content of 27% to obtain blending asphalt; thirdly, the blending asphalt is subjected to chemical demetallization treatment to obtain marine fuel oil, and the specific process of chemical demetallization treatment is as follows: firstly, the obtained blending asphalt, demetallizing agent, demulsifier and water are uniformly mixed by shearing, wherein the demetallizing agent is acetic acid , acetic acid and propionic acid, the amount of the demetallizing agent is 1.0 times the molar amount of calcium in the blended asphalt, the demulsifier model is LH-14, the amount of the demulsifier is 80μg / g of the weight of the blended asphalt, and the water injection amount is 7% of the weight of the blended asphalt; secondly, at a temperature of 85°C, the obtained blended asphalt, demetallizing agent, demulsifier and water are mixed on a shear emulsifier for 50 minutes, and then placed in an electric desalting device for oil-water separation, the electric desalting temperature is 120°C, the electric desalting electric field is 600v / cm, and the electric desalting time is 50min. Under this condition, the metal in the blended asphalt is removed, and finally marine fuel oil is obtained, and its viscosity at 50°C is 126mm 2 / s, acid value is 193mg KOH / g, and ash content is 0.038%. In this embodiment, high-viscosity, high-acid value, and high-ash asphalt are used to prepare marine fuel oil. The final marine fuel oil product meets the product technical requirements of "Marine Fuel Oil" GB17411-2015 in terms of 50°C viscosity, acid value, and ash content, and the amount of light components added is less than 70%, which improves the economy of marine high fuel oil.

[0045] Example 21: The marine fuel oil is prepared according to the following method: In the first step, high viscosity, high acid value and high ash asphalt is used as raw material, and its needle penetration at 25°C is 270 dmm and its viscosity at 50°C is 3.8×10 5 mm 2 / s, acid value is 6.85mg KOH / g, ash content is 0.32%, calcium content is 1096ug / g, thermal cracking process is used for thermal cracking reaction, thermal cracking reaction temperature is 390℃, reaction time is 60min, and cracked asphalt is obtained through thermal cracking reaction; secondly, a blending process is used to stir and mix cracked asphalt with a content of 76%, 24% catalytic diesel and coking wax oil to obtain blended asphalt; thirdly, the blended asphalt is subjected to chemical demetallization treatment to obtain marine fuel oil, and the specific process of chemical demetallization treatment is as follows: firstly, the obtained blended asphalt, demetallizing agent, demulsifier and water are uniformly mixed by shearing, wherein the demetallizing agent is acetic acid and butyric acid, the amount of the demetallizing agent is 1.0 times the molar amount of calcium in the blended asphalt, the demulsifier model is LH-14, the amount of the demulsifier is 80μg / g of the weight of the blended asphalt, and the water injection amount is 6% of the weight of the blended asphalt; secondly, at a temperature of 85°C, the obtained blended asphalt, the demetallizing agent, the demulsifier and water are mixed on a shear emulsifier for 50 minutes, and then placed in an electric desalting device for oil-water separation, the electric desalting temperature is 110°C, the electric desalting electric field is 600v / cm, and the electric desalting time is 50min. Under this condition, the metal in the blended asphalt is removed, and finally marine fuel oil is obtained, and its viscosity at 50°C is 124mm 2 / s, acid value is 1.91mg KOH / g, and ash content is 0.042%. In this embodiment, high-viscosity, high-acid value, and high-ash asphalt are used to prepare marine fuel oil. The final marine fuel oil product meets the product technical requirements of "Marine Fuel Oil" GB17411-2015 in terms of 50°C viscosity, acid value, and ash content, and the amount of light components added is less than 70%, which improves the economy of marine high fuel oil.

[0046] Example 22: The marine fuel oil is prepared according to the following method: In the first step, high viscosity, high acid value and high ash asphalt is used as raw material, and its needle penetration at 25°C is 300 dmm and its viscosity at 50°C is 2.6×10 5 mm 2 / s, acid value is 6.82mg KOH / g, ash content is 0.31%, calcium content is 1060ug / g, thermal cracking process is used for thermal cracking reaction, thermal cracking reaction temperature is 390℃, reaction time is 60min, and cracked asphalt is obtained through thermal cracking reaction; secondly, a blending process is used to stir and mix 80% cracked asphalt, 20% catalytic wax oil and coking diesel to obtain blended asphalt; thirdly, the blended asphalt is chemically demetallized to obtain marine fuel oil, and the specific process of chemical demetallization treatment is as follows: firstly, the obtained blended asphalt, demetallizing agent, demulsifier and water are uniformly mixed by shearing, wherein the demetallizing agent is acetic acid, propionic acid and butyric acid, and the demetallizing agent is acetic acid, propionic acid and butyric acid. The amount of the metal agent is 0.8 times the molar amount of calcium in the blended asphalt, the demulsifier model is LH-14, the amount of the demulsifier is 70μg / g of the weight of the blended asphalt, and the water injection amount is 6% of the weight of the blended asphalt; secondly, at a temperature of 80°C, the obtained blended asphalt, demetallizing agent, demulsifier and water are mixed on a shear emulsifier for 60 minutes, and then placed in an electric desalting device for oil-water separation. The electric desalting temperature is 110°C, the electric desalting electric field is 500v / cm, and the electric desalting time is 60min. Under this condition, the metal in the blended asphalt is removed, and finally marine fuel oil is obtained, whose viscosity at 50°C is 96mm2 / s, acid value is 1.86mg KOH / g, and ash content is 0.035%. This embodiment uses high-viscosity, high-acidity, and high-ash asphalt to prepare marine fuel oil. The final marine fuel oil product meets the product technical requirements of "Marine Fuel Oil" GB17411-2015 in terms of 50°C viscosity, acidity, and ash content, and the amount of light components added is less than 70%, thereby improving the economy of marine high-fuel oil.

[0047] Example 23: The marine fuel oil is prepared according to the following method: In the first step, high viscosity, high acid value and high ash asphalt is used as raw material, and its needle penetration at 25°C is 150 dmm and its viscosity at 50°C is 8.7×10 5 mm 2 / s, acid value is 6.93mg KOH / g, ash content is 0.35%, calcium content is 1120ug / g, thermal cracking process is used for thermal cracking reaction, thermal cracking reaction temperature is 350℃, reaction time is 30min, and cracked asphalt is obtained through thermal cracking reaction; secondly, a blending process is used to stir and mix 70% cracked asphalt, 30% catalytic wax oil and coking diesel to obtain blended asphalt; thirdly, the blended asphalt is subjected to chemical demetallization treatment to obtain marine fuel oil, and the specific process of chemical demetallization treatment is as follows: firstly, the obtained blended asphalt, demetallizing agent, demulsifier and water are uniformly mixed by shearing, wherein the demetallizing agent is acetic acid and Propionic acid, the amount of demetallizing agent is 0.5 times the molar amount of calcium in the blended asphalt, the demulsifier model is LH-14, the amount of demulsifier is 45μg / g of the weight of the blended asphalt, and the amount of water injection is 15% of the weight of the blended asphalt; secondly, at a temperature of 80°C, the obtained blended asphalt, demetallizing agent, demulsifier and water are mixed on a shear emulsifier for 30 minutes, and then placed in an electric desalting device for oil-water separation, the electric desalting temperature is 100°C, the electric desalting electric field is 500v / cm, and the electric desalting time is 45min. Under this condition, the metal in the blended asphalt is removed, and finally marine fuel oil is obtained, and its viscosity at 50°C is 398mm 2 / s, the acid value is 2.52mg KOH / g, and the ash content is 0.113%. In this embodiment, although the light component addition amount of the prepared marine fuel oil is less than 70%, which improves the economy of the marine high fuel oil, the viscosity, acid value and ash content at 50°C do not meet the product technical requirements of "Marine Fuel Oil" GB17411-2015.

[0048] Comparative Example: The marine fuel oil was prepared according to the following method: In the first step, high viscosity, high acid value and high ash asphalt was used as raw material, and its needle penetration at 25°C was 150 dmm and its viscosity at 50°C was 8.7×10 5 mm 2 / s, acid value is 6.93mg KOH / g, ash content is 0.35%, calcium content is 1120ug / g, and a direct blending process is used to mix 25% of cracked asphalt, 75% of catalytic wax oil and coking diesel to obtain a marine fuel oil product with a viscosity of 156mm at 50℃. 2 / s, acid value is 2.46mgKOH / g, and ash content is 0.091%. In this embodiment, although the viscosity, acid value, and ash content of the prepared marine fuel oil at 50°C meet the product technical requirements of "Marine Fuel Oil" GB17411-2015, the amount of light components added is as high as 75%, which reduces the economy of the marine fuel oil.

[0049] The minimum viscosity index of residual marine fuel oil RMG380 at 50°C in GB17411-2015 Marine Fuel Oil is 380mm2 / s, the minimum acid value is 2.5 mg KOH / g, and the minimum ash content is 0.1%. It can be seen from Examples 11 to 22 that the viscosity, acid value and ash content of the marine fuel oil at 50°C of the present invention meet the product technical requirements of "Marine Fuel Oil" GB17411-2015, not only the amount of light components added is less than 70%, but also the proportion of cracked asphalt in the marine fuel oil is increased, thereby improving the economy of marine high fuel oil.

[0050] In summary, the present invention provides a method for preparing residual marine fuel oil by using high-viscosity, high-acid value and high-ash asphalt. The prepared marine fuel oil not only meets the product technical requirements of "Marine Fuel Oil" (GB17411-2015), but also increases the proportion of cracked asphalt in marine fuel oil and improves the economy of marine high fuel oil.

[0051] The above technical features constitute the embodiments of the present invention, which have strong adaptability and implementation effect. Non-essential technical features can be added or reduced according to actual needs to meet the requirements of different situations.

Claims

1. A marine fuel oil, characterized in that The preparation is carried out according to the following steps: the first step is to use high-viscosity, high-acidity and high-ash asphalt as raw material, adopt a thermal cracking process, and obtain cracked asphalt through thermal cracking reaction; the second step is to adopt a blending process to evenly mix the required amount of cracked asphalt and light components to obtain blended asphalt; the third step is to chemically demetallize the blended asphalt to obtain marine fuel oil.

2. The marine fuel oil according to claim 1, characterized in that In the first step, the needle penetration of high viscosity, high acid value and high ash asphalt at 25°C ranges from 10 dmm to 300 dmm, and the viscosity at 50°C is not less than 2.5×10 5 mm 2 / s, the acid value is not less than 6.8mgKOH / g, the ash content is not less than 0.3%, and the thermal cracking reaction temperature is 370℃ to 460℃, and the reaction time is 20min to 90min.

3. The marine fuel oil according to claim 1 or 2, characterized in that The thermal cracking reaction temperature is 390°C to 440°C, and the reaction time is 30min to 60min.

4. The marine fuel oil according to claim 1, 2 or 3, characterized in that In the second step, the light component is one or more of catalytic wax oil, catalytic diesel, coker wax oil, and coker diesel, and in the blended asphalt, the weight percentage of cracked asphalt in the blended asphalt is 40% to 80%, and the weight percentage of the light component in the blended asphalt is 20% to 60%.

5. The marine fuel oil according to any one of claims 1 to 4, characterized in that In the third step, the specific process of chemical demetallization treatment is: firstly, the required amount of blended asphalt, demetallization agent, demulsifier and water are evenly mixed by shearing, and then the oil and water are separated by electrical desalting, and the marine fuel oil is obtained after removing the metal-containing water in the blended asphalt.

6. The marine fuel oil according to claim 5, characterized in that The shear temperature is 80°C to 100°C, the shear time is 20min to 60min, the electro-desalting temperature is 110°C to 140°C, the electro-desalting electric field is 500v / cm to 1200v / cm, the electro-desalting time is 10min to 60min, the demetallizing agent is one or more of acetic acid, propionic acid, butyric acid, acetic anhydride, and acetic-propionic anhydride, and the metal in the metal-containing water in the blended asphalt is calcium, wherein the molar amount of the demetallizing agent is 0.6 to 2.2 times the molar amount of calcium in the blended asphalt.

7. The marine fuel oil according to claim 6, characterized in that The molar amount of the demetallizing agent is 0.8 to 2.0 times the molar amount of calcium in the blended asphalt.

8. The marine fuel oil according to claim 5, 6 or 7, characterized in that The weight ratio of the demulsifier to the blended asphalt is 50 μg / g to 150 μg / g, wherein the weight percentage of water to the blended asphalt is 4% to 12%.

9. The marine fuel oil according to claim 8, characterized in that The weight ratio of the demulsifier to the blended asphalt is 70μg / g to 130μg / g, wherein the weight percentage of water to the blended asphalt is 6% to 10%.

10. A method for preparing marine fuel oil according to claims 2 to 9, characterized in that The process is carried out in the following steps: the first step is to use high-viscosity, high-acidity and high-ash asphalt as raw material, adopt a thermal cracking process, and obtain cracked asphalt through thermal cracking reaction; the second step is to adopt a blending process to evenly mix the required amount of cracked asphalt and light components to obtain blended asphalt; the third step is to chemically demetallize the blended asphalt to obtain a marine fuel oil product.