A low-carbon marine fuel oil and a preparation method thereof

Abstract

The application discloses a kind of low-carbon marine fuel oil and preparation method thereof.The fuel oil includes residual oil 40-70%, catalytic diesel oil 5-15%, methanol 5-40%, stabilizer 0.5~2.5%, cosolvent 1-3%, activator 5-10%, emulsifier 0.1-1% by weight percentage.The sum of the mass fraction of each component is 100%.The low-carbon marine fuel oil of the application can achieve stable storage, oxidation resistance and anti-coking of fuel oil under the premise of reducing carbon emissions, providing a new way for blending new environmentally friendly low-sulfur marine fuel oil.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of fuel oil blending, and particularly relates to a low-carbon marine fuel oil and a preparation method thereof. BACKGROUND

[0002] With the improvement of international environmental protection and carbon emission requirements, marine fuel oil is gradually converted into low-carbon type. The main marine fuel oils include LNG, hydrogen energy, liquid ammonia and the like. However, the use of these new energy sources needs to modify the ship structure and engine, which is time-consuming and difficult, and it is not easy to achieve large-scale application in a short period of time. However, through the low-carbonization of the blending components of marine fuel oil, not only can the carbon emission be reduced, but also the modification and upgrading of the existing equipment can be reduced to adapt to the current use demand of marine vessels. At present, the main blending components of marine fuel oil include residual oil and catalytic diesel, and the main carbon source is the large amount of condensed ring aromatic hydrocarbons in residual oil and the large amount of resin and unsaturated hydrocarbons in catalytic diesel. By adding a part of low-carbon component oil to reduce the carbon content per unit mass, the low-carbonization of marine fuel oil can be realized.

[0003] ZL2012101974219 provides a low-carbon fuel oil and a preparation method thereof. The process mainly adopts methanol or its modified complex and additives such as three-in-one emulsifier for mixing. However, the process uses oleic acid to modify methanol, but oleic acid is easy to oxidize, polymerize and decompose, and its acidity is easy to cause corrosion to the equipment.

[0004] ZL2018107289595 provides a quantum nano low-carbon fuel and a preparation method thereof. The process introduces quantum implantation technology in the production process to recombine and quantify the structure of oil molecules. However, the quantum resonance energy cabin required in the process is not suitable for the low-cost production field of marine fuel oil, which relatively increases the production cost.

[0005] In order to realize the low-carbon emission reduction target of marine fuel oil, a low-carbon marine fuel oil and a preparation method thereof need to be developed. SUMMARY

[0006] In view of the problem that the current fuel oil needs low-carbon emission reduction, the purpose of the present application is to provide a low-carbon marine fuel oil and a production and preparation method thereof. The low-carbon marine fuel oil of the present application can realize the characteristics of stable storage, oxidation resistance and anti-coking of fuel oil under the premise of reducing carbon emission, and provides a new way for blending and producing new environmentally friendly low-sulfur marine fuel oil.

[0007] In order to achieve the above purpose, the present application provides a low-carbon marine fuel oil and a preparation method thereof.

[0008] According to a first aspect of the present application, the present application provides a low-carbon marine fuel oil.

[0009] The low-carbon marine fuel oil of the present application comprises, in percentage by weight, 40-70% of residual oil, 5-15% of catalytic diesel oil, 5-40% of methanol, 0.5-2.5% of stabilizer, 1-3% of cosolvent, 5-10% of activator, 0.4-1% of emulsifier, and the sum of the mass fractions of the components is 100%.

[0010] In the present application, the viscosity of the residual oil ranges from 100 to 1000 mm / s 2 (50℃), and the density ranges from 960 to 990 kg / m 3 (20℃).

[0011] In the present application, the viscosity of the catalytic diesel oil ranges from 1 to 10 mm / s 2 (50℃), and the density ranges from 940 to 980 kg / m 3 (20℃).

[0012] In the present application, the methanol is industrial methanol with a purity of not less than 95%.

[0013] In the present application, the stabilizer is a diethanolamide non-ionic surfactant, including one or more of lauryl diethanolamide, oleic acid diethanolamide, stearic acid diethanolamide, and coconut oil fatty acid diethanolamide, and is preferably coconut oil fatty acid diethanolamide.

[0014] In the present application, the cosolvent is an alcohol with a carbon number of 5-12, which is a single alcohol or a mixed solution of several alcohols.

[0015] In the present application, the activator is a fatty acid methyl ester or a fatty acid ethyl ester, which is a single solution or a mixed solution. The carbon chain of the fatty acid is generally between 12 and 20.

[0016] In the present application, the emulsifier is a non-ionic emulsifier, such as polyoxyethylene, polyol, etc.; preferably OP series, AEO series, Tween series, and Span series.

[0017] The low-carbon marine fuel oil of the present application has a viscosity of not more than 180 mm / s 2 (50℃), a density of not more than 985 kg / m 3 (20℃), a sulfur content of not more than 0.5%, and does not separate after storage for 30 days.

[0018] The present application also provides a preparation method of the low-carbon marine fuel oil, which comprises the following steps:

[0019] (1) heating the residual oil to a temperature T1, adding the stabilizer and stirring uniformly to obtain a mixed oil A;

[0020] (2) mixing the methanol and the cosolvent uniformly, and then adding the activator and mixing uniformly to obtain a mixed solution B;

[0021] (3) mixing liquid B is emulsified with catalytic diesel and emulsifier by an emulsifying pump to obtain mixing liquid C;

[0022] (4) mixing liquid C is continuously stirred by a high-speed shearing machine at temperature T2, assisted by a high-power ultrasonic wave, and solution A is added at a certain speed v to make them uniformly mixed, continuously stirred and ultrasonically treated for 1.5-3 hours to obtain the product.

[0023] According to the method, T1 is 60-100 DEG C, and T2 is 40-60 DEG C.

[0024] According to the method, the power of the high-power ultrasonic wave applied to each liter of the mixing liquid is not less than 20 kW, and the frequency is not less than 400 kHz.

[0025] According to the method, the rate v of adding solution A to each kilogram of mixing liquid C is 0.6 L / h-2.5 L / h.

[0026] In the application, the stabilizer is bonded with hydrogen atoms through lone pair electrons, the number of intermolecular and intramolecular hydrogen bonds in the system is increased to maintain the stability of the system. The chain initiation reaction and chain growth reaction are prevented or inhibited by capturing peroxide radicals, thereby terminating the free radical chain reaction, and the purpose of preventing oxidation is achieved. Meanwhile, the stabilizer also plays a role in diluting the residual oil to improve the mixing degree with light components.

[0027] In the application, the cosolvent is a substance with amphiphilic properties. The molecule has both hydrophilic group -OH and methanol hydroxyl group to form intermolecular complexes and associated compounds, and long carbon chains to interact with hydrocarbon molecules in oil products to adsorb and entangle, so that methanol can be better dissolved in the oil product system.

[0028] In the application, the activator provides electrons through oxygen atoms to form intermolecular hydrogen bonds with methanol / cosolvent to increase the mass of molecular groups. The long carbon chain makes the modified methanol component have similar properties to hydrocarbons in diesel, which can help to increase the compatibility of the system.

[0029] In the application, the emulsifier has good emulsifying effect on macromolecular micelles such as asphaltene in residual oil. The non-ionic emulsifier reduces the surface tension between macromolecular micelles and small molecules to achieve the purpose of uniform mixing and improve the stability of residual oil and catalytic diesel after adding methanol.

[0030] In this invention, the preparation method for low-carbon marine fuel oil adopts a two-step approach. The first step involves treating the residual oil and methanol separately. A stabilizer is dispersed in the residual oil; the methanol is modified and activated to improve its compatibility with the fuel oil, ensuring good miscibility. In the second step, the activated modified methanol is homogenized and emulsified with catalytic diesel oil under the action of an emulsifier. Then, the residual oil is gradually dispersed into the mixture. High-power ultrasound has a strong cavitation effect, which, at a lower temperature, can highly disperse large molecules in the mixture, such as asphaltene colloidal particles, improving the emulsification effect and achieving uniform mixing.

[0031] Methanol is modified and activated using co-solvents and activators. Taking advantage of the high gum content in catalytic diesel, the activated modified methanol is adsorbed near the hydrocarbon molecules in the catalytic diesel, forming a water-in-oil emulsion that facilitates further mixing with residual oil. The residual oil is then viscosity-reduced and emulsified using stabilizers and emulsifiers, increasing hydrogen bonding between it and the methanol / catalytic diesel, thus improving the stability of the methanol blend in the residual oil system and creating a stable low-carbon marine fuel oil system.

[0032] Compared with the prior art, the method for preparing low-carbon marine fuel oil provided by the present invention has the following advantages:

[0033] 1. Through various solvent blending technologies and formulation processes, methanol is mixed with high-carbon fuel oil to form a stable low-carbon marine fuel oil, reducing its hydrocarbon ratio, with a viscosity not exceeding 180 mm / s. 2 (50℃), density not exceeding 985 kg / m³ 3 (20℃), sulfur content not exceeding 0.5%, no stratification after 30 days of storage, effectively achieving the goal of low-carbon emission reduction for marine fuel oil.

[0034] 2. The process route of this invention is simple. The application of high-power ultrasound enables fuel oil to emulsify at a lower temperature, achieving a uniform mixing effect, reducing process energy consumption, and making it easy to operate. Implementation

[0035] The following examples further illustrate the solution and effects of the present invention, but do not constitute a limitation on the present invention.

[0036] The blended residue oil and catalytic diesel oil used in this embodiment were obtained from different refineries, and their main physicochemical properties are shown in Table 1.

[0037] Table 1 Physicochemical properties of feedstock oils from different refineries

[0038] Item Resid 1 Cat. diesel 1 Resid 2 Cat. diesel 2 Viscosity, mm / s 2 (50°C) 163.9 1.759 921.2 2.336 Density, kg / m3 3 (20°C) 988.4 926.3 987.8 973.2 Sulfur content, % 0.42 0.25 0.45 0.30 Example 1

[0039] After 600 g of Residual Oil 1 was heated to 85°C, 15 g of stabilizer coconut oil diethanolamide was added and stirred until uniform to obtain a mixture 1. After 200 g of methanol was mixed uniformly with 20 g of 1-octanol, 80 g of methyl linolenate was added, mixed uniformly, and emulsified with 80 g of catalytic diesel oil 1, 5 g of Tween-60 by an emulsifying pump to obtain a mixture 2. The mixture 2 was continuously stirred at 50°C by a homogenizing high-speed shearing machine, continuously ultrasonicated by a high-power ultrasonic with an auxiliary power of 30 kW and a frequency of 500 kHz, and mixture 1 was added at a rate of 1 L / h, continuously stirred and ultrasonicated for 2 hours to obtain product S1. The stability test method was to place at room temperature and observe whether it was layered. Example 2

[0040] After 450 g of Residual Oil 2 was heated to 95°C, 10 g of stabilizer stearic acid diethanolamide was added and stirred until uniform to obtain a mixture 1. After 350 g of methanol was mixed uniformly with 25 g of 1-decanol, 87 g of ethyl laurate was added, mixed uniformly, and emulsified with 70 g of catalytic diesel oil 2, 8 g of Span-60 by an emulsifying pump to obtain a mixture 2. The mixture 2 was continuously stirred at 55°C by a homogenizing high-speed shearing machine, continuously ultrasonicated by a high-power ultrasonic with an auxiliary power of 25 kW and a frequency of 450 kHz, and mixture 1 was added at a rate of 0.8 L / h, continuously stirred and ultrasonicated for 2 hours to obtain product S2. Example 3

[0041] After 650 g of Residual Oil 1 was heated to 75°C, 7 g of stabilizer lauryl diethanolamine was added and stirred until uniform to obtain a mixture 1. After 100 g of methanol was mixed uniformly with 27 g of n-hexanol, 68 g of methyl palmitate was added, mixed uniformly, and emulsified with 140 g of catalytic diesel oil 2, 8 g of AEO-9 by an emulsifying pump to obtain a mixture 2. The mixture 2 was continuously stirred at 45°C by a homogenizing high-speed shearing machine, continuously ultrasonicated by a high-power ultrasonic with an auxiliary power of 35 kW and a frequency of 450 kHz, and mixture 1 was added at a rate of 1.5 L / h, continuously stirred and ultrasonicated for 2 hours to obtain product S3. Example 4

[0042] After 500 g of Residual Oil 2 was heated to 70°C, 22 g of stabilizer oleic acid diethanolamide was added and stirred until uniform to obtain a mixture 1. After 290 g of methanol was mixed uniformly with 15 g of 1-undecanol, 57 g of methyl stearate was added, mixed uniformly, and emulsified with 110 g of catalytic diesel oil 2, 8 g of OP-10 by an emulsifying pump to obtain a mixture 2. The mixture 2 was continuously stirred at 50°C by a homogenizing high-speed shearing machine, continuously ultrasonicated by a high-power ultrasonic with an auxiliary power of 30 kW and a frequency of 500 kHz, and mixture 1 was added at a rate of 2 L / h, continuously stirred and ultrasonicated for 2 hours to obtain product S4.

[0043] Comparative Example 1

[0044] Prepared as in Example 1, but without adding stabilizer coconut oil diethanolamide during the preparation process, to obtain product D1.

[0045] Comparative Example 2

[0046] Prepared as in Example 1, but without adding cosolvent 1-octanol during the preparation process, to obtain product D2.

[0047] Comparative Example 3

[0048] Prepared as in Example 1, but without adding activator methyl linolenate during the preparation process, to obtain product D3.

[0049] Comparative Example 4

[0050] Prepared as in Example 1, but without adding emulsifier Tween-60 during the preparation process, to obtain product D4.

[0051] Comparative Example 5

[0052] Compared with Example 1, the formulation is consistent, but the preparation process is changed to adding residue oil 1, catalytic diesel oil 1, methanol, stabilizer coconut oil diethanolamide, cosolvent 1-octanol, activator methyl linolenate, and emulsifier Tween-60 at 50°C at the same time, and the homogenizer is continuously sheared and mixed for 2h to obtain product D5.

[0053] The physicochemical properties and stability test results of the sample of the above examples and comparative examples are shown in Table 2.

[0054] Table 2 Physicochemical properties and stability of the sample of examples and comparative examples

[0055] Item S1 S2 S3 S4 D1 D2 D3 D4 D5 Viscosity, mm / s 2 (50 °C) 98 115 101 104 95 93 95 92 100 Density, kg / m3 3 (20°C) 937.2 952.7 940.0 935.2 935.0 937.7 940.1 937.9 939.9 Sulfur content, % 0.27 0.21 0.31 0.24 0.27 0.25 0.29 0.27 0.28 Stability time, d >30 >30 >30 >30 3 6 7 4 16

Claims

1. A method for preparing low-carbon marine fuel oil, characterized in that, Includes the following: (1) Heat the residual oil to temperature T1, add the stabilizer and stir evenly to obtain mixed oil A; (2) Mix methanol and co-solvent evenly, then add activator and mix evenly to obtain mixture B; (3) Mixture B is emulsified together with catalytic diesel and emulsifier through an emulsification pump to obtain mixture C; (4) Mixture C is continuously stirred at temperature T2 using a homogenizing high-speed shear machine, and mixed oil A is added at a certain speed v with the assistance of high-power ultrasonic waves to make the two mix evenly. The mixture is stirred and ultrasonically continuously to obtain the product. The low-carbon marine fuel oil comprises, by weight percentage, 40-70% residual oil, 5-15% catalytic diesel, 5-40% methanol, 0.5-2.5% stabilizer, 1-3% cosolvent, 5-10% activator, and 0.1-1% emulsifier, with the sum of the mass fractions of all components being 100%. The stabilizer is an alkanolamide; the activator is one or more of fatty acid methyl esters and fatty acid ethyl esters, wherein the carbon chain of the fatty acid is between 12 and 22; and the cosolvent is an alcohol with 5 to 12 carbon atoms.

2. The preparation method according to claim 1, characterized in that, T1 is 60-100℃, and T2 is 40-60℃.

3. The preparation method according to claim 1, characterized in that, The rate at which each kilogram of mixed liquid C is added to mixed oil A is 0.6 ~ 2.5 L / h.

4. The preparation method according to claim 1, characterized in that, The power of the high-power ultrasound is not less than 20kW per liter of the mixture, and the frequency is not less than 400kHz.

5. The preparation method according to claim 1, characterized in that, The viscosity range of the residual oil is 100~1000 mm / s 2 (50℃), density range is 960~990 kg / m³ 3 (20℃).

6. The preparation method according to claim 1, characterized in that, The viscosity of the catalytic diesel oil is 1~10 mm / s 2 (50℃), density range is 940~980 kg / m³ 3 (20℃).

7. The preparation method according to claim 1, characterized in that, The purity of the methanol is not less than 95%.

8. The preparation method according to claim 1, characterized in that, The emulsifier is selected from polyoxyethylene or polyols.

9. The preparation method according to claim 1, characterized in that, The viscosity of the low-carbon marine fuel oil shall not exceed 180 mm / s. 2 (50℃), density not exceeding 985 kg / m³ 3 (20℃), sulfur content not exceeding 0.5%, no stratification after 30 days of storage.