Low-carbon marine fuel oil and preparation method thereof

Abstract

The invention discloses low-carbon marine fuel oil and a preparation method thereof. The fuel oil comprises the following components in percentage by weight: 40-70% of residual oil, 5-15% of catalytic diesel oil, 5-40% of methanol, 0.5-2.5% of a stabilizer, 1-3% of a cosolvent, 5-10% of an activator and 0.1-1% of an emulsifier, wherein the sum of the mass fractions of all the components is 100%. According to the low-carbon fuel oil for the ship, stable storage, oxidation resistance and coking resistance of the fuel oil can be realized on the premise of reducing carbon emission, and a new way is provided for blending production of novel environment-friendly low-sulfur fuel oil for the ship.

Description

Technical Field

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

[0002] With the improvement of international environmental protection and carbon emission requirements, marine fuel oil is gradually transforming to low-carbon type. The main marine fuel oils include LNG, hydrogen energy, liquid ammonia, etc., but the use of these new energy sources requires the modification of ship structure and engine, which is time-consuming and difficult, and large-scale application in a short period of time is not easy to achieve. However, through the low-carbonization of marine fuel oil blending components, it is not only possible to reduce carbon emissions, but also reduce the modification and upgrading of existing equipment to meet the current use needs of marine ships. At present, the main blending components of marine fuel oil include residual oil and catalytic diesel. The main carbon sources are a large amount of polycyclic aromatic hydrocarbons in residual oil and a large amount of colloids 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 achieved.

[0003] ZL2012101974219 provides a low-carbon fuel oil and its preparation method, which mainly uses methanol or its modified complex to mix with additives such as three-in-one emulsifier. 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 corrode equipment.

[0004] ZL2018107289595 provides a quantum nano low-carbon fuel and its preparation method, which restructures and quantifies oil molecules by introducing quantum implantation technology in the production process. However, the quantum resonance energy chamber 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 achieve the goal of low-carbon emission reduction of marine fuel oil, it is necessary to develop a low-carbon marine fuel oil and a preparation method. Summary of the invention

[0006] In view of the current problem that fuel oil needs to be low-carbon and reduce emissions, the purpose of the present invention is to provide a low-carbon marine fuel oil and a production method. The low-carbon marine fuel oil of the present invention can achieve the characteristics of stable storage, anti-oxidation and anti-coking of fuel oil under the premise of reducing carbon emissions, and provide a new way to blend and produce new environmentally friendly low-sulfur marine fuel oil.

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

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

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

[0010] In the present invention, the viscosity of the residual oil is in the range of 100-1000 mm / s 2 (50℃), density range is 960~990kg / m 3 (20℃).

[0011] In the present invention, the viscosity of the catalytic diesel is in the range of 1 to 10 mm / s 2 (50℃), density range is 940~980kg / m 3 (20℃).

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

[0013] In the present invention, the stabilizer is a diethanolamide nonionic surfactant, including one or more of lauroyl diethanolamide, oleic acid diethanolamide, stearic acid diethanolamide, and coconut oil fatty acid diethanolamide, preferably coconut oil fatty acid diethanolamide.

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

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

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

[0017] The viscosity of the low-carbon marine fuel oil of the present invention does not exceed 180 mm / s 2 (50℃), density not exceeding 985kg / m 3 (20℃), sulfur content does not exceed 0.5%, and there is no stratification after storage for 30 days.

[0018] The present invention also provides a method for preparing low-carbon marine fuel oil, comprising the following contents: (1) The residual oil is heated to a temperature T1, a stabilizer is added and stirred evenly to obtain a mixed oil A; (2) Mixing methanol and the co-solvent evenly, and then adding the activator and mixing evenly to obtain a mixed solution B; (3) emulsifying the mixed liquid B, catalytic diesel and emulsifier together through an emulsification pump to obtain a mixed liquid C; (4) The mixed solution C is continuously stirred at temperature T2 using a homogenizing high-speed shearing machine, assisted by high-power ultrasonic waves, and solution A is added at a certain speed v to mix the two evenly. The stirring and ultrasonic waves are continued for 1.5-3 hours to obtain the product.

[0019] According to the method of the present invention, T1 is 60-100°C; T2 is 40-60°C.

[0020] According to the method of the present invention, the power of high-power ultrasonic waves applied per liter of mixed liquid is not less than 20 kW and the frequency is not less than 400 kHz.

[0021] According to the method of the present invention, the rate v of adding solution A per kilogram of mixed solution C is 0.6 L / h~2.5 L / h.

[0022] In the present invention, the stabilizer bonds with hydrogen atoms through lone pairs of electrons, increasing the number of intermolecular and intramolecular hydrogen bonds in the system to maintain the stability of the system. The chain initiation reaction and chain growth reaction are prevented or inhibited by capturing peroxy radicals, thereby terminating the free radical chain reaction and achieving the purpose of preventing oxidation. At the same time, it also plays a role in diluting the residual oil to improve the mixing degree with the light components.

[0023] In the present invention, the co-solvent is an amphiphilic substance, whose molecules have both a hydrophilic group -OH that reacts with the hydroxyl group of methanol to form intermolecular complexes and associates, and a long carbon chain that reacts with the hydrocarbon molecules in the oil to adsorb and entangle, so that methanol can be better dissolved in the oil system.

[0024] In the present invention, the activator forms intermolecular hydrogen bonds with methanol / cosolvent through electrons provided by oxygen atoms to increase the mass of molecular groups. The extended carbon chain makes the modified methanol component have similar properties to hydrocarbons in diesel, which can help increase the compatibility of the system.

[0025] In the present invention, the emulsifier has a good emulsifying effect on macromolecular micelles such as asphaltene in the 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.

[0026] In the present invention, the configuration method of low-carbon marine fuel oil adopts a two-step method. In the first step, the residual oil and methanol are treated separately. The stabilizer is dispersed in the residual oil; the methanol is modified and activated to improve its compatibility with the oil product so that the two have good miscibility. In the second step, the modified methanol after activation is homogenized and emulsified with the catalytic diesel under the action of an emulsifier, and then the residual oil is gradually dispersed in the mixed liquid. The high-power ultrasonic wave has a strong cavitation effect, and can make the macromolecular substances in the mixed liquid, such as asphalt colloids, highly dispersed at a relatively low temperature, improve the emulsification effect, and achieve the effect of uniform mixing.

[0027] Methanol is modified and activated by using cosolvents and activators, and then the activated modified methanol is adsorbed near the hydrocarbon molecules of catalytic diesel by using the high content of colloid in catalytic diesel, so that catalytic diesel and methanol form an oil-in-water emulsion state, which is conducive to further mixing with residual oil. The residual oil is reduced in viscosity and emulsified by using stabilizers and emulsifiers to increase the hydrogen bonding effect between it and methanol / catalytic diesel, improve the stability of methanol added to the residual oil system, and form a stable low-carbon marine fuel oil system.

[0028] Compared with the prior art, the method for preparing low-carbon marine fuel oil provided by the present invention has the following advantages: 1. Through a variety of solvent compounding technologies and configuration processes, methanol is mixed with high-carbon fuel oil to form stable low-carbon marine fuel oil, reducing its carbon-hydrogen ratio, with a viscosity not exceeding 180 mm / s 2 (50℃), density not exceeding 985kg / m 3 (20℃), the sulfur content does not exceed 0.5%, and there is no stratification during storage for 30 days, effectively achieving the goal of low-carbon emission reduction of marine fuel oil.

[0029] 2. The process route of the present invention is simple in technology. The application of high-power ultrasound makes the fuel oil emulsified at a lower temperature, achieving a uniform mixing effect, reducing process energy consumption, and being easy to operate. Implementation

[0030] The scheme and effects of the present invention are further illustrated by the following examples, but they do not constitute a limitation of the present invention.

[0031] The blended residual oil and catalytic diesel used in this example were obtained from different refineries, and their main physical and chemical properties are shown in Table 1.

[0032] Table 1 Physical and chemical properties of crude oil from different refineries project Residue 1 Catalytic Diesel 1 Residue 2 Catalytic Diesel 2 <![CDATA[Viscosity, mm / s 2 (at 50 °C)]]> 163.9 1.759 921.2 2.336 <![CDATA[Density, kg / m 3 (at 20 °C)]]> 988.4 926.3 987.8 973.2 Sulfur content, % 0.42 0.25 0.45 0.30 Example 1

[0033] After heating 600g of residual oil 1 to 85°C, 15g of stabilizer coconut oil diethanolamide was added and stirred until uniform to obtain mixed solution 1. After 200g of methanol and 20g of 1-octanol were mixed evenly, 80g of methyl linolenate was added, and after mixing evenly, 80g of catalytic diesel 1 and 5g of Tween-60 were emulsified by an emulsifier pump to obtain mixed solution 2. Mixed solution 2 was continuously stirred at 50°C using a homogenizing high-speed shearing machine, and continuously ultrasonicated with a high-power ultrasonic wave with an auxiliary power of 30kW and a frequency of 500kHz. At the same time, mixed solution 1 was added at a rate of 1L / h, and the ultrasonic wave was continuously stirred for 2 hours to obtain product S1. The stability test method is to place it at room temperature and observe whether it is stratified. Example 2

[0034] After heating 450g of residual oil 2 to 95°C, 10g of stabilizer stearic acid diethanolamide was added and stirred until uniform to obtain mixed solution 1. After 350g of methanol and 25g of 1-decyl alcohol were mixed uniformly, 87g of ethyl laurate was added, and after mixing uniformly, 70g of catalytic diesel 2 and 8g of Span-60 were emulsified by an emulsifier pump to obtain mixed solution 2. Mixed solution 2 was continuously stirred at 55°C using a homogenizing high-speed shearing machine, and high-power ultrasonic waves with an auxiliary power of 25kW and a frequency of 450kHz were continuously ultrasonicated. At the same time, mixed solution 1 was added at a rate of 0.8L / h, and stirring and ultrasonication were continued for 2 hours to obtain product S2. Example 3

[0035] After heating 650g of residual oil 1 to 75°C, 7g of stabilizer lauroyl diethanolamine was added and stirred until uniform to obtain mixed solution 1. After 100g of methanol and 27g of n-hexanol were mixed uniformly, 68g of methyl palmitate was added, and after mixing uniformly, 140g of catalytic diesel 2 and 8g of AEO-9 were emulsified by an emulsifier pump to obtain mixed solution 2. Mixed solution 2 was continuously stirred at 45°C using a homogenizing high-speed shearing machine, and high-power ultrasonic waves with an auxiliary power of 35kW and a frequency of 450kHz were continuously ultrasonicated. At the same time, mixed solution 1 was added at a rate of 1.5L / h, and stirring and ultrasonication were continued for 2 hours to obtain product S3. Example 4

[0036] After heating 500g of residual oil 2 to 70°C, 22g of stabilizer oleic acid diethanolamide was added and stirred until uniform to obtain mixed solution 1. After 290g of methanol and 15g of 1-undecanol were mixed uniformly, 57g of methyl stearate was added, and after mixing uniformly, 110g of catalytic diesel 2 and 8g of OP-10 were emulsified by an emulsifier pump to obtain mixed solution 2. Mixed solution 2 was continuously stirred at 50°C using a homogenizing high-speed shearing machine, and continuously ultrasonicated with a high-power ultrasonic wave with an auxiliary power of 30kW and a frequency of 500kHz. At the same time, mixed solution 1 was added at a rate of 2L / h, and stirring and ultrasonication were continued for 2 hours to obtain product S4.

[0037] Comparative Example 1 The product D1 was obtained in the same manner as in Example 1, but without adding the stabilizer coconut oil diethanolamide.

[0038] Comparative Example 2 The product D2 was obtained in the same manner as in Example 1, but without adding the co-solvent 1-octanol.

[0039] Comparative Example 3 The product D3 was obtained in the same manner as in Example 1, but without adding the activator methyl linolenate.

[0040] Comparative Example 4 Product D4 was obtained in the same manner as in Example 1 except that the emulsifier Tween-60 was not added during the preparation process.

[0041] Comparative Example 5 Compared with Example 1, the formula is the same, but the preparation process is changed to add residual oil 1, catalytic diesel 1, methanol, stabilizer coconut oil diethanolamide, co-solvent 1-octanol, activator methyl linolenate, emulsifier Tween-60 at the same time at 50°C, and use a homogenizing high-speed shearing machine to continuously shear and mix for 2 hours to obtain product D5.

[0042] The physicochemical properties and stability test results of the above examples and comparative examples are shown in Table 2.

[0043] Table 2 Physicochemical properties and stability of samples of examples and comparative examples project S1 S2 S3 S4 D1 D2 D3 D4 D5 <![CDATA[Viscosity, mm / s 2 (at 50 °C)]]> 98 115 101 104 95 93 95 92 100 <![CDATA[Density, kg / m 3 (at 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 Stabilization time, d >30 >30 >30 >30 3 6 7 4 16

Claims

1. A low-carbon marine fuel oil, characterized in that: The invention comprises, by weight percentage, 40-70% of residual oil, 5-15% of catalytic diesel, 5-40% of methanol, 0.5-2.5% of stabilizer, 1-3% of cosolvent, 5-10% of activator, and 0.1-1% of emulsifier, and the sum of the mass fractions of each component is 100%; wherein the stabilizer is alkanolamide.

2. The low-carbon marine fuel oil according to claim 1, characterized in that: The viscosity of the residual oil ranges from 100 to 1000 mm / s 2 (50℃), density range is 960~990kg / m 3 (20℃).

3. The low-carbon marine fuel oil according to claim 1, characterized in that: The viscosity of the catalytic diesel is 1-10 mm / s 2 (50℃), density range is 940~980kg / m 3 (20℃).

4. The low-carbon marine fuel oil according to claim 1, characterized in that: The purity of the methanol is not less than 95%.

5. The low-carbon marine fuel oil according to claim 1, characterized in that: The co-solvent is an alcohol having 5 to 12 carbon atoms.

6. The low-carbon marine fuel oil according to claim 1, characterized in that: The activator is one or more of fatty acid methyl ester and fatty acid ethyl ester; wherein the carbon chain of the fatty acid is between 12 and 22.

7. The low-carbon marine fuel oil according to claim 1, characterized in that: The emulsifier is selected from polyoxyethylenes or polyols.

8. The low-carbon marine fuel oil 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 985kg / m 3 (20℃), sulfur content does not exceed 0.5%, and there is no stratification after storage for 30 days.

9. The method for preparing the low-carbon marine fuel oil according to any one of claims 1 to 8, comprising the following contents: (1) The residual oil is heated to a temperature T1, a stabilizer is added and stirred evenly to obtain a mixed oil A; (2) Mixing methanol and the co-solvent evenly, and then adding the activator and mixing evenly to obtain a mixed solution B; (3) emulsifying the mixed liquid B, catalytic diesel and emulsifier together through an emulsification pump to obtain a mixed liquid C; (4) The mixed solution C is continuously stirred at temperature T2 using a homogenizing high-speed shearing machine, assisted by high-power ultrasonic waves, and solution A is added at a certain speed v to mix the two evenly. The product is obtained by continuous stirring and ultrasonication.

10. The preparation method according to claim 9, characterized in that: T1 is 60-100℃, T2 is 40-60℃.

11. The preparation method according to claim 9, characterized in that: The rate of adding solution A per kilogram of mixed solution C is 0.6 ~2.5 L / h.

12. The preparation method according to claim 9, characterized in that: The power of the high-power ultrasonic wave is not less than 20 kW per liter of mixed liquid, and the frequency is not less than 400 kHz.