Marine high-efficiency composite heavy oil additive and preparation method thereof

Abstract

The invention discloses a marine high-efficiency composite heavy oil additive and a preparation method thereof. The heavy oil additive is prepared from the following components in parts by weight: 5-12 parts of ferric acetylacetonate, 8-18 parts of modified polyether amine, 8-15 parts of sodium lignin sulfonate, 6-10 parts of sophorolipid, 3-8 parts of sodium dodecyl benzene sulfonate, 5-10 parts of polyglycerol ester, 5-12 parts of ethyl tert-butyl ether and 40-60 parts of D80 solvent oil. The low-metal-residue catalytic system and the biodegradable surfactant are creatively adopted, combustion catalysis and oil sludge inhibition and decomposition are synchronously achieved, and through the synergistic effect of organic-biological components, the combustion efficiency and stability of the marine heavy oil can be remarkably improved.

Description

Technical Field

[0001] This invention belongs to the field of heavy oil additive technology, and mainly relates to a high-efficiency composite heavy oil additive for marine use and its preparation method, which has the functions of improving combustion efficiency, inhibiting sludge formation and decomposing accumulated sludge. Background Technology

[0002] Marine heavy fuel oil contains high levels of sulfur, asphalt, and colloidal substances, which easily produce incomplete combustion products (such as soot and sulfur oxides) during combustion. Furthermore, sludge deposits form during storage and combustion, leading to fuel system blockage, equipment corrosion, and increased maintenance costs. Combustion performance is typically improved by adding heavy fuel oil additives such as combustion improvers and dispersants.

[0003] Traditional heavy oil additives often focus on a single function (such as combustion improvement or cleaning), which can only solve some problems and cannot comprehensively improve the combustion effect of heavy oil. For example, (1) traditional combustion improvers are mainly ferrocene or isooctanoic acid metal salts, but lack the effect of inhibiting sludge; (2) some dispersants (such as polyisobutylene bis(succinimide)) can disperse sludge, but their combustion improvement effect is limited; (3) sludge decomposition technology mostly relies on physical or chemical treatment processes and is not optimized in conjunction with the combustion process. In addition, some additives may also cause corrosion to the combustion system and pipelines, increasing the cost of use and maintenance difficulty.

[0004] Patent document CN118599584A discloses a high-efficiency and environmentally friendly heavy oil additive and its preparation and use method. The additive components are: 1-5 parts calcium petroleum sulfonate, 1-5 parts polyisobutylene glycol imine, 2-6 parts Span, 3-15 parts cerium isooctanoate, 5-20 parts magnesium naphthenate, 50-80 parts solubilizer, 5-20 parts ferrocene, and 0-15 parts stabilizer. However, this additive uses a large amount of metal salts as combustion aids, and its combustion products are CeO2 and MgO particles, which are non-biodegradable metal oxides. Long-term use will lead to excessive particulate matter in flue gas. In addition, ferrocene decomposes at high temperatures to generate iron oxide residues, and its synthesis process involves chlorinated hydrocarbon solvents, posing a risk of persistent organic pollutants (POPs). Polyisobutylene glycol imine has insufficient dispersion efficiency for asphaltenes micelles, and calcium petroleum sulfonate easily reacts with sulfides in fuel to form calcium sulfate precipitates, clogging fuel filters. Summary of the Invention

[0005] The purpose of this invention is to provide a high-efficiency composite heavy oil additive for marine use and its preparation method, so as to solve the technical problems of low combustion efficiency, serious sludge deposition and high pollutant emissions in the prior art.

[0006] To solve the above-mentioned technical problems, the present invention provides the following technical solution: This invention discloses a high-efficiency composite heavy oil additive for marine use, which is formulated from the following components in parts by weight: 5-12 parts of acetylacetone iron, 8-18 parts of modified polyetheramine, 8-15 parts of sulfonated sodium lignin, 6-10 parts of sophorolipid, 3-8 parts of sodium dodecylbenzenesulfonate, 5-10 parts of polyglycerol ester, 5-12 parts of ethyl tert-butyl ether, and 40-60 parts of D80 solvent oil; the total number of parts is 100. The modified polyetheramine is an alkyl-linked branched polyetheramine modified by alkylation of ethylene oxide and dodecylamine, with a molecular weight range of 800–1200 Da and an alkyl chain carbon number ≥ C. 12 As a dispersant and emulsifier, it improves the compatibility and stability of additives; the preparation method can refer to the method disclosed in literature CN116239765A; for example, Huntsman's JEFFAMINE diamine ED-900 modified polyamide; The sulfonated sodium lignin is a sulfonated lignin dispersant produced by desaccharification, separation, and sulfonation of lignin, sulfur dichloride aqueous solution, and sulfite as the main raw materials. It has a molecular weight of 10,000–15,000 Da and a degree of sulfonation of 0.8–1.8 mol / kg. For example, Mead Westvaco's lignin dispersants Reax 85A and Reax 910 are used as anionic surfactants. The sophorolipid is a mixed type of sophorolipid with a viscosity of 1000-2000 mPa.s and CAS: 148409-20-5. For example, Shandong Suihua Biotechnology's S1022 sophorolipid, as a biosurfactant and emulsifier, enhances the activity of the oil-water interface. The polyglycerol ester is a polyglycerol fatty acid ester formed by esterification of natural glycerol and fatty acids at high temperature, with a molecular weight of 500-2000 Da. For example, the polyglycerol fatty acid ester of Jiaxing Zhongcheng Environmental Protection Technology Co., Ltd. is used as an emulsifier and stabilizer to improve the dispersibility of additives in heavy oil.

[0007] Preferably, the mass ratio of sodium sulfonate to sophorolipid is (1.1-1.8):1, and the two can form an amphiphilic micelle structure.

[0008] Preferably, the addition temperature of the ethyl tert-butyl ether needs to be controlled at 40±2℃ to achieve a synergistic solubilizing effect with the hydrogen bond of polyglycerol ester.

[0009] The preparation method of a marine high-efficiency composite heavy oil additive of the present invention includes the following steps: (1) heating D80 solvent oil to 30-50°C, adding sulfonated sodium lignin and stirring until completely dissolved; (2) adding acetylacetone iron, modified polyetheramine, sophorolipid and sodium dodecylbenzenesulfonate in sequence, and stirring evenly at 40-60°C; (3) adding polyglycerol ester and ethyl tert-butyl ether, continuing to stir evenly, and filtering to obtain the finished product.

[0010] The stirring speed in step (2) is 800-1200 rpm and the stirring time is 60-120 min.

[0011] The present invention describes a method for applying a high-efficiency composite heavy oil additive for marine use: add 0.05% to 0.1% of the heavy oil mass to the fuel system, with a mixing temperature of 20 to 80°C, without the need for additional emulsification treatment.

[0012] The heavy oil is marine fuel oil of 180# to 380# with a sulfur content of ≥2.5%.

[0013] Compared with the prior art, the present invention has the following advantages: This invention innovatively employs a low-metal residue catalytic system and a biodegradable surfactant to simultaneously achieve combustion catalysis, sludge inhibition and decomposition. Through the compounding of dispersants and stabilizers, the long-term stability of the additive in heavy oil is ensured. The high-efficiency composite heavy oil additive for marine use can significantly improve the combustion efficiency and stability of marine heavy oil through the synergistic effect of organic and biological components. When the addition amount is 0.05% to 0.1% of the heavy oil mass, the fuel saving rate is 3% to 6%, and the carbon dioxide emissions are reduced by 4% to 7%, making it suitable for widespread application in the field of marine heavy oil. Detailed Implementation

[0014] The following examples illustrate the specific implementation process and effects of the present invention. Those skilled in the art should recognize that these examples are merely illustrative and not intended to limit the invention. Any modifications or variations to the examples within the scope of the present invention are within the scope of the claims.

[0015] Example 1 A high-efficiency composite heavy oil additive for marine use comprises the following parts by weight: 7 parts acetylacetone iron, 14 parts modified polyetheramine, 9 parts sulfonated sodium lignin, 7 parts sophorolipid, 5 parts sodium dodecylbenzenesulfonate, 6 parts polyglycerol ester, 7 parts ethyl tert-butyl ether, and 45 parts D80 solvent oil. The preparation method includes the following steps: (1) Heat D80 solvent oil to 40°C, add sulfonated sodium lignin, and stir at 800 rpm until completely dissolved; (2) Add acetylacetone iron, modified polyetheramine, sophorolipid and sodium dodecylbenzenesulfonate in sequence, heat to 50°C, and stir at 1000 rpm for 90 min; (3) Control the system temperature to 40℃, then add polyglycerol ester and ethyl tert-butyl ether, and continue stirring for 30 min; (4) After filtration, a transparent liquid is obtained and stored in a sealed container.

[0016] Example 2 A high-efficiency composite heavy oil additive for marine use comprises the following parts by weight: 8 parts acetylacetone iron, 14 parts modified polyetheramine, 11 parts sulfonated sodium lignin, 7 parts sophorolipid, 5 parts sodium dodecylbenzenesulfonate, 7 parts polyglycerol ester, 8 parts ethyl tert-butyl ether, and 40 parts D80 solvent oil. The preparation method includes the following steps: (1) Heat D80 solvent oil to 50°C, add sulfonated sodium lignin, and stir at 1200 rpm until completely dissolved; (2) Add acetylacetone iron, modified polyetheramine, sophorolipid and sodium dodecylbenzenesulfonate in sequence, heat to 60°C, and stir at 1000 rpm for 120 min; (3) Control the system temperature to 40℃, then add polyglycerol ester and ethyl tert-butyl ether, and continue stirring for 30 min; (4) After filtration, a transparent liquid is obtained and stored in a sealed container.

[0017] Example 3 A high-efficiency composite heavy oil additive for marine use comprises the following parts by weight: 5 parts acetylacetone iron, 10 parts modified polyetheramine, 8 parts sulfonated sodium lignin, 7 parts sophorolipid, 3 parts sodium dodecylbenzenesulfonate, 5 parts polyglycerol ester, 5 parts ethyl tert-butyl ether, and 57 parts D80 solvent oil. The preparation method includes the following steps: (1) Heat D80 solvent oil to 30°C, add sulfonated sodium lignin, and stir at 800 rpm until completely dissolved; (2) Add acetylacetone iron, modified polyetheramine, sophorolipid and sodium dodecylbenzenesulfonate in sequence, heat to 50°C, and stir at 1000 rpm for 60 min; (3) Control the system temperature to 40℃, then add polyglycerol ester and ethyl tert-butyl ether, and continue stirring for 30 min; (4) After filtration, a transparent liquid is obtained and stored in a sealed container.

[0018] Comparative Example 1 Comparative Example 1 is a comparative example of Example 3, and consists of the following parts by weight: 5 parts ferric acetylacetone, 10 parts modified polyetheramine, 8 parts sulfonated sodium lignin, 3 parts sodium dodecylbenzenesulfonate, 5 parts polyglycerol ester, 5 parts ethyl tert-butyl ether, and 64 parts D80 solvent oil. The preparation method is the same as in Example 3.

[0019] Comparative Example 2 Comparative Example 2 is a comparative example of Example 3, and consists of the following parts by weight: 5 parts ferric acetylacetone, 10 parts modified polyetheramine, 8 parts sulfonated sodium lignin, 7 parts sophorolipid, 3 parts sodium dodecylbenzenesulfonate, 5 parts ethyl tert-butyl ether, and 62 parts D80 solvent oil. The preparation method is the same as in Example 3.

[0020] Test Experiment Example The additives prepared in Examples 1-3 and Comparative Examples 1-2 were added to 180# heavy oil at mass fractions of 0.08%, 0.1%, and 0.05%, respectively. The experiment used a MAN B&W 6S35ME-B9 inline 6-cylinder low-speed diesel engine with a piston stroke of 1550 mm and a cylinder bore of 350 mm, classifying it as a large-bore, long-stroke low-speed diesel engine. Two different operating points were set for the engine speed: 108 r / min and 139 r / min, corresponding to 50% and 100% of the commonly used power of a marine low-speed diesel engine (3250 kW), respectively. After the engine load stabilized, data from various measuring devices were recorded within the same time period. The results are shown in Table 1.

[0021] Table 1. Test results of the blank group, Examples 1-3 and Comparative Examples 1-2 As can be seen from the results in Table 1, Examples 1 to 3 of the present invention all showed excellent performance at different addition ratios (0.05% to 0.10%), with fuel consumption rate reduced by 3% to 6% and carbon dioxide emissions reduced by 4% to 7% compared to the blank group. The stability test value (ASTM D7061) decreased from 9.3 in the blank group to 5.8 to 6.1, and the performance was less affected by fluctuations in the formulation ratio, demonstrating extremely strong applicability and stability.

[0022] The results of Comparative Examples 1 and 2 further demonstrate that the synergistic effect of the various organic-biological components in the formulation of this invention is the key to achieving performance breakthroughs. Comparative Example 1 lacks sophorolipids, resulting in insufficient biosurface activity and a decrease in the dispersion and emulsification effects of oil sludge; Comparative Example 2 lacks polyglycerol esters, leading to poor dispersion stability of the additive in heavy oil, resulting in a significant reduction in the oil-saving, emission-reduction, and oil-stabilizing effects of the additive, with performance only slightly better than the blank group, failing to meet practical requirements.

[0023] This invention significantly improves the combustion efficiency and stability of marine heavy oil by utilizing the synergistic effect of its components, effectively solving the problem of clean and efficient utilization of high-sulfur heavy oil, and providing an innovative and reliable solution for energy conservation and carbon reduction in the field of marine power.

Claims

1. A high-efficiency composite heavy oil additive for marine use, characterized in that, It is formulated from the following components in parts by weight: 5-12 parts acetylacetone iron, 8-18 parts modified polyetheramine, 8-15 parts sulfonated sodium lignin, 6-10 parts sophorolipid, 3-8 parts sodium dodecylbenzenesulfonate, 5-10 parts polyglycerol ester, 5-12 parts ethyl tert-butyl ether, and 40-60 parts D80 solvent oil; the total number of parts is 100.

2. The marine high-efficiency composite heavy oil additive according to claim 1, characterized in that, The modified polyetheramine is an alkyl-linked branched polyetheramine modified by alkylation of ethylene oxide and dodecylamine, with a molecular weight range of 800–1200 Da and an alkyl chain carbon number ≥ C. 12 .

3. The marine high-efficiency composite heavy oil additive according to claim 1, characterized in that, The sulfonated sodium lignin is a sulfonated lignin dispersant made from lignin, sulfur dichloride aqueous solution and sulfite as the main raw materials, through desaccharification, separation and sulfonation. It has a molecular weight of 10,000 to 15,000 Da and a degree of sulfonation of 0.8 to 1.8 mol / kg.

4. The marine high-efficiency composite heavy oil additive according to claim 1, characterized in that, The sophorolipid is a mixed sophorolipid with a viscosity of 1000–2000 mPa·s.

5. The high-efficiency composite heavy oil additive for marine use according to claim 1, characterized in that, The polyglycerol ester is a polyglycerol fatty acid ester formed by esterification of natural glycerol and fatty acids at high temperature, with a molecular weight of 500-2000 Da.

6. The marine high-efficiency composite heavy oil additive according to claim 1, characterized in that, The mass ratio of the sulfonated sodium lignin to sophorolipid is (1.1-1.8):

1.

7. The marine high-efficiency composite heavy oil additive according to claim 1, characterized in that, The addition temperature of the ethyl tert-butyl ether needs to be controlled at 40±2℃.

8. The preparation method of the high-efficiency composite heavy oil additive for marine use according to any one of claims 1 to 7, characterized in that, The process includes the following steps: (1) heating D80 solvent oil to 30-50°C, adding sulfonated sodium lignin and stirring until completely dissolved; (2) adding acetylacetone iron, modified polyetheramine, sophorolipid and sodium dodecylbenzenesulfonate in sequence, and stirring evenly at 40-60°C; (3) adding polyglycerol ester and ethyl tert-butyl ether, continuing to stir evenly, and filtering to obtain the finished product.

9. The preparation method of the high-efficiency composite heavy oil additive for marine use according to claim 8, characterized in that, The stirring speed in step (2) is 800-1200 rpm and the stirring time is 60-120 min.

10. The application method of the high-efficiency composite heavy oil additive for marine use according to any one of claims 1 to 7, characterized in that, Add 0.05% to 0.1% of the heavy oil mass to the fuel system, with a mixing temperature of 20 to 80°C.

Images