Method for reducing sludge blockage of ship oil separator by marine biological fuel oil

Abstract

The invention relates to a method for reducing sludge blockage of a ship oil separator by marine biological fuel oil, which comprises the following steps: preparing a bacteriostatic agent into a bacteriostatic agent aqueous dispersion, coating the bacteriostatic agent aqueous dispersion in a storage container of the marine biological fuel oil, and directly storing the marine biological fuel oil after the inner wall of the storage container is dried. Compared with the prior art, the bacteriostatic agent is coated on the inner walls of the ship oil tank and the oil tank for storing the marine biological fuel oil, and is used for storing the marine biological fuel oil after being dried, and the bacteriostatic effect of the bacteriostatic agent on bacteria in the biological fuel oil is utilized; according to the marine biological fuel oil, an environment which is not beneficial to the survival of a mixture of bacteria, algae and molds is formed in the oil tank and the oil tank of the ship, the storage function of the oil tank and the oil tank of the ship is improved, the marine biological fuel oil is endowed with an antibacterial function, the shelf life of the marine biological fuel oil is effectively prolonged, the combustion quality of the biological fuel oil is improved, and the possibility of sludge blockage of an oil separator is reduced.

Description

Technical Field

[0001] The invention belongs to the technical field of biofuel oil and relates to a method for reducing the clogging of a ship oil separator by sludge caused by marine biofuel oil. Background Art

[0002] Marine biofuel refers to a marine alternative fuel made by mixing marine fuel oil and biodiesel in a certain proportion. Compared with standard land applications, the application of biofuel oil mixtures in marine ship environments is more likely to form sludge. The formation of insoluble substances under marine conditions may be through a new mechanism. The physical and chemical indicators of marine fuel oil are of great significance to the safe use of marine oil products. Internationally, ISO 8217 has clear regulations on the performance indicators of marine fuel oil. However, there is currently a lack of relevant quality standards and patents for marine biofuel oil, which affects the safe use of marine biofuel oil. A study by the Washington State Ferry Company in the United States conducted a four-month ship test. The test results confirmed that the use of B20 biodiesel blended fuel in the test resulted in excessive sludge, which caused filter clogging, and a large amount of sludge was also found in the ship's oil separator. During the period when ships use marine biofuel oil, the composition of marine biofuel oil is complex. Depending on the different raw materials contained in the preparation of biofuel oil, the composition of biofuel oil will also vary greatly, resulting in a possible decrease in its safety for the fuel system. In particular, long-term exposure to air and high humidity will seriously affect the quality of biofuel oil. Since marine biofuel oil is more easily oxidized than traditional petroleum diesel, the instability after long-term storage may cause precipitation and changes in physical and chemical properties in the biofuel oil. The products formed will also lead to serious usage problems such as the formation of deposits, increased corrosion and blockage of the engine fuel injection system.

[0003] The preliminary study of the present invention has found through the results of engine bench tests and literature research that although diesel marine biofuel oil prepared by blending fatty acid methyl esters based on waste edible oils, the problem that diesel marine biofuel oil may breed bacteria still needs special attention. Especially after the marine biofuel oil is damp, the mixture of bacteria, algae and mold will multiply in large numbers after contaminating the storage tank. Since bacteria can feed on fuel, they will produce a sticky, film-like surface layer in the fuel system. The excrement grown from the bacteria can block the oil separator and filter, resulting in insufficient fuel supply, and even wear the injector and cause engine failure. Summary of the invention

[0004] The purpose of the present invention is to provide a method for reducing the sludge blockage of ship oil separators caused by ship biofuel oil, using antibacterial agents to improve the performance of ship biofuel oil and avoid the deterioration of oil quality after being damp, adding antibacterial agents to ship oil tanks and oil cabinets storing biofuel oil, and directly using them to inhibit the storage of biofuel oil after the inner wall is dried, so as to solve the problem that bacteria are easily bred and oil separators and filters are blocked after the oil quality deteriorates.

[0005] The purpose of the present invention can be achieved by the following technical solutions:

[0006] The first aspect of the present invention provides a method for reducing the clogging of ship oil separator sludge caused by ship biofuel oil. The method comprises preparing an antibacterial agent into an antibacterial agent aqueous dispersion and coating the dispersion on the inner wall of a storage container for the ship biofuel oil. The inner wall of the storage container is dried and then directly used for storing the ship biofuel oil.

[0007] Furthermore, the marine biofuel oil storage container is a metal container.

[0008] Furthermore, the metal container is a ship's oil tank or oil cabinet.

[0009] Further, the amount of the antibacterial agent is 1-5wt% of the mass of the biofuel oil; the concentration of the antibacterial agent aqueous dispersion is 0.01-0.03wt%. Preferably, the amount of the antibacterial agent is 1-2.5wt% of the mass of the biofuel oil; the concentration of the antibacterial agent aqueous dispersion is 0.02wt%.

[0010] Furthermore, the antibacterial agent is selected from at least one of a natural antibacterial agent or an artificially synthesized antibacterial agent.

[0011] Furthermore, the natural antibacterial agent is selected from at least one of chitosan, tea tree oil, garlic extract, clove oil, citric acid, Pseudomonas aeruginosa or olive oil.

[0012] Furthermore, the synthetic antibacterial agent is selected from at least one of triclosan, triclocarban, phenoxyethanol, parabens, isothiazolinone, peroxybenzoic acid or methylparaben.

[0013] Furthermore, the marine biofuel oil is B24 marine biofuel oil.

[0014] Furthermore, the B24 marine biofuel oil includes 24 wt% of biodiesel 100 and 76 wt% of high sulfur fuel oil.

[0015] Furthermore, the antibacterial agent is a chitosan-based antibacterial agent, and the preparation method of the chitosan-based antibacterial agent comprises the following steps:

[0016] 1) dissolving tetramethylpiperidinyloxyl radical / laccase chitosan (TLCS) or chitosanase-tetramethylpiperidinyloxyl radical / laccase chitosan (CTLCS) in acetic acid solution, adding lysozyme and stirring to carry out cross-linking reaction;

[0017] 2) adding alkaline substances to adjust the pH to 7, adding ethanol and centrifuging to obtain a chitosan-based antibacterial agent.

[0018] Furthermore, in step 1), the feed ratio of tetramethylpiperidinyloxyl radical / laccase chitosan or chitosanase-tetramethylpiperidinyloxyl radical / laccase chitosan, acetic acid solution and lysozyme is (400-700) mg: (75-85) mL: (46-55) mg; the concentration of the acetic acid solution is 0.08-0.15 M. Preferably, the concentration of the acetic acid solution is 0.1 M.

[0019] Furthermore, in step 1), in the cross-linking reaction, the reaction temperature is 4-6°C, and the reaction time is 45-50 hours. Preferably, in the cross-linking reaction, the reaction temperature is 5°C, and the reaction time is 48 hours.

[0020] Further, in step 2), the alkaline substance is any one of sodium hydroxide, potassium hydroxide or calcium hydroxide; and the drying temperature is 50-60° C. Preferably, the drying temperature is 50° C.

[0021] The present invention applies an aqueous dispersion of an antibacterial agent to the inner wall of a ship's oil tank and an oil tank storing marine biofuel oil, and uses the dispersion for storing marine biofuel oil after drying. The antibacterial agent has an antibacterial effect on bacteria in biofuel oil, so that an environment unfavorable for the survival of a mixture of bacteria, algae and mold is formed inside the ship's oil tank and the oil tank, thereby improving the storage function of the ship's oil tank and the oil tank, and giving them an antibacterial function, thereby effectively extending the shelf life of the marine biofuel oil, improving the combustion quality of the biofuel oil, and reducing the possibility of sludge blockage in the oil separator.

[0022] Compared with the prior art, the present invention has the following characteristics:

[0023] 1) The present invention prepares the antibacterial agent into an antibacterial agent aqueous dispersion and applies it to a storage container for marine biofuel oil. The inner wall of the storage container is dried and directly used to store the marine biofuel oil. The antibacterial agent has an antibacterial effect on bacteria in the marine biofuel oil, so that an environment that is not conducive to the survival of a mixture of bacteria, algae and mold is formed inside the ship's oil tank and oil tank, which not only improves the storage function of the ship's oil tank and oil tank, but also gives them an antibacterial function, effectively prolongs the shelf life of the marine biofuel oil, improves the combustion quality of the biofuel oil, and reduces the possibility of sludge blockage in the oil separator;

[0024] 2) The present invention also prepared a new chitosan-based antibacterial agent based on the existing TLCS and CTLCS, and used it to store marine biofuel oil. After 30 days, it was found that the prepared new chitosan-based antibacterial agent had less sludge than the single TLCS or CTLCS, indicating that the new chitosan-based antibacterial agent prepared by the present invention is more beneficial to reducing the possible risk of sludge blockage of ship oil separators caused by marine biofuel oil. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 It is a schematic diagram of the sludge in Comparative Example 4;

[0026] Figure 2 It is a schematic diagram of the sludge in Example 2;

[0027] Figure 3 This is a schematic diagram of the sludge in Example 3. DETAILED DESCRIPTION

[0028] The present invention is described in detail below in conjunction with the accompanying drawings and specific embodiments. This embodiment is implemented based on the technical solution of the present invention, and provides a detailed implementation method and specific operation process, but the protection scope of the present invention is not limited to the following embodiments.

[0029] The following are more detailed implementation cases, which further illustrate the technical solutions of the present invention and the technical effects that can be obtained.

[0030] In the following examples, unless otherwise specified, raw materials, reagents or processing techniques are all conventional commercial products or conventional processing techniques in the art.

[0031] In the following examples, the marine biofuel oil is B24 marine biofuel oil (24wt% biodiesel 100+76wt% high sulfur fuel oil) from Shanghai Zhongran Marine Fuel Co., Ltd.; the preparation methods of TLCS and CTLCS can be referred to the literature (Zhu Li. Research on the preparation, properties and application of chitosan-based antibacterial agents in the antibacterial preservation of strawberries and fresh Tremella [D]. Jilin University, 2019.).

[0032] Embodiment 1:

[0033] The antibacterial agent A is prepared into an antibacterial agent A aqueous dispersion (0.02wt%), and 2.5wt% of the antibacterial agent A relative to the mass of the marine biofuel oil is applied to the inner wall of the oil tank in the form of the antibacterial agent A aqueous dispersion. After the inner wall of the oil tank is dried, it is directly used to store the marine biofuel oil to reduce the possible risk of sludge blockage of the ship's oil separator by the marine biofuel oil. The specific preparation steps of the antibacterial agent A are as follows:

[0034] Take 0.5g TLCS and dissolve it in 80ml (0.1M) acetic acid solution and stir. After it is completely dissolved, add 50mg lysozyme, stir at room temperature for 30 minutes, and then place the solution at 5°C for cross-linking for 48 hours. After the reaction is completed, adjust the pH to 7 with sodium hydroxide solution, add an appropriate amount of anhydrous ethanol to fully precipitate chitosan, centrifuge and wash several times (pay attention to the treatment of the recovered washing liquid and mark it with a fixed volume, do not throw it away at will to prevent environmental pollution), and the obtained solid is rotary evaporated to dryness at 50°C to prepare antibacterial agent A.

[0035] The Oxford cup method was used to determine the antibacterial effect of antibacterial agent A on Staphylococcus aureus (ATCC29213) and Escherichia coli (ATCC25922). The diameters of the inhibition zones of antibacterial agent A on the two bacterial groups were 13.89 mm and 13.13 mm, respectively, that is, the diameters of the inhibition zones of antibacterial agent A on the two bacterial groups were greater than 10 mm. As shown in Table 1, the antibacterial activity of antibacterial agent A on Staphylococcus aureus and Escherichia coli was moderately sensitive, and it could play an important role in the antibacterial effect of biofuel.

[0036] Table 1 Empirical evaluation table of antibacterial zone diameter and antibacterial effect

[0037]

[0038]

[0039] The results are as follows;

[0040] Antibacterial agent A was added to the inner wall of the ship's oil tank and dried for storage of marine biofuel oil. After 30 days, the amount of sludge was measured to be 0.21 kg, which greatly reduced the blockage of the ship's oil separator caused by sludge.

[0041] Embodiment 2:

[0042] The difference between Example 2 and Example 1 is that the antibacterial agent A is replaced by the antibacterial agent B, and the remaining steps are the same as those of Example 1. The specific preparation steps of the antibacterial agent B are as follows:

[0043] Take 0.5g CTLCS and dissolve it in 80ml (0.1M) acetic acid solution and stir. After it is completely dissolved, add 50mg lysozyme, stir at room temperature for 30 minutes, and then place the solution at 5°C for cross-linking for 48 hours. After the reaction is completed, adjust the pH to 7 with sodium hydroxide solution, add an appropriate amount of anhydrous ethanol to fully precipitate chitosan, centrifuge the precipitate and wash it several times (pay attention to handle the recovered washing liquid and mark it with constant volume, do not throw it away at will to prevent environmental pollution), and the obtained solid is rotary evaporated to dryness at 50°C to prepare antibacterial agent B.

[0044] The Oxford cup method was used to determine the antibacterial effect of antibacterial agent B on Staphylococcus aureus (ATCC29213) and Escherichia coli (ATCC25922). The diameters of the inhibition zones of antibacterial agent B on the two bacterial groups were 13.21 mm and 12.63 mm, respectively, that is, the diameters of the inhibition zones of antibacterial agent B on the two bacterial groups were greater than 10 mm. As shown in Table 1, the antibacterial activity of antibacterial agent B on Staphylococcus aureus and Escherichia coli was moderately sensitive, and it could play an important role in the antibacterial effect of biofuel.

[0045] The results are as follows:

[0046] Antibacterial agent B was added to the inner wall of the ship's oil tank and dried for use in storing marine biofuel oil. After 30 days, the sludge content was measured to be 0.25 kg, which greatly reduced the blockage of the ship's oil separator caused by sludge.

[0047] Embodiment 3:

[0048] The difference between this embodiment and embodiment 1 is that the antibacterial agent A is replaced by antibacterial agent A + antibacterial agent B, wherein the amount of antibacterial agent A is 1.25wt% of the marine biofuel oil, the amount of antibacterial agent B is 1.25wt% of the marine biofuel oil, and the remaining steps are the same as in embodiment 1.

[0049] The results are as follows:

[0050] Antibacterial agent A + antibacterial agent B were added to the inner wall of the ship's oil tank and oil tank and dried for storage of marine biofuel oil. After 30 days, the sludge amount was measured to be 0.15 kg. It can be seen that the sludge amount in this embodiment is less than that in Example 1 and Example 2, indicating that antibacterial agent A + antibacterial agent B have a synergistic effect and have better antibacterial effect than antibacterial agent A or antibacterial agent B alone.

[0051] Embodiment 4:

[0052] The difference between this embodiment and embodiment 1 is that the antibacterial agent A is replaced with chitosan, and the remaining steps are the same as those in embodiment 1.

[0053] The results are as follows:

[0054] Chitosan was added to the inner wall of the ship's oil tank and dried for use in storing marine biofuel oil. After 30 days, the amount of sludge was measured to be 0.62 kg, which greatly reduced the blockage of the ship's oil separator caused by sludge.

[0055] Embodiment 5:

[0056] The difference between this embodiment and embodiment 1 is that the antibacterial agent A is replaced with triclocarban, and the remaining steps are the same as those in embodiment 1.

[0057] The results are as follows:

[0058] Triclocarban was added to the inner wall of the ship's oil tank and dried for use in storing marine biofuel oil. After 30 days, the amount of sludge was measured to be 0.60 kg, which greatly reduced the blockage of the ship's oil separator caused by sludge.

[0059] Comparative Example 1:

[0060] The difference between this comparative example and Example 1 is that the antibacterial agent A is replaced by TLCS, and the other steps are the same as those in Example 1.

[0061] The results are as follows:

[0062] TLCS was added to the inner wall of the ship's oil tank and dried for storage of marine biofuel oil. After 30 days, the sludge amount was measured to be 0.52 kg. Compared with Example 1, the sludge amount of this comparative example was more than that of Example 1, indicating that the antibacterial agent A has a better antibacterial effect than TLCS.

[0063] Comparative Example 2:

[0064] The difference between this comparative example and Example 2 is that the antibacterial agent B is replaced by CTLCS, and the other steps are the same as those in Example 2.

[0065] The results are as follows:

[0066] CTLCS was added to the inner wall of the ship's oil tank and dried for storage of marine biofuel oil. After 30 days, the sludge amount was measured to be 0.55 kg. Compared with Example 2, the sludge amount of this comparative example was more than that of Example 2, indicating that the antibacterial agent B has a better antibacterial effect than CTLCS.

[0067] Comparative Example 3:

[0068] The antibacterial agent A (in an amount of 2.5 wt% of the marine biofuel oil) is directly added to the marine biofuel oil to reduce the possible risk of sludge blockage of the ship's oil separator by the marine biofuel oil.

[0069] The results are as follows:

[0070] The antibacterial agent A was directly added to the marine biofuel oil. After 30 days, the sludge amount was measured to be 0.45 kg. Compared with Example 1, the sludge amount in this comparative example was greater than that in Example 1, indicating that the antibacterial agent added to the inner wall of the ship's oil tank after drying has a better antibacterial effect than directly adding it to the oil, indicating that coating the aqueous dispersion of the antibacterial agent A on the inner wall and then drying it can more directly prevent the growth of bacteria on the inner wall of the oil tank, and directly adding it to the marine biofuel oil will reduce the antibacterial effect to a certain extent.

[0071] Comparative Example 4:

[0072] Without adding any antibacterial agent, the inner wall of the ship's oil tank and oil tank was dried and used to store biofuel oil. After 30 days, the sludge amount was measured to be 2.16kg, which is much higher than the sludge amount with the addition of antibacterial agent.

[0073] The above description of the embodiments is to facilitate the understanding and use of the invention by those skilled in the art. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the above embodiments, and improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the present invention should be within the scope of protection of the present invention.

Claims

1. A method for reducing the clogging of ship oil separators by marine biofuel oil, characterized in that: The method comprises the following steps: preparing an antibacterial agent into an antibacterial agent aqueous dispersion and coating the dispersion on the inner wall of a storage container for marine biofuel oil; the inner wall of the storage container is directly used for storing the marine biofuel oil after being dried.

2. The method for reducing the sludge blockage of ship oil separators caused by marine biofuel oil according to claim 1, characterized in that: The dosage of the antibacterial agent is 1-5wt% of the mass of the biofuel oil; the concentration of the antibacterial agent aqueous dispersion is 0.01-0.03wt%.

3. The method for reducing the clogging of ship oil separators by marine biofuel oil according to claim 1, characterized in that: The antibacterial agent is selected from at least one of a natural antibacterial agent or an artificially synthesized antibacterial agent.

4. The method for reducing the clogging of ship oil separators by marine biofuel oil according to claim 3, characterized in that: The natural antibacterial agent is selected from at least one of chitosan, tea tree oil, garlic extract, clove oil, citric acid, Pseudomonas aeruginosa or olive oil.

5. The method for reducing the clogging of ship oil separators by marine biofuel oil according to claim 3, characterized in that: The synthetic antibacterial agent is selected from at least one of triclosan, triclocarban, phenoxyethanol, parabens, isothiazolinone, peroxybenzoic acid or methylparaben.

6. The method for reducing the clogging of ship oil separators by marine biofuel oil according to claim 1, characterized in that: The marine biofuel oil is B24 marine biofuel oil.

7. The method for reducing the clogging of ship oil separators by marine biofuel oil according to claim 1, characterized in that: The antibacterial agent is a chitosan-based antibacterial agent, and the preparation method of the chitosan-based antibacterial agent comprises the following steps: 1) dissolving tetramethylpiperidinyloxy free radical / laccase chitosan or chitosanase-tetramethylpiperidinyloxy free radical / laccase chitosan in acetic acid solution, adding lysozyme and stirring to carry out cross-linking reaction; 2) adding alkaline substances to adjust the pH to 7, adding ethanol and centrifuging to obtain a chitosan-based antibacterial agent.

8. The method for reducing the clogging of ship oil separators by marine biofuel oil according to claim 7, characterized in that: In step 1), the feed ratio of tetramethylpiperidinyloxyl free radical / laccase chitosan or chitosanase-tetramethylpiperidinyloxyl free radical / laccase chitosan, acetic acid solution and lysozyme is (400-700) mg: (75-85) mL: (46-55) mg; the concentration of the acetic acid solution is 0.08-0.15M.

9. The method for reducing the clogging of ship oil separators by marine biofuel oil according to claim 7, characterized in that: In step 1), in the cross-linking reaction, the reaction temperature is 4-6° C. and the reaction time is 45-50 h.

10. The method for reducing the clogging of ship oil separators by marine biofuel oil according to claim 7, characterized in that: In step 2), the alkaline substance is any one of sodium hydroxide, potassium hydroxide or calcium hydroxide; and the drying temperature is 50-60°C.

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