Oil dispersant for ships and preparation method thereof

Abstract

The invention discloses an oil dispersant for ships, and belongs to the technical field of oil for ships. The oil dispersant for the ship comprises the following components in parts by weight: 15-20 parts of a solvent, 10-20 parts of a composite surfactant solution, 10-15 parts of high-dispersion modified soil, 2-8 parts of vegetable oil, 1-5 parts of tert-butylhydroquinone, 1-2 parts of a yeast extract, 1-2 parts of a colloidal substance, 1-2 parts of sodium benzoate and 1-3 parts of a pH regulator, the composite surfactant solution is obtained by graft modification of a modified polymer, a chemical surfactant and a bio-based surfactant; the high-dispersion modified soil is obtained by modifying bentonite, montmorillonite and magnesium silicate clay. The prepared oil dispersant for the ship not only has efficient dispersion performance and good stability, but also improves the use efficiency and environmental protection performance of the oil for the ship.

Description

Technical Field

[0001] The invention belongs to the technical field of marine oil, and particularly relates to a marine oil dispersant and a preparation method thereof. Background Art

[0002] With the rapid development of the global shipping industry, the problem of marine environmental pollution is becoming increasingly serious, especially the oily wastewater that ships inevitably produce and discharge during navigation. These oily wastewaters include ship cabin sewage, ballast water, tank washing water, etc., which contain a large amount of petroleum pollutants. If these oily wastewaters are directly discharged into the ocean without effective treatment, they will cause serious pollution and damage to the marine ecological environment, threatening the survival of marine life and the sustainable use of marine resources. Therefore, how to effectively treat ship oily wastewater has become one of the key issues that need to be urgently solved in the shipping industry and environmental protection field.

[0003] In the process of treating ship oily wastewater, oil dispersants have become an important treatment method because they can effectively disperse oil into fine particles and suspend them in water, which is convenient for subsequent treatment or natural degradation. The main function of oil dispersants is to decompose oil into tiny particles and suspend them stably in water, thereby preventing the aggregation and redeposition of oil. Traditional oil dispersants mainly rely on the action of surfactants, which reduce the oil-water interfacial tension so that the oil is dispersed into tiny particles under mechanical stirring or natural flow conditions. There are many types of oil in ship oily wastewater, including fuel, lubricating oil, hydraulic oil, etc. Different types of oil have different physical and chemical properties. Traditional oil dispersants often show poor stability and unsustainable dispersion effect in extreme marine environments such as high temperature, high salt, strong acid and alkali, and it is difficult to meet the actual needs of ship oily wastewater treatment. Therefore, it is of great significance to develop an efficient, environmentally friendly and widely adaptable marine oil dispersant to solve the technical problems of low dispersion efficiency, poor stability, low efficiency of marine oil use and poor environmental performance of marine oil dispersants in the prior art. Summary of the invention

[0004] The object of the present invention is to provide a marine oil dispersant and a preparation method thereof, so as to solve the technical problems of low dispersion efficiency and poor stability of the marine oil dispersant in the prior art, low utilization efficiency of the marine oil and poor environmental performance.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] The invention provides a marine oil dispersant, which is composed of the following components in parts by weight: 15-20 parts of a solvent, 10-20 parts of a composite surfactant solution, 10-15 parts of highly dispersed modified soil, 2-8 parts of vegetable oil, 1-5 parts of tert-butylhydroquinone, 1-2 parts of yeast extract, 1-2 parts of a colloid, 1-2 parts of sodium benzoate and 1-3 parts of a pH regulator; the composite surfactant solution is obtained by grafting and modifying a modified polymer with a chemical surfactant and a bio-based surfactant; and the highly dispersed modified soil is obtained by modifying bentonite, montmorillonite and magnesium silicate clay.

[0007] Furthermore, the preparation method of the composite surfactant solution comprises the following steps:

[0008] S1. preparing a modified polymer solution: dissolving the modified polymer in deionized water, heating, and stirring until the modified polymer is completely dissolved to obtain a modified polymer solution;

[0009] S2. preparing a surfactant solution: dissolving a chemical surfactant and a bio-based surfactant in deionized water, heating, and stirring until completely dissolved to obtain a surfactant solution;

[0010] S3, mixing: mixing the modified polymer solution and the surfactant solution, stirring evenly to obtain a mixed solution of the modified polymer and the surfactant;

[0011] S4, grafting: weigh benzophenone and add it to the mixed solution of modified polymer and surfactant, and irradiate the mixed solution with ultraviolet light to obtain a composite surfactant solution.

[0012] Furthermore, the modified polymer in S1 is a mixture of polyvinyl alcohol and polyacrylic acid, the mass ratio of polyvinyl alcohol, polyacrylic acid and water is 1:1:(60-70), heated to 60-65°C, stirred at a speed of 60-120rpm, and stirred for 5-20min; the chemical surfactant in S2 is a mixture of SDS and Tween 80, SDS and Tween The mass ratio of chemical surfactant, bio-based surfactant and water is 2: (2.5-5.8): (60-80), heated to 50-60 ° C, stirred at 25-40 rpm, and stirred for 5-20 min; the concentration of benzophenone in S4 is 0.1-1.0 wt%, and the mixed solution is irradiated with ultraviolet light for 30-40 min.

[0013] Furthermore, the preparation method of highly dispersed modified soil comprises the following steps:

[0014] Q1. Weigh a modifier 1, dissolve it in deionized water, stir and heat to obtain a modifier solution 1, add bentonite to deionized water, stir evenly to obtain a bentonite suspension, mix the modifier solution with the bentonite suspension, treat with ultrasound to obtain a modified bentonite suspension, centrifuge the modified bentonite suspension, discard the filtrate, then put it into a freeze dryer, perform freeze drying, and after completion, obtain modified bentonite;

[0015] Q2, weighing modifier 2, dissolving it in deionized water to obtain modifier solution 2, adding montmorillonite to deionized water, stirring evenly to obtain montmorillonite suspension, mixing the modifier solution with the montmorillonite suspension, ultrasonically treating to obtain a modified montmorillonite suspension, centrifuging the modified montmorillonite suspension, discarding the filtrate, and then placing it in a freeze dryer for freeze drying, after which modified montmorillonite is obtained;

[0016] Q3, weighing modifier three, dissolving it in deionized water to obtain modifier solution three, adding magnesium silicate clay to deionized water, stirring evenly to obtain magnesium silicate clay suspension, mixing the modifier solution with the magnesium silicate clay suspension, ultrasonically treating to obtain modified magnesium silicate clay suspension, centrifuging the modified magnesium silicate clay suspension, discarding the filtrate, and then placing it in a freeze dryer for freeze drying. After completion, modified magnesium silicate clay is obtained;

[0017] Q4. Modified bentonite, modified montmorillonite and modified magnesium silicate clay are mixed to obtain highly dispersed modified soil.

[0018] Further, the modifier 1 in Q1 is hexadecyltrimethylammonium bromide, the stirring speed is 60-150rpm, the stirring time is 60-120min, the temperature is heated to 50-65°C, the mass concentration of the modifier 1 is 1-5wt%, the mass ratio of bentonite to deionized water is (0.8-1):10, the mass ratio of the modifier 1 to bentonite is 1:(2-8), the frequency of ultrasonic treatment is 100-200Hz, the time of ultrasonic treatment is 30-60min, and the centrifugal speed is 2000-4000 rpm, centrifugation time is 10-15min, pre-freezing temperature is -40℃, vacuum degree is 10Pa, drying time is 24-28h; in Q2, the second modifier is γ-aminopropyltriethoxysilane, the stirring speed is 80-150rpm, the stirring time is 30-60min, heating to 50-65℃, the mass concentration of the second modifier is 1-3wt%, the mass ratio of montmorillonite to deionized water is (0.8-1):10, the mass ratio of the second modifier to montmorillonite is 1:(3-8), and the frequency of ultrasonic treatment is 10 0-200Hz, ultrasonic treatment time is 30-60min, centrifugal speed is 2000-4000rpm, centrifugal time is 10-15min, pre-freezing temperature is -40°C, vacuum degree is 10Pa, drying time is 24-28h; modifier three in Q3 is polydimethylsiloxane, stirring speed is 80-150rpm, stirring time is 30-60min, heating to 50-65°C, mass concentration of modifier three is 1-2wt%, and mass ratio of modified magnesium silicate clay to deionized water is (0 .8-1):10, the mass ratio of modifier three to modified magnesium silicate clay is 1:(4-10), the frequency of ultrasonic treatment is 100-200Hz, the time of ultrasonic treatment is 30-60min, the centrifugal speed is 2000-4000rpm, the centrifugal time is 10-15min, the pre-freezing temperature is -40℃, the vacuum degree is 10Pa, and the drying time is 24-28h; the mass ratio of modified bentonite, modified montmorillonite and modified magnesium silicate clay in Q4 is (1-3):(1-4):(0.5-2).

[0019] The solvent is one or more of water, ethanol and medical white oil; the colloid is a mixture of gum arabic and xanthan gum, and the mass ratio of gum arabic to xanthan gum is 1:1; the pH regulator is one or more of 0.2-1.0wt% sodium carbonate solution, 0.1-0.5wt% sodium bicarbonate and 0.5-2.0wt% ammonia water.

[0020] A method for preparing a marine oil dispersant comprises the following steps:

[0021] M1. Solvent pretreatment: Add the solvent into a clean stirring tank, heat and stir to obtain the preheated solvent;

[0022] M2. Mixing: First add the composite surfactant solution, stir evenly, then slowly add the highly dispersed modified soil, stir evenly, then add the vegetable oil, tert-butylhydroquinone, yeast extract, colloid and sodium benzoate in sequence to obtain a marine oil mixture, and finally add the pH adjuster to obtain a marine oil dispersant.

[0023] Furthermore, M1 is heated to 40-45° C., M2 is stirred at a speed of 120-200 rpm, and the pH of the marine oil dispersant is 7-8.

[0024] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0025] 1. The present invention enables the dispersant to form a stable emulsion under the interaction of oil and water by adding a composite surfactant solution and a highly dispersed modified soil, thereby improving the use efficiency of the oil. Water, ethanol and medical white oil are selected as solvents with low volatility and high biocompatibility to enhance the stability and safety of the dispersant. In addition, the addition of vegetable oil not only enhances the lubricity of the dispersant, but also helps to reduce the viscosity of the dispersant, enhance its fluidity, and facilitate operation in practical applications. The antioxidant properties of tert-butylhydroquinone further enhance the long-term stability of the dispersant and reduce the property changes that may occur during long-term storage. The introduction of yeast extract and colloids adds additional bioactive ingredients to the formula, further optimizes the dispersion effect, forms an enhanced synergistic effect, and helps to achieve more efficient oil dispersion.

[0026] 2. The present invention combines chemical surfactants with bio-based surfactants to achieve strong surface activity while also introducing good biocompatibility. Classical surfactants can effectively reduce oil-water interfacial tension and promote the dispersion of oil droplets, while bio-based surfactants can not only enhance the dispersion effect, but also achieve good biodegradability and reduce potential environmental pollution. In addition, the grafting reaction in the composite surfactant solution is carried out by ultraviolet irradiation, and polar or functional side groups are introduced on the polymer chain, which further enhances the stability and durability of the dispersant, avoids phase separation or precipitation that may occur during the dispersion process, and ensures that the dispersion effect of marine oil is maintained at a high level during long-term navigation, thereby improving the utilization rate of oil, reducing fuel consumption, and maximizing economic benefits.

[0027] 3. The present invention obtains a highly dispersed modified soil with a larger specific surface area and stronger ion exchange capacity by modifying bentonite, montmorillonite and magnesium silicate clay, which can better adsorb surrounding liquid molecules and improve the stability of the dispersed phase. The combination of modified bentonite, montmorillonite and magnesium silicate clay makes it show better dispersibility and thickening in the oil-water mixed system. The increased viscosity can not only effectively prevent the combination of oil droplets and reduce the oil-water separation phenomenon, but also remain stable under high temperature and high pressure environments, and adapt to the special requirements of ship operations. In addition, the highly dispersed modified soil brings good rheological properties to the dispersion, making the operation of the dispersion more convenient and improving the efficiency of the dispersion operation. DETAILED DESCRIPTION

[0028] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0029] Embodiment 1:

[0030] This embodiment discloses a method for preparing a composite surfactant solution, comprising the following steps:

[0031] S1. Prepare a modified polymer solution: dissolve 1 g of polyvinyl alcohol and 1 g of polyacrylic acid in 70 mL of deionized water, heat to 60° C., and stir until completely dissolved to obtain a modified polymer solution;

[0032] S2. Prepare a surfactant solution: dissolve 1 g SDS, 1 g Tween 80, 1 g alkyl glycoside, 1 g rhamnolipid and 0.5 g sophorolipid in 80 mL deionized water, heat to 50° C., and stir until completely dissolved to obtain a surfactant solution;

[0033] S3, mixing: mixing the modified polymer solution and the surfactant solution, stirring evenly to obtain a mixed solution of the modified polymer and the surfactant;

[0034] S4. Grafting: Weigh 0.2 g of benzophenone and add it to the mixed solution of the modified polymer and the surfactant, and irradiate the mixed solution with ultraviolet light for 30 minutes to obtain a composite surfactant solution.

[0035] This embodiment discloses a method for preparing highly dispersed modified soil, comprising the following steps:

[0036] Q1. Weigh 1 g of hexadecyltrimethylammonium bromide and dissolve it in 100 mL of deionized water. Stir at a speed of 60 rpm for 60 min and heat to 50 ° C to obtain a modifier solution. Add 8 g of bentonite to deionized water and stir evenly to obtain a bentonite suspension. Mix the modifier solution with the bentonite suspension. The frequency of ultrasonic treatment is 100 Hz for 30 min to obtain a modified bentonite suspension. Centrifuge the modified bentonite suspension at 2000 rpm for 10 min, discard the filtrate, and then put it into a freeze dryer. The pre-freezing temperature is -40 ° C, the vacuum degree is 10 Pa, and the drying time is 24 h to obtain a modified bentonite.

[0037] Q2, weigh 1g of γ-aminopropyltriethoxysilane, dissolve it in 100mL of deionized water, stir at a speed of 80rpm, stir for 30min, heat to 50°C, obtain modifier solution 2, add 8g of montmorillonite to deionized water, stir evenly, obtain montmorillonite suspension, mix the modifier solution with the montmorillonite suspension, ultrasonicate at a frequency of 100Hz, ultrasonicate for 30min, obtain modified montmorillonite suspension, centrifuge the modified montmorillonite suspension at 2000rpm for 10min, discard the filtrate, then put it into a freeze dryer, pre-freeze at -40°C, vacuum 10Pa, dry for 24h, and obtain modified montmorillonite;

[0038] Q3, weigh 1g of polydimethylsiloxane, dissolve it in 100mL of deionized water, stir at a speed of 80rpm, stir for 30min, heat to 50°C, obtain modifier solution three, add 8g of magnesium silicate clay to deionized water, stir evenly, obtain magnesium silicate clay suspension, mix the modifier solution with the magnesium silicate clay suspension, ultrasonic treatment frequency is 100Hz, ultrasonic treatment time is 30min, obtain modified magnesium silicate clay suspension, centrifuge the modified magnesium silicate clay suspension at 2000rpm for 10min, discard the filtrate, then put it into a freeze dryer, pre-freeze temperature -40°C, vacuum degree 10Pa, dry for 24h, and obtain modified magnesium silicate clay;

[0039] Q4. Mix 1 g of modified bentonite, 1 g of modified montmorillonite and 0.5 g of modified magnesium silicate clay to obtain highly dispersed modified soil.

[0040] The present embodiment discloses a marine oil dispersant, which is composed of the following ingredients in parts by weight: 10 parts of water, 3 parts of ethanol, 2 parts of medical white oil, 10 parts of composite surfactant solution, 10 parts of highly dispersed modified soil, 2 parts of vegetable oil, 1 part of tert-butylhydroquinone, 1 part of yeast extract, 0.5 parts of gum arabic, 0.5 parts of xanthan gum, 1 part of sodium benzoate and 1 part of 0.5wt% sodium carbonate solution.

[0041] This embodiment discloses a method for preparing a marine oil dispersant, comprising the following steps:

[0042] M1. Solvent pretreatment: Add the solvent into a clean stirring tank, heat it to 40°C, and stir it evenly to obtain the preheated solvent;

[0043] M2. Mixing: First add the composite surfactant solution, stir evenly, then slowly add the highly dispersed modified soil, stir evenly, then add the vegetable oil, tert-butylhydroquinone, yeast extract, colloid and sodium benzoate in sequence to obtain a marine oil mixture, and finally add a pH adjuster to adjust the pH to 7 to obtain a marine oil dispersant.

[0044] Embodiment 2:

[0045] This embodiment discloses a method for preparing a composite surfactant solution, comprising the following steps:

[0046] S1. Prepare a modified polymer solution: dissolve 1 g of polyvinyl alcohol and 1 g of polyacrylic acid in 65 mL of deionized water, heat to 62° C., and stir until completely dissolved to obtain a modified polymer solution;

[0047] S2. Prepare a surfactant solution: dissolve 1 g SDS, 2 g Tween 80, 2 g alkyl glycoside, 1 g rhamnolipid and 0.6 g sophorolipid in 70 mL deionized water, heat to 55° C., and stir until completely dissolved to obtain a surfactant solution;

[0048] S3, mixing: mixing the modified polymer solution and the surfactant solution, stirring evenly to obtain a mixed solution of the modified polymer and the surfactant;

[0049] S4. Grafting: Weigh 0.8 g of benzophenone and add it to the mixed solution of the modified polymer and the surfactant, and irradiate the mixed solution with ultraviolet light for 35 minutes to obtain a composite surfactant solution.

[0050] This embodiment discloses a method for preparing highly dispersed modified soil, comprising the following steps:

[0051] Q1. Weigh 3 g of hexadecyltrimethylammonium bromide and dissolve it in 100 mL of deionized water. Stir at a speed of 100 rpm for 80 min and heat to 55 ° C to obtain a modifier solution. Add 9 g of bentonite to deionized water and stir evenly to obtain a bentonite suspension. Mix the modifier solution with the bentonite suspension. The frequency of ultrasonic treatment is 150 Hz for 45 min to obtain a modified bentonite suspension. Centrifuge the modified bentonite suspension at 3000 rpm for 12 min, discard the filtrate, and then put it into a freeze dryer. The pre-freezing temperature is -40 ° C, the vacuum degree is 10 Pa, and the drying time is 26 h to obtain a modified bentonite.

[0052] Q2, weigh 2g of γ-aminopropyltriethoxysilane, dissolve it in 100mL of deionized water, stir at a speed of 100rpm, stir for 45min, heat to 55°C, obtain modifier solution 2, add 9g of montmorillonite to deionized water, stir evenly, obtain montmorillonite suspension, mix the modifier solution with the montmorillonite suspension, ultrasonicate at a frequency of 150Hz, ultrasonicate for 45min, obtain modified montmorillonite suspension, centrifuge the modified montmorillonite suspension at 3000rpm for 12min, discard the filtrate, then put it into a freeze dryer, pre-freeze at -40°C, vacuum 10Pa, dry for 26h, and obtain modified montmorillonite;

[0053] Q3, weigh 1.5g polydimethylsiloxane, dissolve it in 100mL deionized water, stir at a speed of 100rpm, stir for 45min, heat to 55°C, obtain modifier solution three, add 9g magnesium silicate clay to deionized water, stir evenly, obtain magnesium silicate clay suspension, mix the modifier solution with the magnesium silicate clay suspension, ultrasonic treatment frequency is 150Hz, ultrasonic treatment time is 45min, obtain modified magnesium silicate clay suspension, centrifuge the modified magnesium silicate clay suspension at 3000rpm for 12min, discard the filtrate, then put it into a freeze dryer, pre-freeze temperature -40°C, vacuum degree 10Pa, drying time 26h, obtain modified magnesium silicate clay;

[0054] Q4. Mix 2g of modified bentonite, 3g of modified montmorillonite and 1g of modified magnesium silicate clay to obtain highly dispersed modified soil.

[0055] The present embodiment discloses a marine oil dispersant, which is composed of the following components in parts by weight: 10 parts of water, 5 parts of ethanol and 3 parts of medical white oil, 15 parts of composite surfactant solution, 12 parts of highly dispersed modified soil, 6 parts of vegetable oil, 3 parts of tert-butylhydroquinone, 1.5 parts of yeast extract, 0.6 parts of gum arabic, 0.7 parts of xanthan gum, 1.5 parts of sodium benzoate and 1.5 parts of 0.2wt% sodium bicarbonate.

[0056] This embodiment discloses a method for preparing a marine oil dispersant, comprising the following steps:

[0057] M1. Solvent pretreatment: Add the solvent into a clean stirring tank, heat it to 42°C, and stir it evenly to obtain the preheated solvent;

[0058] M2. Mixing: First add the composite surfactant solution, stir evenly, then slowly add the highly dispersed modified soil, stir evenly, then add the vegetable oil, tert-butylhydroquinone, yeast extract, colloid and sodium benzoate in sequence to obtain a marine oil mixture, and finally add a pH adjuster to adjust the pH to 7.5 to obtain a marine oil dispersant.

[0059] Embodiment 3:

[0060] This embodiment discloses a method for preparing a composite surfactant solution, comprising the following steps:

[0061] S1. Prepare a modified polymer solution: dissolve 1 g of polyvinyl alcohol and 1 g of polyacrylic acid in 60 mL of deionized water, heat to 65° C., and stir until completely dissolved to obtain a modified polymer solution;

[0062] S2. Prepare a surfactant solution: dissolve 1 g SDS, 3 g Tween 80, 3 g alkyl glycoside, 2 g rhamnolipid and 0.8 g sophorolipid in 60 mL deionized water, heat to 60° C., and stir until completely dissolved to obtain a surfactant solution;

[0063] S3, mixing: mixing the modified polymer solution and the surfactant solution, stirring evenly to obtain a mixed solution of the modified polymer and the surfactant;

[0064] S4. Grafting: Weigh 1.5 g of benzophenone and add it to the mixed solution of the modified polymer and the surfactant, and irradiate the mixed solution with ultraviolet light for 40 minutes to obtain a composite surfactant solution.

[0065] This embodiment discloses a method for preparing highly dispersed modified soil, comprising the following steps:

[0066] Q1. Weigh 5 g of hexadecyltrimethylammonium bromide and dissolve it in 100 mL of deionized water. Stir at a speed of 150 rpm for 120 min and heat to 65 ° C to obtain a modifier solution. Add 10 g of bentonite to deionized water and stir evenly to obtain a bentonite suspension. Mix the modifier solution with the bentonite suspension. The frequency of ultrasonic treatment is 200 Hz for 60 min to obtain a modified bentonite suspension. Centrifuge the modified bentonite suspension at 4000 rpm for 15 min, discard the filtrate, and then put it into a freeze dryer. The pre-freezing temperature is -40 ° C, the vacuum degree is 10 Pa, and the drying time is 28 h to obtain a modified bentonite.

[0067] Q2, weigh 3g of γ-aminopropyltriethoxysilane, dissolve it in 100mL of deionized water, stir at a speed of 150rpm, stir for 60min, heat to 65°C, obtain modifier solution 2, add 10g of montmorillonite to deionized water, stir evenly, obtain montmorillonite suspension, mix the modifier solution with the montmorillonite suspension, ultrasonic treatment frequency is 200Hz, ultrasonic treatment time is 60min, obtain modified montmorillonite suspension, centrifuge the modified montmorillonite suspension at 4000rpm for 15min, discard the filtrate, then put it into a freeze dryer, pre-freeze temperature -40°C, vacuum degree 10Pa, drying time 28h, obtain modified montmorillonite;

[0068] Q3, weigh 2g of polydimethylsiloxane, dissolve it in 100mL of deionized water, stir at a speed of 150rpm, stir for 60min, heat to 65°C, obtain modifier solution three, add 10g of magnesium silicate clay to deionized water, stir evenly, obtain magnesium silicate clay suspension, mix the modifier solution with the magnesium silicate clay suspension, ultrasonic treatment frequency is 200Hz, ultrasonic treatment time is 60min, obtain modified magnesium silicate clay suspension, centrifuge the modified magnesium silicate clay suspension at 4000rpm for 15min, discard the filtrate, then put it into a freeze dryer, pre-freeze temperature -40°C, vacuum degree 10Pa, drying time 28h, obtain modified magnesium silicate clay;

[0069] Q4. Mix 3g of modified bentonite, 4g of modified montmorillonite and 2g of modified magnesium silicate clay to obtain highly dispersed modified soil.

[0070] The present embodiment discloses a marine oil dispersant, which is composed of the following ingredients in parts by weight: 10 parts of water, 4 parts of ethanol, 3 parts of medical white oil, 20 parts of composite surfactant solution, 15 parts of highly dispersed modified soil, 8 parts of vegetable oil, 5 parts of tert-butylhydroquinone, 2 parts of yeast extract, 1 part of gum arabic, 1 part of xanthan gum, 2 parts of sodium benzoate and 1 part of 1.0wt% ammonia water.

[0071] This embodiment discloses a method for preparing a marine oil dispersant, comprising the following steps:

[0072] M1. Solvent pretreatment: Add the solvent into a clean stirring tank, heat it to 45°C, and stir it evenly to obtain the preheated solvent;

[0073] M2. Mixing: First add the composite surfactant solution, stir evenly, then slowly add the highly dispersed modified soil, stir evenly, then add the vegetable oil, tert-butylhydroquinone, yeast extract, colloid and sodium benzoate in sequence to obtain a marine oil mixture, and finally add a pH adjuster to adjust the pH to 8 to obtain a marine oil dispersant.

[0074] Comparative Example 1:

[0075] Comparative Example 1 Compared with Example 3, in the preparation process of the composite surfactant solution in Comparative Example 1, no modified polymer was added, and other conditions remained unchanged.

[0076] Comparative Example 2:

[0077] Comparative Example 2 Compared with Example 3, in the preparation process of the highly dispersed modified soil in Comparative Example 2, multiple modifiers were not added, and other conditions remained unchanged.

[0078] Comparative Example 3:

[0079] Comparative Example 3 Compared with Example 3, in the preparation process of the marine oil dispersant in Comparative Example 3, no highly dispersed modified soil is added, and other conditions remain unchanged.

[0080] Comparative Example 4:

[0081] Comparative Example 4 Compared with Example 3, in the preparation process of the marine oil dispersant in Comparative Example 4, no colloid was added, and other conditions remained unchanged.

[0082] Experimental example

[0083] The samples prepared in Examples 1-3 and Comparative Examples 1-4 were subjected to performance tests. The dispersion efficiency and oil droplet size distribution of the samples were tested according to ASTM D2267-04 (2012) "Standard Test Method for Properties of Petroleum Product Dispersants", the stability of the samples was tested according to GB / T 2912.1-2009, and the biodegradability of the samples was tested according to OECD 301B "Rapid Determination of Biodegradability - CEC-L-33-T-82". The test results are shown in Table 1:

[0084] Table 1

[0085]

[0086]

[0087] It can be seen from the test results in Table 1 that the marine oil dispersants prepared in Examples 1-3 of the present invention have excellent dispersion efficiency, stability and environmental performance. By comparing Comparative Example 2 with Examples 1-3, it can be seen that in the preparation process of the composite surfactant solution, adding a modified polymer can effectively improve the dispersion efficiency, stability and environmental performance of the marine oil dispersant; by comparing Comparative Example 2 with Examples 1-3, it can be seen that in the preparation process of the highly dispersed modified soil, adding a modifier can effectively improve the dispersion efficiency, stability and environmental performance of the marine oil dispersant; by comparing Comparative Example 3 with Examples 1-3, it can be seen that adding highly dispersed modified soil can effectively improve the dispersion efficiency, stability and environmental performance of the marine oil dispersant; by comparing Comparative Example 4 with Examples 1-3, it can be seen that adding a colloid can effectively improve the dispersion efficiency, stability and environmental performance of the marine oil dispersant.

[0088] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

[0089] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to only specific implementation methods. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A marine oil dispersant, characterized in that: The invention is composed of the following components in parts by weight: 15-20 parts of solvent, 10-20 parts of composite surfactant solution, 10-15 parts of highly dispersed modified soil, 2-8 parts of vegetable oil, 1-5 parts of tert-butylhydroquinone, 1-2 parts of yeast extract, 1-2 parts of colloid, 1-2 parts of sodium benzoate and 1-3 parts of pH regulator; the composite surfactant solution is obtained by grafting and modifying a modified polymer with a chemical surfactant and a bio-based surfactant; the highly dispersed modified soil is obtained by modifying bentonite, montmorillonite and magnesium silicate clay.

2. A marine oil dispersant according to claim 1, characterized in that: The preparation method of the composite surfactant solution comprises the following steps: S1. preparing a modified polymer solution: dissolving the modified polymer in deionized water, heating, and stirring until the modified polymer is completely dissolved to obtain a modified polymer solution; S2. preparing a surfactant solution: dissolving a chemical surfactant and a bio-based surfactant in deionized water, heating, and stirring until completely dissolved to obtain a surfactant solution; S3, mixing: mixing the modified polymer solution and the surfactant solution, stirring evenly to obtain a mixed solution of the modified polymer and the surfactant; S4, grafting: weigh benzophenone and add it to the mixed solution of modified polymer and surfactant, and irradiate the mixed solution with ultraviolet light to obtain a composite surfactant solution.

3. A marine oil dispersant according to claim 2, characterized in that: The modified polymer in S1 is a mixture of polyvinyl alcohol and polyacrylic acid, the mass ratio of polyvinyl alcohol, polyacrylic acid and deionized water is 1:1:(60-70), heated to 60-65°C, stirred at 60-120rpm, and stirred for 5-20min; the chemical surfactant in S2 is a mixture of sodium dodecyl sulfate and Tween 80, SDS and Tween The mass ratio of chemical surfactant, bio-based surfactant and water is 2: (2.5-5.8): (60-80), heated to 50-60°C, stirred at 25-40rpm, and stirred for 5-20min; the concentration of benzophenone in S4 is 0.1-1.0wt%, and the mixed solution is irradiated with ultraviolet light for 30-40min.

4. A marine oil dispersant according to claim 1, characterized in that: The preparation method of highly dispersed modified soil comprises the following steps: Q1. Weigh a modifier 1, dissolve it in deionized water, stir and heat to obtain a modifier solution 1, add bentonite to deionized water, stir evenly to obtain a bentonite suspension, mix the modifier solution with the bentonite suspension, treat with ultrasound to obtain a modified bentonite suspension, centrifuge the modified bentonite suspension, discard the filtrate, then put it into a freeze dryer, perform freeze drying, and after completion, obtain modified bentonite; Q2, weighing modifier 2, dissolving it in deionized water to obtain modifier solution 2, adding montmorillonite to deionized water, stirring evenly to obtain montmorillonite suspension, mixing the modifier solution with the montmorillonite suspension, ultrasonically treating to obtain a modified montmorillonite suspension, centrifuging the modified montmorillonite suspension, discarding the filtrate, and then placing it in a freeze dryer for freeze drying, after which modified montmorillonite is obtained; Q3, weighing modifier three, dissolving it in deionized water to obtain modifier solution three, adding magnesium silicate clay to deionized water, stirring evenly to obtain magnesium silicate clay suspension, mixing the modifier solution with the magnesium silicate clay suspension, ultrasonically treating to obtain modified magnesium silicate clay suspension, centrifuging the modified magnesium silicate clay suspension, discarding the filtrate, and then placing it in a freeze dryer for freeze drying. After completion, modified magnesium silicate clay is obtained; Q4. Modified bentonite, modified montmorillonite and modified magnesium silicate clay are mixed to obtain highly dispersed modified soil.

5. A marine oil dispersant according to claim 4, characterized in that: The modifier 1 in Q1 is hexadecyltrimethylammonium bromide, the stirring speed is 60-150rpm, the stirring time is 60-120min, the temperature is heated to 50-65°C, the mass concentration of the modifier 1 is 1-5wt%, the mass ratio of bentonite to deionized water is (0.8-1):10, the mass ratio of the modifier 1 to bentonite is 1:(2-8), the frequency of ultrasonic treatment is 100-200Hz, the time of ultrasonic treatment is 30-60min, the speed of centrifugation is 2000-4000rpm, the time of centrifugation is 10-15min, the pre-freezing temperature is -40°C, the vacuum degree is 10Pa, and the drying time is 24-28h.

6. A marine oil dispersant according to claim 4, characterized in that: The modifier 2 in Q2 is γ-aminopropyltriethoxysilane, the stirring speed is 80-150rpm, the stirring time is 30-60min, the temperature is heated to 50-65°C, the mass concentration of the modifier 2 is 1-3wt%, the mass ratio of montmorillonite to deionized water is (0.8-1):10, the mass ratio of the modifier 2 to montmorillonite is 1:(3-8), the frequency of ultrasonic treatment is 100-200Hz, the time of ultrasonic treatment is 30-60min, the speed of centrifugation is 2000-4000rpm, the time of centrifugation is 10-15min, the pre-freezing temperature is -40°C, the vacuum degree is 10Pa, and the drying time is 24-28h.

7. A marine oil dispersant according to claim 4, characterized in that: The modifier three in Q3 is polydimethylsiloxane, the stirring speed is 80-150rpm, the stirring time is 30-60min, the temperature is heated to 50-65°C, the mass concentration of the modifier three is 1-2wt%, the mass ratio of the modified magnesium silicate clay to deionized water is (0.8-1):10, the mass ratio of the modifier three to the modified magnesium silicate clay is 1:(4-10), the frequency of the ultrasonic treatment is 100-200Hz, the time of the ultrasonic treatment is 30-60min, the centrifugal speed is 2000-4000rpm, the centrifugal time is 10-15min, the pre-freezing temperature is -40°C, the vacuum degree is 10Pa, and the drying time is 24-28h; the mass ratio of the modified bentonite, modified montmorillonite and modified magnesium silicate clay in Q4 is (1-3):(1-4):(0.5-2).

8. A marine oil dispersant according to claim 1, characterized in that: The solvent is one or more of water, ethanol and medical white oil; the colloid is a mixture of gum arabic and xanthan gum, and the mass ratio of gum arabic to xanthan gum is 1:1; the pH regulator is one or more of 0.2-1.0wt% sodium carbonate solution, 0.1-0.5wt% sodium bicarbonate and 0.5-2.0wt% ammonia water.

9. A method for preparing a marine oil dispersant, characterized in that: The following steps are involved: M1. Solvent pretreatment: Add the solvent into a clean stirring tank, heat and stir to obtain the preheated solvent; M2. Mixing: First add the composite surfactant solution, stir evenly, then slowly add the highly dispersed modified soil, stir evenly, then add the vegetable oil, tert-butylhydroquinone, yeast extract, colloid and sodium benzoate in sequence to obtain a marine oil mixture, and finally add the pH adjuster to obtain a marine oil dispersant.

10. The method for preparing a marine oil dispersant according to claim 9, characterized in that: M1 is heated to 40-45°C, M2 is stirred at a speed of 120-200 rpm, and the pH of the marine oil dispersant is 7-8.

Images