Preparation method of high-efficiency marine oil spill dispersant based on double surfactant compound system

Abstract

The present application relates to a kind of preparation method of high-efficiency marine oil spill dispersant based on gemini surfactant complex system, the present application is mixed uniformly after biological surfactant and gemini surfactant, join organic solvent ultrasonic mixing, obtain high-efficiency marine oil spill dispersant;The mass content of biological surfactant is 10%-25%, and the mass content of gemini surfactant is 5%-20%.The high-efficiency marine oil spill dispersant of the present application is resistant to temperature, salt, acid and alkali, and has good effect, can stabilize a variety of oil phases (n-alkane, aromatic hydrocarbon, diesel, soybean oil, olive oil, crude oil, etc.) in different salinity, different pH environment.Biological toxicity is low, and it will not affect the growth of bacteria, and can be widely suitable for marine environment.

Description

Technical fields:

[0001] This invention relates to a method for preparing a highly efficient marine oil spill dispersant based on a gemini surfactant compound system, belonging to the field of water pollution prevention and control technology. Background technology:

[0002] With increasingly frequent offshore oil extraction and transportation activities, marine oil spills are becoming more common. Currently, the main methods for handling marine oil spills include physical, chemical, and biological methods. Oil spill dispersants are a commonly used emergency measure for dealing with marine oil spills. Commonly known as "oil dispersants," they reduce the viscosity and surface tension of the spilled oil, facilitating emulsification and dispersion, promoting sufficient contact and mixing between oil and water, and making the oil easier for biodegradation in water. This makes them one of the effective chemical methods for reducing marine oil spill pollution. Dispersants are typically composed of several surfactants dissolved in one or more organic solvents. Surfactants can rapidly reduce the interfacial tension between oil and water, dispersing crude oil into small droplets that diffuse into seawater. Because they significantly increase the oil-water interfacial area, oil spill dispersants can reduce oil spills reaching land and promote subsequent biodegradation of crude oil, thereby achieving the goal of remediating marine environmental pollution.

[0003] Traditional oil spill dispersants mainly consist of two parts: chemical surfactants and solvents. The compound system of sodium diisooctyl succinate sulfonate and Tween 80 is currently the most widely used oil spill dispersant formulation. Solvents are a crucial component of dispersants; they promote the dissolution of surfactants and enhance the binding between oil spills and surfactants, thereby improving the emulsification and dispersion effect of the dispersant. In the national standard GB18188.1-2000, technical conditions for oil spill dispersants, oil spill dispersants are divided into two categories: conventional dispersants and concentrated dispersants. Conventional dispersants consist of a mixture of aliphatic hydrocarbon solvents and surfactants, with the surfactant content not exceeding 30%. Concentrated dispersants typically contain oxidized aliphatic hydrocarbon solvents, and the surfactant content is generally 50%–75%; however, existing conventional oil spill dispersants generally suffer from low emulsification rates.

[0004] Chinese patent document CN 104962239 A discloses an environmentally friendly oil spill dispersant and its preparation method. The specific preparation method involves compounding anionic and nonionic surfactants, adding ethylene glycol butyl ether and the stabilizer polyethylene glycol (PEG), to obtain an environmentally friendly oil spill dispersant. However, this oil spill dispersant has a 30-second emulsification rate of only 24.3%, which is low. The high proportion of organic solvents used poses a potential hazard to marine life.

[0005] Chinese patent document CN106964299 A discloses a highly stable oil spill dispersant and its preparation method. The specific preparation method involves mixing hydrophobic chitosan particles with a surfactant solution to form a highly stable oil spill dispersant. However, this method requires a stirring speed of up to 5000 r / min during emulsion preparation, resulting in high energy consumption and potential difficulties in applying it to real marine environments.

[0006] Chinese patent document CN 102060338 A discloses an oil dispersant for rapidly eliminating floating oil on water surfaces and its preparation method. The main components of the dispersant are nonionic surfactants, anionic surfactants, diglycerides, alkyl glycosides, oxygen-containing solvents, ethanol, hydrocarbon solvents, etc. The formulation of this dispersant is relatively complex.

[0007] In summary, the dispersants currently used in China still have problems such as low emulsification rate, high proportion of organic solvents, and certain potential hazards to marine organisms and microorganisms, which can easily lead to secondary pollution and affect the marine ecological environment. Summary of the Invention:

[0008] To address the shortcomings of existing technologies, especially the problems of low emulsification rate, high organic solvent ratio, and difficulty in practical application of existing dispersants, this invention provides a method for preparing a highly efficient marine oil spill dispersant based on a gemini surfactant compound system. The oil spill dispersant obtained by this invention is applicable to a variety of environments and is environmentally friendly.

[0009] This invention is achieved through the following technical solution:

[0010] A method for preparing a highly efficient marine oil spill dispersant based on a gemini surfactant compound system includes the following steps:

[0011] After uniformly mixing biosurfactant and gemini surfactant, an organic solvent is added and ultrasonically mixed to obtain a highly efficient marine oil spill dispersant.

[0012] The biosurfactant content is 10%-25% by mass, and the gemini surfactant content is 5%-20% by mass.

[0013] According to a preferred embodiment of the present invention, the gemini surfactant is ethylene-based (decyl / tetradecyl dimethyl ammonium chloride), ethylene-based bis(tetradecyl dimethyl ammonium chloride), or ethylene-based bis(hexadecyl trimethyl ammonium chloride).

[0014] According to a preferred embodiment of the present invention, the gemini surfactant is ethylene-based (decyl / tetradecyl dimethyl ammonium chloride) or ethylene-based bis(tetradecyl dimethyl ammonium chloride).

[0015] Most preferably, the gemini surfactant is ethylene-based (decyl / tetradecyl dimethyl ammonium chloride).

[0016] According to a preferred embodiment of the present invention, the biosurfactant is rhamnolipid, sophorolipid, xanthan gum, or alkyl glycoside.

[0017] More preferably, the biosurfactant is rhamnolipid or sophorolipid.

[0018] According to the present invention, the organic solvent is preferably dipropylene glycol butyl ether or ethylene glycol butyl ether.

[0019] According to a preferred embodiment of the present invention, the biosurfactant content is 15%-22% by mass, and the gemini surfactant content is 8%-15% by mass.

[0020] The present invention uses a gemini surfactant, in which two hydrophilic groups are linked together and two hydrophobic groups are arranged side by side to form a whole surfactant. During the implementation of the present invention, it was unexpectedly discovered that controlling the mass content of gemini surfactant to 8%-15% and the type of gemini surfactant can significantly improve the emulsification effect and the applicable environment. It has good emulsification effect on n-tetradecane, toluene, diesel oil, soybean oil and olive oil.

[0021] A highly efficient marine oil spill dispersant based on a gemini surfactant compound system was prepared using the method described above.

[0022] Compared with the prior art, the technical features and advantages of the present invention are as follows:

[0023] 1. This invention provides a highly efficient marine oil spill dispersant using the simplest method. It exhibits excellent oil spill response. According to industry standard (HY044-1997), the emulsification rate of this dispersant reaches over 60% in 30 seconds and over 30% in 10 minutes, both exceeding industry standard requirements and demonstrating broad application prospects. It is suitable for emergency response to marine oil spill accidents.

[0024] 2. The high-efficiency marine oil spill dispersant of the present invention reduces the impact of chemical surfactants on marine organisms and has no significant effect on the growth of high-efficiency petroleum hydrocarbon degrading bacteria.

[0025] 3. The organic solvent used in this invention has low volatility, which can effectively increase the solubility of surfactants and promote oil overflow emulsification.

[0026] 4. The high-efficiency marine oil spill dispersant of the present invention has good temperature resistance, salt resistance, and acid and alkali resistance. It can stabilize various oil phases (n-alkanes, aromatics, diesel, soybean oil, olive oil, crude oil, etc.) under different salinity and pH environments.

[0027] 5. The high-efficiency marine oil spill dispersant of this invention has a simple formulation, good emulsification and dispersion effects, and excellent oil spill dispersion performance, meeting national standards and exhibiting low biotoxicity. It will not affect bacterial growth and is widely suitable for marine environments. Attached image description:

[0028] Figure 1 The images show the appearance of emulsions prepared with the three dispersants obtained in Examples 1, 2, and 3 at a concentration of 1 wt% after being sealed and left at room temperature for 24 hours; in the images, ① represents Example 1, ② represents Example 2, and ③ represents Example 3.

[0029] Figure 2 The images show the appearance of emulsions prepared with the three dispersants obtained in Examples 1, 2, and 3 at a concentration of 1 wt% at different pH values ​​after being sealed and left at room temperature for 24 hours; in the images, ① represents Example 1, ② represents Example 2, and ③ represents Example 3.

[0030] Figure 3 The images show the appearance of emulsions prepared with the three dispersants obtained in Examples 1, 2, and 3 at a concentration of 1 wt% under different salinities after being sealed and left at room temperature for 24 hours; in the images, ① represents Example 1, ② represents Example 2, and ③ represents Example 3.

[0031] Figure 4 The images show the appearance of emulsions of different types of oil phases prepared with the three dispersants obtained in Examples 1, 2, and 3 at a concentration of 1 wt% after being sealed and left at room temperature for 24 hours; in the images, ① is Example 1, ② is Example 2, and ③ is Example 3.

[0032] Figure 5 This figure shows the growth of bacteria after they were spread on a culture medium containing the samples prepared in Examples 1, 2, and 3 and incubated at 30°C for 48 hours. In the figure, ① represents Example 1, ② represents Example 2, and ③ represents Example 3.

[0033] Figure 6 The images show the appearance of mixtures prepared from the three dispersants in Comparative Examples 1-3 at a concentration of 1 wt% after being sealed and left at room temperature for 24 hours; in the images, ① is Comparative Example 1, ② is Comparative Example 2, and ③ is Comparative Example 3.

[0034] Figure 7 The images show the appearance of mixtures prepared from the three dispersants of Comparative Examples 4-6 at a concentration of 1 wt% after being sealed and left at room temperature for 24 hours; in the images, ① is Comparative Example 4, ② is Comparative Example 5, and ③ is Comparative Example 6.

[0035] Figure 8 The figures show the appearance of mixtures prepared from the three dispersants of Comparative Examples 7-9 at a concentration of 1 wt% after being sealed and left at room temperature for 24 hours; in the figures, ① is Comparative Example 7, ② is Comparative Example 8, and ③ is Comparative Example 9. Detailed implementation method:

[0036] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the protection scope of the present invention.

[0037] Example 1

[0038] Preparation of a high-efficiency marine oil spill dispersant based on a gemini surfactant compound system:

[0039] (1) Ethylene (decyl / tetradecyl dimethyl ammonium chloride) was subjected to vacuum rotary evaporation at 45°C for 1 h and drying at 105°C for 24 h to obtain the purified product;

[0040] (2) The mass percentages of each component in the marine oil spill dispersant are as follows: 21.5% rhamnolipid, 8.5% ethylene (decyl / tetradecyl dimethyl ammonium chloride), and 70% dipropylene glycol butyl ether.

[0041] First, mix rhamnolipid and ethylene (decyl / tetradecyl dimethyl ammonium chloride) in the above proportion and stir evenly. Then add dipropylene glycol butyl ether and sonicate for 5 minutes to mix them thoroughly. The resulting mixture is dispersant No. 1.

[0042] Example 2

[0043] Preparation of a high-efficiency marine oil spill dispersant based on a gemini surfactant compound system:

[0044] (1) Ethylene bis(tetradecyl dimethyl ammonium chloride) was subjected to vacuum rotary evaporation at 45°C for 1 h and drying at 105°C for 24 h to obtain the purified product;

[0045] (2) The mass percentages of each component in the marine oil spill dispersant are as follows: 15% rhamnolipid, 15% ethylene bis(tetradecyl dimethyl ammonium chloride), and 70% dipropylene glycol butyl ether.

[0046] First, mix rhamnolipid and ethylene (decyl / tetradecyl dimethyl ammonium chloride) in the above proportion and stir evenly. Then add dipropylene glycol butyl ether and sonicate for 5 minutes to mix them thoroughly. The resulting mixture is dispersant No. 2.

[0047] Example 3

[0048] Preparation of a high-efficiency marine oil spill dispersant based on a gemini surfactant compound system:

[0049] (1) Ethylene bis(hexadecyltrimethylammonium chloride) was subjected to vacuum rotary evaporation at 45°C for 1 h and drying at 105°C for 24 h to obtain the purified product;

[0050] (2) The mass percentages of each component in the marine oil spill dispersant are as follows: 15% rhamnolipid, 15% ethylene bis(hexadecyltrimethylammonium chloride), and 70% dipropylene glycol butyl ether.

[0051] First, mix rhamnolipid and ethylene (decyl / tetradecyl dimethyl ammonium chloride) in the above proportion and stir until uniform. Then, add dipropylene glycol butyl ether and sonicate for 5 minutes to mix them thoroughly. The resulting mixture is dispersant No. 3.

[0052] Experimental Example 1:

[0053] 1. The dispersants prepared in Examples 1-3 were dispersed in pure water at a mass fraction of 1.0 wt%. An oil phase was added to the aqueous phase, with volume fractions controlled at 15%, 25%, 40%, and 50%, respectively. The oil phase was diesel oil, with a pH of 7.0 and a salinity of 0. The oil-water mixture was vortexed at 1000 rpm for 15 min and allowed to stand for 24 h to obtain oil-in-water emulsions prepared with different oil volume fractions. The appearance of the emulsions prepared with different oil volume fractions after being sealed and placed at room temperature for 24 h is shown in the figure. Figure 1 As can be seen, the dispersant of the present invention has good emulsifying and dispersing effects and long-term stability.

[0054] 2. The dispersants prepared in Examples 1-3 were dispersed in pure water at a mass fraction of 1.0 wt%. An oil phase was added to the aqueous phase, controlling the oil phase volume fraction to be 50%. The oil phase was diesel oil, and the aqueous phases had pH values ​​of 5, 6, 7, 8, and 9, with a salinity of 0. The oil-water mixtures were vortexed at 1000 rpm for 15 min and allowed to stand for 24 h to obtain emulsions prepared at different pH values. The appearance of the emulsions prepared with the dispersants at different pH values ​​after standing at room temperature for 24 h is shown in the figure. Figure 2 As shown, this novel oil spill dispersant has good acid and alkali resistance and good environmental adaptability, and can be applied to oil spill treatment in different environments.

[0055] 3. The dispersants prepared in Examples 1-3 were dispersed in artificial seawater at a mass fraction of 1.0 wt%. An oil phase was added to the aqueous phase, controlling the oil phase volume fraction to be 50%. The oil phase was diesel oil with salinities of 0, 0.5%, 1%, 2%, and 3% and a pH of 7. The oil-water mixture was shaken at 1000 rpm for 15 minutes using a vortex shaker and allowed to stand for 24 hours to obtain emulsions prepared at different salinities. The appearance of the emulsions obtained at different salinities after being sealed and left at room temperature for 24 hours is shown in the figure. Figure 3As shown, the dispersant of the present invention has good salt resistance and good environmental adaptability, and can be applied to oil spill treatment in different environments.

[0056] 4. The dispersants prepared in Examples 1-3 were dispersed in pure water at a mass fraction of 1.0 wt%. Different oil phases were added to the aqueous phase, controlling the volume fraction of the oil phase to be 50%. The oil phases were n-tetradecane, toluene, diesel oil, soybean oil, and olive oil, with a salinity of 0 and a pH of 7. The oil-water mixture was vortexed at 1000 rpm for 15 min and allowed to stand for 24 h to obtain an oil-in-water emulsion. The appearance of the emulsions obtained with different oil phases after being sealed and left at room temperature for 24 h is shown in the figure. Figure 4 As shown, the dispersant of the present invention has good emulsifying effects on n-tetradecane, toluene, diesel oil, soybean oil, and olive oil, and can be applied to oil spill treatment in marine environments.

[0057] 5. Mix the dispersant prepared in Examples 1-3 with crude oil at a mass ratio of 0.2:1, add it to 50 mL of artificial seawater, shake and emulsify for 3 min, let it stand for 30 s and 10 min respectively, then extract the dispersed crude oil with a certain volume of chloroform, measure the crude oil content in chloroform using a UV spectrophotometer, and calculate the emulsification rate of the dispersant.

[0058] The dispersant in Example 1 achieved an emulsification rate of 70.26% at 30 seconds and 33.2% at 10 minutes.

[0059] The dispersant in Example 2 achieved an emulsification rate of 74.58% at 30 seconds and 34.6% at 10 minutes.

[0060] The dispersant in Example 3 achieved an emulsification rate of 64.43% at 30 seconds and 32.84% at 10 minutes.

[0061] 6. The bacteria were spread onto a culture medium containing 30 mg / L of the dispersant samples prepared in Examples 1-3, and incubated at 30°C for 48 hours. The bacterial growth was then observed. The results are as follows: Figure 5 As shown, bacteria can grow normally after 48 hours, indicating that the dispersant of the present invention does not inhibit the growth of marine microorganisms.

[0062] Bacterial name: AP-1, sequence number: MZ675665.1, acquisition method: obtained from water samples collected in the oil spill area in the laboratory. Reference: Acinetobacter junii strain AP-1 16S ribosomal RNAgene, partial sequence, GenBank: MZ675665.1.

[0063] 7. The dispersants prepared in Examples 1-3 were compared with other dispersants, and the results are shown in Table 1:

[0064] Table 1 compares the performance indicators of this invention with the values ​​specified in industry standard HY044-1997 and existing technologies.

[0065]

[0066] Comparative Example 1:

[0067] The preparation of the high-efficiency marine oil spill dispersant described in Example 1 differs from that in:

[0068] The ethylene group (decyl / tetradecyl dimethyl ammonium chloride) was replaced with diethyl maleate bis(octadecyl dimethyl ammonium chloride), and the rest was carried out as in Example 1.

[0069] Comparative Example 2:

[0070] The preparation of the high-efficiency marine oil spill dispersant described in Example 1 differs from that in:

[0071] The propylene bis(decyl dimethyl ammonium chloride) was used instead of the ethylene (decyl / tetradecyl dimethyl ammonium chloride), and the rest was carried out as in Example 1.

[0072] Comparative Example 3:

[0073] The preparation of the high-efficiency marine oil spill dispersant described in Example 1 differs from that in:

[0074] The ethylene group (decyl / tetradecyl dimethyl ammonium chloride) was replaced with octadecyl diester quaternary ammonium salt, and the rest was carried out as in Example 1.

[0075] Comparative Example 4:

[0076] The preparation of the high-efficiency marine oil spill dispersant described in Example 1 differs from that in that:

[0077] The mass percentages of the components in the marine oil spill dispersant are as follows: 30% rhamnolipin and 70% dipropylene glycol butyl ether.

[0078] Comparative Example 5:

[0079] The preparation of the high-efficiency marine oil spill dispersant described in Example 1 differs from that in:

[0080] The mass percentages of each component in the marine oil spill dispersant are as follows: 30% xanthan gum and 70% dipropylene glycol butyl ether.

[0081] Comparative Example 6:

[0082] The preparation of the high-efficiency marine oil spill dispersant described in Example 1 differs from that in:

[0083] The mass percentages of each component in the marine oil spill dispersant are as follows: 30% sophorolipid and 70% dipropylene glycol butyl ether.

[0084] Comparative Example 7:

[0085] The preparation of the high-efficiency marine oil spill dispersant described in Example 1 differs from that in:

[0086] The mass percentages of each component in the marine oil spill dispersant are as follows: 29% rhamnolipin, 1% ethylene (decyl / tetradecyl dimethyl ammonium chloride), and 70% dipropylene glycol butyl ether.

[0087] Comparative Example 8:

[0088] The preparation of the high-efficiency marine oil spill dispersant described in Example 2 differs from that in:

[0089] The mass percentages of each component in the marine oil spill dispersant are as follows: 29% rhamnolipin, 1% ethylene bis(tetradecyl dimethyl ammonium chloride), and 70% dipropylene glycol butyl ether.

[0090] Comparative Example 9:

[0091] The preparation of the high-efficiency marine oil spill dispersant described in Example 3 differs from that in:

[0092] The mass percentages of each component in the marine oil spill dispersant are as follows: 29% rhamnolipid, 1% ethylene bis(hexadecyltrimethylammonium chloride), and 70% dipropylene glycol butyl ether.

[0093] Comparative Experiment Example 1:

[0094] 1. The dispersants prepared in Comparative Examples 1-3 were dispersed in pure water at a mass fraction of 1.0 wt%. An oil phase with a volume fraction of 50% (diesel oil) was added to the aqueous phase. The oil phase had a pH of 7.0 and a salinity of 0. The oil-water mixture was vortexed at 1000 rpm for 15 min and allowed to stand for 24 h to obtain the final mixture. The appearance of the mixture after being sealed and left at room temperature for 24 h is shown in the image below. Figure 6 It can be seen that the dispersants obtained from other gemini surfactants do not have an emulsifying and dispersing effect.

[0095] 2. The dispersant prepared in Comparative Examples 4-6 was dispersed in pure water at a mass fraction of 1.0 wt%. An oil phase with a volume fraction of 50% was added to the aqueous phase; the oil phase was diesel oil, with a pH of 7.0 and a salinity of 0. The oil-water mixture was vortexed at 1000 rpm for 15 min and allowed to stand for 24 h to obtain the final mixture. The appearance of the mixture after being sealed and left at room temperature for 24 h is shown in the image below. Figure 7 It can be seen that the emulsifying and dispersing effect of the dispersant obtained by pure biosurfactant is much smaller than that of the present invention.

[0096] 3. The dispersant prepared in Comparative Examples 7-9 was dispersed in pure water at a mass fraction of 1.0 wt%. An oil phase with a volume fraction of 50% was added to the aqueous phase; the oil phase was diesel oil, with a pH of 7.0 and a salinity of 0. The oil-water mixture was vortexed at 1000 rpm for 15 min and allowed to stand for 24 h to obtain the final mixture. The appearance of the mixture after being sealed and left at room temperature for 24 h is shown in the image below. Figure 8 It can be seen that the emulsification and dispersion effect of the dispersant obtained with too low a Gemini surfactant is far less than that of the present invention.

[0097] In summary, the mass content and type of Gemini surfactants can significantly improve emulsification and improve the applicable environment, and have good emulsification effects on n-tetradecane, toluene, diesel oil, soybean oil, and olive oil.

Claims

1. A method for preparing a high-efficiency marine oil spill dispersant based on a gemini surfactant compound system, comprising the following steps: After uniformly mixing biosurfactant and gemini surfactant, an organic solvent is added and ultrasonically mixed to obtain a highly efficient marine oil spill dispersant. The biosurfactant content is 10%-25% by mass, and the gemini surfactant content is 5%-20% by mass. The aforementioned gemini surfactant is ethylene-based (decyl / tetradecyl dimethyl ammonium chloride), ethylene-based bis(tetradecyl dimethyl ammonium chloride), or ethylene-based bis(hexadecyl trimethyl ammonium chloride); The biosurfactant is rhamnolipid, sophorolipid, xanthan gum, or alkyl glycoside; The organic solvent is dipropylene glycol butyl ether or ethylene glycol butyl ether.

2. The production method according to claim 1, characterized by, The aforementioned gemini surfactant is ethylene-based (decyl / tetradecyl dimethyl ammonium chloride) or ethylene-based bis(tetradecyl dimethyl ammonium chloride).

3. The preparation method according to claim 1, characterized in that, The described twin surfactant is ethylene-based (decyl / tetradecyl dimethyl ammonium chloride).

4. The method of claim 1, wherein, The biosurfactant is rhamnolipid or sophorolipid.

5. The preparation method according to claim 1, characterized in that, The biosurfactant content is 15%-22% by mass, and the gemini surfactant content is 8%-15% by mass.

6. A highly efficient marine oil spill dispersant based on a gemini surfactant compound system, prepared by the method described in any one of claims 1-5.

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