Concentrated marine oil spill dispersant and use thereof

Abstract

The application provides a concentrated offshore oil spill dispersant and application thereof, and the dispersant comprises a first non-ionic surfactant Tween 80, a second non-ionic surfactant Span 20, a third non-ionic surfactant polyoxyethylene stearate, an additive propylene glycol and a solvent No. 3 white oil. The concentrated offshore oil spill dispersant is prepared by directly heating and compounding, hydrogen bonds are formed between the additive propylene glycol and Tween 80, the solubilization of polyoxyethylene stearate makes Tween 80, Span 20 and the solvent white oil form a clear and transparent microemulsion product, the similar molecular polarity between the solvent and the oil spill is utilized to improve the contact area of the surfactant and the oil spill, improve the efficiency of the dispersant in dispersing the oil spill, and the application is environment-friendly.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of water pollution prevention, in particular to a concentrated offshore oil spill dispersant and application thereof. BACKGROUND

[0002] In recent years, with the substantial increase in land and offshore oil production and offshore storage capacity, offshore oil spill accidents occur frequently, and oil spill pollution has become the type of marine pollution with the highest frequency, the widest distribution and the greatest harm. In order to seek an economic and effective treatment approach, many countries in the world have made great progress in physics, chemistry and biology, among which the use of oil spill dispersant is one of the chemical methods for rapid treatment of oil spill. Oil spill dispersant, also known as dispersant, is mainly composed of three parts: surfactant, solvent and additive. The surfactant plays a major role in the dispersant, which is composed of lipophilic group and hydrophilic group, and has affinity to oil and water, and at the same time, changes the interaction of oil-water interface to reduce the surface tension of oil film, so that the oil spill forms a small water-in-oil emulsion under the action of mechanical stirring or wave. The solvent is commonly used in alcohol and hydrocarbon, which makes the surfactant molecules and the oil spill mutually soluble and reduces the viscosity of the two, and dilutes the oil and reduces the freezing point of the oil, facilitating the emulsification of the oil. The additive is an additional component in the oil spill dispersant, which has a small content and is generally composed of wetting agent and stabilizer, and its main function is to improve the quality of the product.

[0003] The emulsified and dispersed oil spill dispersant has the characteristics of good oil removal effect, simple use and no restriction by sea conditions. The research on oil spill dispersant in China started in the 1970s, and the product is mainly used for oil spill treatment in offshore and shallow sea oil fields, but the performance indicators are still inferior to foreign products. At present, oil spill dispersant still needs to be partially imported, and some products have the disadvantages of high toxicity, low stability and emulsification rate, high price and the like, so it is necessary to develop an efficient and economic environmental friendly oil spill dispersant to meet the demand of domestic market.

[0004] The patent application with publication number CN102335493A discloses a biological oil spill dispersant, which is characterized by emulsifying the oil spill by surfactant and simultaneously using microorganisms for rapid biological remediation when the oil spill accident occurs. The surfactant used is rhamnolipid, which is not ideal in dispersing and emulsifying effect. Moreover, the use of yeast preservation and fermentation means has limited scale and poor effect. Therefore, it is a key research in the technical field to develop an efficient and economic environmental friendly oil spill dispersant. SUMMARY

[0005] In view of the deficiencies of the prior art, the present application provides a concentrated offshore oil spill dispersant, which is prepared by directly heating and compounding, utilizes the hydrogen bond coupling between the auxiliary propylene glycol and Tween 80, utilizes the solubilization of the stearic acid polyoxyethylene ether to dissolve Tween 80 and Span 20 in the solvent white oil, utilizes the similar molecular polarity between the solvent and the oil spill to improve the contact area of the surfactant and the oil spill, and improves the efficiency of the dispersant in dispersing the oil spill, and is environmentally friendly.

[0006] To achieve the above technical solution, the present application provides a concentrated offshore oil spill dispersant, which comprises: a first non-ionic surfactant Tween 80, a second non-ionic surfactant Span 20, a third non-ionic surfactant stearic acid polyoxyethylene ether, an auxiliary propylene glycol, and a solvent white oil No. 3.

[0007] S1, the first non-ionic surfactant Tween 80 is selected and added to the auxiliary propylene glycol, and then uniformly mixed, and then stirred at a temperature of 30-40℃ and a rotation speed of 600-1000r / min for 5-10min to obtain a mixture A;

[0008] S2, the second non-ionic surfactant Span 20 and the third non-ionic surfactant stearic acid polyoxyethylene ether are added to anhydrous ethanol, uniformly mixed, and then stirred at a temperature of 40-50℃ and a rotation speed of 800-1200r / min for 10-15min to fully dissolve, and then anhydrous ethanol is removed by reduced pressure distillation to obtain a mixture B;

[0009] S3, the mixture B is added to the solvent white oil No. 3, uniformly mixed at a temperature of 40-50℃ and a rotation speed of 800-1200r / min for 10-15min, and then the temperature is adjusted to 45-55℃ and the rotation speed is adjusted to 1000-1500r / min, and then the mixture A is added dropwise in the system to form a homogeneous and clear concentrated oil spill dispersant product.

[0010] Preferably, the first non-ionic surfactant Tween 80 is 10%-15% by mass fraction, the second non-ionic surfactant Span 20 is 15%-20% by mass fraction, the third non-ionic surfactant stearic acid polyoxyethylene ether is 15%-20% by mass fraction, the auxiliary propylene glycol is 5%-10% by mass fraction, and the solvent white oil No. 3 is 40%-50% by mass fraction.

[0011] Preferably, the first non-ionic surfactant Tween 80 is 15% by mass fraction, the second non-ionic surfactant Span 20 is 15% by mass fraction, the third non-ionic surfactant stearic acid polyoxyethylene ether is 15% by mass fraction, the auxiliary propylene glycol is 5% by mass fraction, and the solvent white oil No. 3 is 50% by mass fraction.

[0012] Preferably, in the step S1, the first nonionic surfactant Tween 80 is added into the auxiliary propylene glycol, mixed uniformly, then stirred at a temperature of 35℃ and a speed of 800r / min for 5min to obtain a mixture A.

[0013] Preferably, in the step S2, the second nonionic surfactant Span 20 and the third nonionic surfactant polyoxyethylene stearic acid ether are added into anhydrous ethanol, mixed uniformly, stirred at a temperature of 45℃ and a speed of 1000r / min for 10min to make them fully dissolved, then anhydrous ethanol is removed by distillation under reduced pressure to obtain a mixture B.

[0014] Preferably, in the step S3, the mixture B is added into the solvent No. 3 white oil, mixed uniformly at a temperature of 45℃ and a speed of 1000r / min for 10min, then the temperature is adjusted to 50℃ and the speed to 1200r / min, the mixture A is added dropwise in the system to form a homogeneous and clear concentrated oil spill dispersant product.

[0015] The application also provides an application of the concentrated offshore oil spill dispersant, wherein the dispersant prepared by the application is used for treating oil spill pollution on the water surface of the sea, a harbor, a river, a lake and a stream, or used for treating floating oil of cooling water and other discharged oil-containing sewage of a refinery, or used for dispersing treatment of floating oil of discharged water of an oil field, or used for oil removal cleaning of the inner and outer walls of a harbor wall, a dock, a trestle, a ship deck, a beach, an external body of an internal combustion engine, an oil tank and an oil pipe.

[0016] Preferably, when the water surface oil spill pollution is treated, the salinity of the water body is 0-35‰, the pH is 6.0-8.5, the oil agent ratio is 1:10-1:30, and the water body temperature is 0-20℃.

[0017] The concentrated offshore oil spill dispersant and the application thereof have the following beneficial effects:

[0018] The concentrated offshore oil spill dispersant is prepared by direct heating and compounding, hydrogen bond coupling is formed between the auxiliary propylene glycol and Tween 80, Tween 80 and Span 20 are dissolved in the solvent white oil by the solubilization of polyoxyethylene stearic acid ether, the similar molecular polarity between the solvent and the oil spill is utilized to increase the contact area of the surfactant and the oil spill, the 30s emulsification rate of the crude oil is 63%, the efficiency of the dispersant in dispersing the oil spill is improved, the 10min emulsification rate of the crude oil is 22%, the pH of the concentrated offshore oil spill dispersant is 7.0, the kinematic viscosity is 37.8mm 2 / s, the ignition point is greater than 70℃, the appearance is clear and transparent without stratification, the half death time of fish acute toxicity experiment is greater than 24h, and the biodegradability evaluation index is 33%, which is environmentally friendly. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 A flow chart of the steps of the present application.

[0020] Figure 2 Comparison chart of emulsification effect of concentrated offshore oil spill dispersant prepared in Example 1 on crude oil

[0021] A - no oil spill dispersant added test group; B - oil spill dispersant added test group

[0022] Figure 3 Comparison chart of emulsification stability of concentrated offshore oil spill dispersant prepared in Example 1 on crude oil

[0023] A - emulsified for 30s test group; B - emulsified for 10min test group

[0024] Figure 4 Comparison chart of emulsification stability of concentrated offshore oil spill dispersant prepared in Example 1 on motor oil (light oil)

[0025] A - emulsified for 30s test group; B - emulsified for 10min test group

[0026] Figure 5 Comparison chart of dispersion of concentrated offshore oil spill dispersant products prepared in Examples 1-5 DETAILED DESCRIPTION

[0027] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art without creative labor fall within the protection scope of the present application.

[0028] According to the quality ratio of different embodiments in Table 1, the first non-ionic surfactant Tween 80 is selected to add the auxiliary propylene glycol, mixed uniformly, then stirred at a temperature of 35℃ and a speed of 800r / min for 5min, to obtain the mixed material A. The second non-ionic surfactant Span 20 and the third non-ionic surfactant polyoxyethylene stearate (SG-6) are added in anhydrous ethanol, mixed uniformly, stirred at a temperature of 45℃ and a speed of 1000r / min for 10min to make them fully dissolved, and then anhydrous ethanol is removed by reduced pressure distillation to obtain the mixed material B. The mixed material B is added into the solvent No.3 white oil, mixed uniformly at a temperature of 45℃ and a speed of 1000r / min for 10min, and then the temperature is adjusted to 50℃ and the speed to 1200r / min, and the mixed material A is added dropwise in the system to form a homogeneous and clear concentrated oil spill dispersant product. In the embodiment, the manufacturers of Tween 80, Span 20 and polyoxyethylene stearate (SG-6) are Nantong Aches Chemical Co., Ltd. The white oil is type 3#, and the manufacturer is Guangdong Zhonghai Nanlian Energy Co., Ltd.

[0029] Table 1: different quality ratios of embodiments

[0030] Example 1 2 3 4 5 Comparative Example 1 Comparative Example 2 Tween 80 15 10 10 15 15 15 15 Ethylene glycol 5 5 5 10 5 0 5 SG-6 15 15 20 15 20 15 5 Span 20 15 20 15 15 20 15 15 White oil No. 3 50 50 50 45 40 50 60

[0031] The above embodiments 1-5 are measured, and the concentrated offshore oil spill dispersant of the embodiments is detected, and the specific detection is as follows:

[0032] (1) The pH, ignition point, kinematic viscosity and dispersion rate to crude oil of the prepared concentrated offshore oil spill dispersant are measured according to the method of national standard GB 18188.2000 and the internationally used BFT method.

[0033] (2) Zebrafish acute toxicity test: the zebrafish acute toxicity test is carried out according to the static water test method of the national standard of China. Before the test, the test zebrafish group is acclimated in the same environmental conditions (including pH, dissolved oxygen, temperature, etc.) as the test time and the continuous aeration dilution water for more than one week, so as to adapt to the test environment. During the acclimation period, the water is changed every day and the bait is fed once a day, and in order to keep the water environment clean, the feces and food residues are removed every day. 24h before the test, stop feeding, if the mortality of the fish during the acclimation period is more than 10%, the batch of fish is discarded and not used, and the test fish has no obvious disease and visible deformity. Before the formal test, individuals with similar size, complete fish, good expansion and good water resistance are selected from the acclimation for use.

[0034] (3) Biodegradability: the biodegradability of the developed oil spill dispersant is evaluated according to the ratio of BOD5 to COD, i.e. the biodegradability index of the national standard. The results are shown in Table 2.

[0035] Table 2 test results under different embodiments

[0036]

[0037]

[0038] Note: Due to the lack of hydrogen bonding between the auxiliary propylene glycol and Tween 80, the solubilization of stearic acid polyoxyethylene ether (SG-6) is greatly weakened, resulting in the formation of a clear and transparent microemulsion system between Tween 80 and the solvent white oil, and the formation of a complete dispersant product.

[0039] As can be seen from Table 2, the concentrated offshore oil spill dispersant prepared by the method (Examples 1-5) has a surfactant content of 50%-60%, which meets the requirements of the national standard GB 18188.1-2000, and the emulsification rate of Example 1 is the highest, with a 30s emulsification rate of 63% for crude oil and a 10min emulsification rate of 22% for crude oil, and the biodegradability is higher than the national standard requirement (>30%). Moreover, the pH of the concentrated offshore oil spill dispersant is greater than 7.0, the kinematic viscosity is greater than 29.7mm 2 / s, the ignition point is greater than 70℃, the appearance is clear and transparent without stratification, the half death time of fish acute toxicity test is greater than 24h, and it is environmentally friendly. Moreover, the concentrated offshore oil spill dispersant developed by the present application has a simple production process, low energy consumption, and is suitable for large-scale industrial production.

[0040] As can be seen from Table 2, the concentrated offshore oil spill dispersant prepared in Example 2 has some W / O reverse droplets due to the large amount of Span 20 added, which can cause poor emulsion stability. The concentrated offshore oil spill dispersant prepared in Example 3 has a large amount of SG-6 added, which can easily destroy the micelles composed of Tween 80, causing oil droplets to separate, and the large area of black shadow in the figure is caused by the oil droplets sticking to the glass slide after breaking through the micelles. The concentrated offshore oil spill dispersant prepared in Example 4 has a large amount of propylene glycol added due to the poor emulsification capacity, resulting in fewer micelles formed by the surfactant, and the oil droplets wrapped are large and unstable. The concentrated offshore oil spill dispersant prepared in Example 5 has a large amount of surfactant added, resulting in good emulsification effect but high kinematic viscosity, which is not conducive to practical application and spraying, and the biodegradability is slightly poor.

[0041] As can be seen from Table 2, the addition amount of stearic acid polyoxyethylene ether (SG-6) in Comparative Example 2 is small, the emulsification efficiency is greatly reduced, the 30s emulsification rate for crude oil is only 27%, the 10min emulsification rate for crude oil is only 3%, and the 30℃ kinematic viscosity is also reduced to 21.2mm 2 / s, which shows that the adding amount of the polyoxyethylene stearate (SG-6) has an important influence on the performance of the whole product, and the adding amount of the polyoxyethylene stearate (SG-6) should not be less than 15%.

[0042] Referring to Figure 5 (Testing bottle is fixed on a horizontal shaft, and the horizontal shaft is driven to rotate around the shaft center by 360° by a motor through gear transmission. The rotation speed is 33+1 r per minute, the seawater temperature is 10℃, and the seawater salinity is 33-35. The standard oil is sprayed on the surface of seawater in the testing bottle by using a syringe, and then the oil spill dispersant is sprayed at an oil agent ratio of 1:0.2, and after 2 minutes of 360° rotation, 30 seconds or 10 minutes of static state, a drop of oil-water mixture is quickly taken out from the same height of the testing bottle and observed under a 100 times microscope) It can be seen that the blank sample without adding the oil spill dispersant can also make the oil droplets suspended under the water surface for a short time under the shock, but once the shock environment is lost, the oil droplets will quickly float on the water surface. The oil droplets in examples 1 to 5 are wrapped by surfactant micelles to form O / W emulsion, so that the oil droplets cannot be aggregated again.

[0043] Comparing Figure 3 and Figure 4 It can be seen that the product has good dispersing effect on different quality of oil spills, and the dispersing stability for heavy oil is better than that for light oil.

[0044] The application further provides an application of the concentrated marine oil spill dispersant. The dispersant prepared by the application is used for treating oil spill pollution on the water surface of the sea, a port, a lake and a river, or for treating floating oil of cooling water and other discharged oil-containing sewage of a refinery, or for dispersing treatment of floating oil of discharged water of an oil field, or for oil removal cleaning of the inner and outer walls of a port wall, a dock, a trestle, a ship deck, a beach, an external body of an internal combustion engine, an oil tank, and an oil pipe. When the dispersant is used for treating the oil spill pollution on the water surface, the salinity of the water body is 0-35‰, the pH is 6.0-8.5, the agent-oil ratio is 1:10-1:30, and the water body temperature is 0-20℃.

[0045] The above is only a preferred embodiment of the application, but the application should not be limited to the contents disclosed in the embodiment and the drawings, so that equivalent or modified products completed without departing from the disclosed spirit of the application fall within the protection scope of the application.

Claims

1. A concentrated marine oil spill dispersant, characterized in that Comprising: The first nonionic surfactant Tween 80, the second nonionic surfactant Span 20, the third nonionic surfactant polyoxyethylene stearate, the auxiliary propylene glycol and the solvent No. 3 white oil, the dispersant is prepared by the following method: S1, select the first nonionic surfactant Tween 80, add the auxiliary propylene glycol, mix uniformly, then stir at the temperature of 30-40℃ and the speed of 600-1000r / min for 5-10min, get the mixture A; S2, add the second nonionic surfactant Span 20 and the third nonionic surfactant polyoxyethylene stearate in anhydrous ethanol, mix uniformly, stir at the temperature of 40-50℃ and the speed of 800-1200r / min for 10-15min to make it fully dissolved, remove the anhydrous ethanol by distillation under reduced pressure, get the mixture B; S3, add the mixture B into the solvent No. 3 white oil, mix uniformly at the temperature of 40-50℃ and the speed of 800-1200r / min for 10-15min, then adjust the temperature to 45-55℃ and the speed to 1000-1500r / min, add the mixture A dropwise in the system, form the homogeneous and clear concentrated oil spill dispersant product.

2. The concentrated offshore oil spill dispersant according to claim 1, characterized in that: The first nonionic surfactant Tween 80 is 10%-15% by mass fraction, the second nonionic surfactant Span 20 is 15%-20%, the third nonionic surfactant polyoxyethylene stearate is 15%-20%, the auxiliary propylene glycol is 5%-10%, and the solvent No. 3 white oil is 40%-50%.

3. The concentrated offshore oil spill dispersant according to claim 2, characterized in that: The first nonionic surfactant Tween 80 is 15% by mass fraction, the second nonionic surfactant Span 20 is 15%, the third nonionic surfactant polyoxyethylene stearate is 15%, the auxiliary propylene glycol is 5%, and the solvent No. 3 white oil is 50%.

4. The concentrated offshore oil spill dispersant according to claim 1, characterized in that: The step S1, select the first nonionic surfactant Tween 80, add the auxiliary propylene glycol, mix uniformly, then stir at the temperature of 35℃ and the speed of 800r / min for 5min, get the mixture A.

5. The concentrated marine oil spill dispersant according to claim 4, characterized in that: The step S2, add the second nonionic surfactant Span 20 and the third nonionic surfactant polyoxyethylene stearate in anhydrous ethanol, mix uniformly, stir at the temperature of 45℃ and the speed of 1000r / min for 10min to make it fully dissolved, remove the anhydrous ethanol by distillation under reduced pressure, get the mixture B.

6. The concentrated marine oil spill dispersant according to claim 5, characterized in that: The step S3, add the mixture B into the solvent No. 3 white oil, mix uniformly at the temperature of 45℃ and the speed of 1000r / min for 10min, then adjust the temperature to 50℃ and the speed to 1200r / min, add the mixture A dropwise in the system, form the homogeneous and clear concentrated oil spill dispersant product.

7. Use of a concentrated marine oil spill dispersant, characterized in that The dispersant of any one of claims 1-6 is used for treating overflow oil pollution on the surface of sea, harbor, lake and river, or for treating floating oil of cooling water and other discharged oil-containing sewage of oil refinery, or for dispersing treatment of floating oil of discharged water of oil field, or for deoiling cleaning of oil tank, oil tank, oil pipe, and the inner and outer wall of oil tank, oil tank, oil pipe of harbor shore, dock, trestle, ship deck, beach, internal combustion engine.

8. Use of a concentrated marine oil spill dispersant according to claim 7, characterised in that, When the dispersant is used for treating overflow oil pollution on the surface of water, the salinity of water body is 0-35‰, the pH is 6.0-8.5, the oil / dispersant ratio is 1:10-1:30, and the water temperature is 0-20℃.

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