CN104962239A - Eco-friendly oil spill dispersant and preparation method thereof - Google Patents
Eco-friendly oil spill dispersant and preparation method thereof Download PDFInfo
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- CN104962239A CN104962239A CN201510292114.2A CN201510292114A CN104962239A CN 104962239 A CN104962239 A CN 104962239A CN 201510292114 A CN201510292114 A CN 201510292114A CN 104962239 A CN104962239 A CN 104962239A
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Abstract
The invention relates to an eco-friendly oil spill dispersant and a preparation method thereof. The preparation method comprises selecting an anionic surfactant and first and second nonionic surfactants, carrying out compounding, adding ethylene glycol monobutyl ether as a solvent and PEG as a stabilizing agent into the compound and carrying out compounding to obtain the eco-friendly oil spill dispersant. The anionic surfactant is rhamnolipid. The first nonionic surfactant is sophorolipid. The second nonionic surfactant is alkyl carbohydrate. The eco-friendly oil spill dispersant has a HLB value of 8.36-14.72 and kinematic viscosity of 4.98-5.68mm<2>/s.
Description
Technical field
The present invention relates to water pollution prevention and control field, be specifically related to a kind of environmentally friendly oil-spill dispersant and preparation method thereof.
Background technology
The petroleum pollution in ocean overwhelming majority is from mankind's activity, wherein with ship, offshore oil and gas exploitation, and littoral discharge of industrial wastes is main, due to habitat of oil and area of consumption skewness, therefore, world's year petroliferous over half be sea borne by oil carrier, this just brings the threat of petroleum pollution to the ocean accounting for earth surface 71%, the sudden petroleum pollutions such as particularly oil tanker collision, marine oil field leakage.The destruction of petroleum pollution in ocean to Marine ecosystems is difficult to retrieve.Oil is across the sea floating, diffuses to form oil film rapidly.Oil film forms the reoxygenation effect hindering water body, affects marine plankton growth, destroys marine ecology balance, can destroy beachscape in addition, affect beach aesthetic values.
Oil-spill dispersant is by kinds of surface promoting agent and strong infiltrative solvent composition, mainly for the treatment of marine oil overflow and cleaning greasy dirt, is the necessary article administering petroleum pollution in ocean.The mechanism of action of oil-spill dispersant is by oil slick emulsification, forms fine particle and is scattered in water, be mainly applicable to the oil spilling process of exposed waters.
Prior art is also few about the document of oil-spill dispersant, such as, describe in CN 102335493A a kind of for there is oil spill accident time carry out oil spilling emulsification by tensio-active agent and carry out the biological oil spilling dispersing agent of quick bio repair simultaneously with microorganism, it is characterized in that the fat corrected milk(FCM) rate of this oil-spill dispersant can reach or exceed the requirement of oil-spill dispersant product GB, and containing degraded oil spilling microorganism in dispersion agent, can with oil co-cultivation remarkable content of all kinds of main organic hydrocarbon component in degraded oil after 24 hours, directly eliminate these poisonous components fast to the pollution of physical environment and harm.Although the tensio-active agent used is rhamnolipid, undesirable in dispersion and emulsion effect.And use yeast preservation fermentation means, use scale limited, poor effect.
But the oil-spill dispersant that prior art exists is unsatisfactory in dispersion and emulsion effect, therefore developing a kind of efficient, eco-friendly oil-spill dispersant is that research in art is crucial.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, develop a kind of environmentally friendly oil-spill dispersant (emulsifying agent).
Technical scheme of the present invention is as follows.
A first aspect of the present invention relates to a kind of environmentally friendly oil-spill dispersant, comprises anion surfactant, the first nonionogenic tenside, the second nonionogenic tenside, stablizer PEG and solvent ethylene glycol butyl ether;
Described anion surfactant is rhamnolipid, and the first described nonionogenic tenside is sophorolipid, and the second described nonionogenic tenside is alkyl sugar;
In mass fraction, described anion surfactant is 0.0785-2.35 part;
First described nonionogenic tenside 0.083-4.105 part;
Second described nonionogenic tenside 0.1325-4.015 part;
Described solvent is 4.955 parts;
The HLB value of described environmentally friendly oil-spill dispersant is between 8.36 ~ 14.72, and kinematic viscosity is between 4.98 ~ 5.68mm
2between/s.
To the 30s emulsification rate of crude oil between 5.0% ~ 26.5%.
Preferably, anion surfactant is 0.2400 part; First nonionogenic tenside is 0.7450 part; Second nonionogenic tenside is 4.0150 parts.
Preferably, anion surfactant is 1.1450 parts; First nonionogenic tenside is 0.3610 part; Second nonionogenic tenside is 3.4900 parts.
A second aspect of the present invention relates to the preparation method of above-mentioned a kind of environmentally friendly oil-spill dispersant,
According to the mass fraction of each component, first select anion surfactant and first, second nonionogenic tenside to carry out composite, then add solvent ethylene glycol butyl ether and stablizer PEG carries out composite, obtain the environmentally friendly oil-spill dispersant of described one.
A third aspect of the present invention relates to the application of above-mentioned a kind of environmentally friendly oil-spill dispersant, for the treatment of the overflow petroleum pollution on the water surface in ocean, harbour, river, rivers and lakes; Or float oil handling for refinery water coolant and other discharge oily(waste)water; Or the dissipation process for oil field discharge water oil slick or the ectosome for harbor wall, dock, trestle, boat deck, beach, oil engine and cargo tank, oil tank, oil pipe the de-oiling cleaning of inside and outside wall.
Preferably, during for the treatment of overflow petroleum pollution on the described water surface, water salinity is 0 ~ 35 ‰, pH is 6.0 ~ 8.5, and agent-oil ratio is 1:10-1:30.
Preferably, agent-oil ratio is 1:10.
Preferably, water temperature is 0 ~ 20 DEG C.
In the present invention, the HLB value of oil-spill dispersant calculates carries out the calculating of biased sample HLB value according to formula below:
In the present invention, the mensuration of the emulsification rate of oil-spill dispersant measures according to the method for GB GB/T-6369-2008.
After oil-spill dispersant fully mixes in certain proportion with crude oil, then be added in seawater (or artificial seawater), through vibration, form emulsion.After stratification, with the oil in solvent extraction emulsion layer.Measure the optical density value of extraction liquid, find corresponding emulsification oil mass from typical curve, thus calculate the size of emulsification rate.Calculation formula is as follows:
C is the concentration measured, and v is the volume of extraction liquid, and m is the quality of the mixture of oil-spill dispersant (emulsifying agent) and the oil added.
In the present invention, the mensuration of viscosity adopts NDJ-79 rotary viscosimeter instrument (Shanghai Sen Di scientific instruments equipment company limited) working sample kinetic viscosity.At the zero point of adjusting viscosity meter, the oil-spill dispersant prepared is joined in viscometer, open viscosity apparatus, take reading after stable reading, obtain kinetic viscosity.The density of Simultaneously test sample.Kinetic viscosity is obtained kinematic viscosity divided by the density of sample solution.
In this area, toxic effect evaluating is the important indicator evaluating oil-spill dispersant performance.In acute toxicity test for aquatic organism, conventional median lethal concentration LC50 characterizes.Median lethal concentration LC50 refers in certain hour, makes the concentration of toxicant needed for the dead half of biological subject.The method calculating LC50 adopts method of linear interpolation conventional in this area.
Method of linear interpolation (straight-line interpolation) refers to makes a concentration-dead response line, a numerical value required by interpolation according to the animal dead percentage ratio of two or more experimental concentration group.Method of linear interpolation is a kind of short-cut method of graphiccalculation LC50, is widely used in Aquatic Toxicity Test.When asking median lethal concentration with method of linear interpolation, at least must there are such two concentration in the concentration group of Setup Experiments: want for one to cause the experimental animal on 50% dead; Another mortality ratio occurred then will lower than 50%.According to the mortality ratio of biological subject under the different concns, different time of each oil-spill dispersant, try to achieve the LC50 value of 96h with method of linear interpolation mapping.
The test organisms that the present invention chooses is halogen worm (Artemia), it is the extremely euryhalinous zooplankton of one, belong to the secondary consumer in ocean, distributed more widely all over the world, its resource is very abundant, be the abundant bait such as protein of raising shrimp, crab, fish, and the susceptibility of halogen worm to the exogenous poisonous substance of many kinds is high, has been widely used as the biological subject of toxicity test abroad.According to preliminary result, with halogen worm for biological subject, the present invention have studied oil-spill dispersant to the halogen worm Acute Toxicity of 96 hours.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described in detail.
According to the quality proportioning of different experiments group # in table 1, first select rhamnolipid and sophorolipid, alkyl glycoside to carry out composite, then add solvent ethylene glycol butyl ether and stablizer PEG carries out composite, obtain the environmentally friendly oil-spill dispersant of described one.
Table 1
Measure above-mentioned experimental group embodiment 1-11, result is as shown in table 2.
Table 2
Table 2 can be found out, the HLB value of described environmentally friendly oil-spill dispersant is between 8.36 ~ 14.72, and kinematic viscosity is between 4.98 ~ 5.68mm
2between/s.And also have larger difference to the 30s emulsification rate of crude oil, between 5.0% ~ 26.5%.Wherein, the formulated milk rate being numbered embodiment 11 is the highest, reaches 26.5%, and this formula is the alkyl glycoside containing the rhamnolipid of 0.2400g, the sophorolipid of 0.7450g and 4.0150g in the butyl glycol ether of 4.955g.The formulated milk rate being numbered RSA-8 is also higher, reaches 24.3%.This formula is the alkyl glycoside containing the rhamnolipid of 1.1450g, the sophorolipid of 0.3610g and 3.4900g in the butyl glycol ether of 4.955g.
The emulsification rate of composite rear surface promoting agent improves greatly, wherein, is numbered 2.5 times and 5.4 times that embodiment 11 oil-spill dispersant emulsification rate is respectively single rhamnolipid, sophorolipid and alkyl glycoside emulsification rate; Above-mentioned analytical results shows, the composite rear generation synergy of kinds of surface promoting agent, improves greatly to the more single tensio-active agent of the emulsification rate of crude oil.
Oil spilling emulsifying agent of the present invention achieves unforeseeable technique effect.Oil-spill dispersant embodiment 11 of the present invention meets the requirement of GB 18188.1-2000.
By testing the dead concentration of halogen worm under 96 hours conditions, known, median lethal concentration LC50 is between 8179.06-8201.01mg/L, its toxicity is much larger than main flow oil-spill dispersant toxicity (about 41.05) on market, and this illustrates that the toxic effect of the oil-spill dispersant of the present invention's exploitation is better than main flow oil-spill dispersant in the market.
Claims (10)
1. an environmentally friendly oil-spill dispersant, is characterized in that, comprises anion surfactant, the first nonionogenic tenside, the second nonionogenic tenside, stablizer PEG and solvent ethylene glycol butyl ether;
Described anion surfactant is rhamnolipid, and the first described nonionogenic tenside is sophorolipid, and the second described nonionogenic tenside is alkyl sugar;
In mass fraction, described anion surfactant is 0.0785-2.35 part.
First described nonionogenic tenside 0.083-4.105 part.
Second described nonionogenic tenside 0.1325-4.015 part.
Described solvent is 4.955 parts.
The HLB value of described environmentally friendly oil-spill dispersant is between 8.36 ~ 14.72, and kinematic viscosity is between 4.98 ~ 5.68mm
2between/s.
2. the environmentally friendly oil-spill dispersant of one according to claim 1, is characterized in that, to the 30s emulsification rate of crude oil between 5.0% ~ 26.5%, under 96 hours conditions, halogen worm median lethal concentration LC50 is between 8179.06-8201.01mg/L.
3. the environmentally friendly oil-spill dispersant of one according to claim 1, is characterized in that, described anion surfactant is 0.2400 part; The first described nonionogenic tenside is 0.7450 part; The second described nonionogenic tenside is 4.0150 parts.
4. the environmentally friendly oil-spill dispersant of one according to claim 1, is characterized in that, described anion surfactant is 1.1450 parts; The first described nonionogenic tenside is 0.3610 part; The second described nonionogenic tenside is 3.4900 parts.
5. prepare the method for the environmentally friendly oil-spill dispersant described in claim 1-4 any one for one kind, it is characterized in that, according to the mass fraction of each component, first anion surfactant and first, second nonionogenic tenside is selected to carry out composite, add solvent ethylene glycol butyl ether again and stablizer PEG carries out composite, obtain the environmentally friendly oil-spill dispersant of described one.
6. the environmentally friendly oil-spill dispersant of one for preparing of a method according to claim 5.
7. an application for the dispersion agent described in claim 1-4 any one or dispersion agent according to claim 6, is characterized in that, for the treatment of the overflow petroleum pollution on the water surface in ocean, harbour, river, rivers and lakes; Or float oil handling for refinery water coolant and other discharge oily(waste)water; Or the dissipation process for oil field discharge water oil slick or the ectosome for harbor wall, dock, trestle, boat deck, beach, oil engine and cargo tank, oil tank, oil pipe the de-oiling cleaning of inside and outside wall.
8. application according to claim 7, is characterized in that, during for the treatment of overflow petroleum pollution on the described water surface, water salinity is 0 ~ 35 ‰, pH is 6.0 ~ 8.5, and agent-oil ratio is 1:10-1:30.
9. application according to claim 8, is characterized in that, agent-oil ratio is 1:10.
10. application according to claim 8, is characterized in that, water temperature is 0 ~ 20 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106082392A (en) * | 2016-05-07 | 2016-11-09 | 国家海洋局北海环境监测中心 | A kind of method that can repair marine oil spill pollution environment-friendly high-efficiency |
| CN106811313A (en) * | 2016-12-08 | 2017-06-09 | 中海石油环保服务（天津）有限公司 | A kind of environmentally friendly oil sludge and sand cleaning agent and its preparation and application |
| CN108276459A (en) * | 2018-01-08 | 2018-07-13 | 扬州工业职业技术学院 | A kind of NAPG-SiO2Nano material and its application as oil-spill dispersant |
| CN111534281A (en) * | 2020-04-01 | 2020-08-14 | 中国海洋大学 | Environment-friendly oil spilling dispersing agent and preparation method thereof |
-
2015
- 2015-06-01 CN CN201510292114.2A patent/CN104962239A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106082392A (en) * | 2016-05-07 | 2016-11-09 | 国家海洋局北海环境监测中心 | A kind of method that can repair marine oil spill pollution environment-friendly high-efficiency |
| CN106811313A (en) * | 2016-12-08 | 2017-06-09 | 中海石油环保服务（天津）有限公司 | A kind of environmentally friendly oil sludge and sand cleaning agent and its preparation and application |
| CN108276459A (en) * | 2018-01-08 | 2018-07-13 | 扬州工业职业技术学院 | A kind of NAPG-SiO2Nano material and its application as oil-spill dispersant |
| CN111534281A (en) * | 2020-04-01 | 2020-08-14 | 中国海洋大学 | Environment-friendly oil spilling dispersing agent and preparation method thereof |
| CN111534281B (en) * | 2020-04-01 | 2023-01-20 | 中国海洋大学 | Environment-friendly oil spilling dispersing agent and preparation method thereof |
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Application publication date: 20151007 |