A kind of bion oil-spill dispersant and preparation method thereof
Background technology
In recent years, along with developing rapidly of China's economic, to the quick increase of the oil equal energy source consumption of materials, the exploration exploitation of oil etc., accumulating refining amount also increase considerably.But owing to reasons such as misoperation or accident leakages, there is the excessive or discharging of oil in regular meeting, and oil spill accident takes place, and can cause serious environmental to pollute.Such oil spill has become in the various oil pollutions, and what particularly offshore oil pollution type occurrence frequency was the highest, distribution area is the widest, the extent of injury is maximum is a kind of.Oil pollution not only can cause the acute and slow poisoning of human body, more can growth, breeding and the whole ecological system of nature biotechnology be had an immense impact on.Like the petroleum component of human body suction high concentration, can cause the serious hindrance of nervous centralis immediately, tremble, the skin paleness, the chaotic and minimizing of pulse, reflection stops during especially severe, and bladder and proctoparalysis are at last because of heart failure death; Contain polycyclic aromatic hydrocarbon in the petroleum component, the not straight mineral oil that the contact petroleum distillation obtains can cause dermatitis, more can bring out human body and produce cutaneum carcinoma; Petroleum component can make planktonic organism acute poisonings such as algae and death just can exert an influence to the early development of fish-egg and fish when petroleum concentration is very low; Simultaneously, the birds that entail dangers to relies on aquatile to make a living, a large amount of oil spillings make the birds wing be stained with greasy dirt and can not circle in the air.Petroleum component also can influence the quality of marine product.Fish and shellfish have peculiar smell because of the oil pollution in the seawater.Show that according to data fish and shellfish are that life can be stained with the oil flavor in 24 hours in the seawater of 0.01mg/L at oil-containing; If concentration rises to 0.1mg/L, just peculiar smell can be arranged in 2-3 hour.
In view of above reason, the improvement oil pollution is imperative, has caused the great attention of country; In order to seek cost-effective governance way, scientific workers carry out broad research, make great efforts to seek a kind of safe, reliable, cost-effective improvement method.Wherein using chemical oil-spill dispersant is one of common mature technology of present fast processing marine oil overflow.Oil-spill dispersant can reduce the interfacial tension between oil spilling and the water through surfactant, thereby the rapid emulsification of oil is dispersed in the water.Can not adopt machinery recovery or fire-prone in emergency circumstances many, spray oil-spill dispersant in time, be the major measure of eliminating oil pollution and preventing fire.The development work of China's chemical classes oil-spill dispersant starts from the seventies in 20th century; Its product is mainly used in the oil spilling in offshore and oil field, shallow sea and handles; But performance indications and international advanced product still have gap; Some product exists that toxicity is big, stability and shortcoming such as emulsification rate is low, the scope of application is narrow, cost an arm and a leg, and therefore is necessary to develop a kind of new and effective oil-spill dispersant to adapt to the demand of domestic and international market.
Biological restoration is meant utilizes especially microorganism of biology, induces or accelerate the degradation process of noxious pollutant in the environment, finally is converted into the biotechnology of innocuous substance.Compare with traditional chemistry, physical treatment method, bioremediation technology has advantage: (1) pollutant is degraded, removes in the original place; (2) repair time is shorter; (3) handle on the spot, easy and simple to handle, surrounding environment is disturbed few; (4) less reparation funds are merely traditional chemical, physics is repaired 30%~50% of funds; (5) the human chance that directly exposes to the open air under these pollutants reduces; (6) do not produce secondary pollution, leftover problem is few.Bioremediation technology also normal and other chemistry, physics restorative procedure are united use, so that more effectively decompose and remove polluter.
On our earth, exist the various microorganism species of counting in necessarily.These microorganism fungus kinds are decomposed different debirs with own distinctive mode, thereby obtain oneself to grow, breed and needed goods and materials of other metabolic activity and energy.Meanwhile, these debirs are finally resolved into water and the carbon dioxide nontoxic, harmless to the Nature and Man class.On average, microorganism will breed a generation in per 20 to 30 minutes, this means that its quantity also will double.But obvious, in a specific system, microbial numbers can not unrestrictedly increase, and will finally reach a balance.Many factors will influence microbial numbers, such as their variation (debirs) of food source; The variation of environmental factor is like variation of acid-base value, temperature, humidity, oxygen concentration etc.
Based on the desirability to oxygen, microorganism fungus kind is divided into aerobic bacteria, anaerobic bacteria and double oxygen bacterium.Aerobic bacteria needs under the condition of aerobic, can grow and breeding; Anaerobic bacteria is surviving under the condition of anaerobic: the oxygen bacterium equal growth and breeding well under the situation of aerobic and anaerobic of holding concurrently.Though the bacterial classification that occurring in nature exists also can digest debirs as food, the time of cost is very long, possible decades even upward century-old.Therefore, can really be used for actual, realize business-like bacterial classification, necessarily at first extract from occurring in nature, then in the laboratory through special screening, and then cultivate the high-performance microorganism species of the extremely well-adapted that comes out.These high-performance microorganism species are more effective than the microbial population that exists in the nature, and they are thousands of times of occurring in nature flora to the decomposition rate of debirs, thereby can in one is asked when short, debirs be resolved into water and carbon dioxide.
Debirs are the important food sources of microorganism fungus kind, particularly as growth of microorganism, the needed important carbon source of breeding.In addition, some vitamin, mineral matter and amino acid like elements such as vitamin B1, riboflavin, calcium, phosphorus, potassium, leucine, tryptophan etc., also are growth of microorganism and keep active necessary nutriment.And these nutriments often do not exist in debirs.In fact, the shortage of any nutriment all possibly have a strong impact on microbial growth and breeding.Therefore, must in microorganism, add these necessary nutriments and can full out decompose, digest debirs the most efficiently to guarantee microorganism.
For animal and vegetable oil and petroleum-type derivative mineral wet goods is the organic matter on basis with the carbon-chain structure, and containing carbon number and be 5~9 hydrocarbon compound is volatile organic matter, and bigger toxicity is arranged when high concentration; Contain carbon number and be the minimum and easily biological-degradable of 10~22 hydrocarbon compound toxicity; Containing carbon number is hypotoxicity more than 22 hydrocarbon compound, low aqueous solubility, and be solid state, not easily biological-degradable at normal temperatures; And for phenyl ring class and cycloalkane compound, particularly Fourth Ring and Geng Duo the ring hydrocarbon, like anthracene, pitch, pitch etc., be difficult for most biolytic; The more difficult complete biodegradable of double bond containing hydrocarbon; And the easiest complete biodegradable of saturated alkane of straight chain.
Up to now, the microorganism of known ability degraded oil hydro carbons is genus surplus in the of totally 100, kind more than 200, and they belong to bacterium, actinomyces, mould and algae.Wherein common bacterium has bacillus, pseudomonad etc.; Yeast, aspergillus, mould etc. are arranged in the fungi; Microorganism tends to produce biosurfactants such as some glycolipids, polysaccharide, protein and lipoprotein in the biodegradation process to organic pollution materials; This type material can the cut oil hydrocarbon, can strengthen the degree biological capable of using of petroleum hydrocarbon to a certain extent, improves the validity of biological restoration.
Summary of the invention
When leaking oil spilling to existing traditional chemical oil-spill dispersant product treatment, it is many to consume reagent, and the oil spilling degradation speed is slow, and processing time period is long, only transfer the pollution can not pollution degradation etc. weak point; The present invention provides a kind of oil spilling bion oil-spill dispersant that contains the surfactant and the oil spilling microorganism fungus kind of degrading fast simultaneously.This bion oil-spill dispersant is applied to oil spill accident when handling, and compares with existing chemical oil-spill dispersant, has fast and convenient, energy-saving and cost-reducing, environmental emission reduction, directly falls remarkable advantage such as dirt, can obviously improve the degradation effect to petroleum pollution.It also can be applicable to the on-the-spot biological restoration of other multiple petrochemical industry series products when urgent leakage pollution accident takes place.
The main creation point of bion oil-spill dispersant of the present invention is the microorganism fungus kind that in the oil spilling agent that contains surfactant, adds the degraded oil spilling simultaneously, and this handles the oil spilling field in the oil spilling agent is initiative.
Bion oil-spill dispersant treatment fluid of the present invention is made up of host, contains microorganism 0.1~30 weight % of surfactant 0.1~40 weight %, degraded oil spilling in the host, assistant agent 0.1~20 weight %, and surplus is a water.
Surfactant in the bion oil-spill dispersant treatment fluid host of the present invention is a rhamnolipid; Sophorolipid; The marine alga glycolipid; Lipopeptid; Lipoprotein; Phosphatidyl-ethanolamine; Phosphatidyl glycerol; APEO; Polyethenoxy ether; APG; Alkyltrimethylammonium second lactone; APES; The alkyl ether carboxy acid salt; Sorbitan oleate; Polyoxyethylene sorbitol acid anhydride oleate; Alkylbenzenesulfonate; Alkyl phosphate and salt thereof; The mixture of one or more in many alkylsurfuric acids ester sodium salt.
The assistant agent of bion oil-spill dispersant treatment fluid of the present invention is one or more the mixture in vitamin, mineral matter, corn steep liquor, dusty yeast, isopropyl alcohol, ethylene glycol, amino acid, aminoglycoside, polyethylene glycol, ethylene glycol ethyl ether, butyl glycol ether and the propane diols butyl ether.
The microorganism of the degraded oil spilling of bion oil-spill dispersant treatment fluid of the present invention is one or more the mixture in bacillus or the saccharomycete.Flora number in the every gram of the microorganism of above-mentioned degraded oil spilling is not less than 1 * 10
5Individual.
In the bion oil-spill dispersant of the present invention except the surfactant that contains chemical synthesis; Also contain the synthetic biosurfactant of microorganism simultaneously; The surfactant of two types of separate sources plays a role simultaneously; Make bion oil-spill dispersant of the present invention have better emulsification dispersing characteristic, this also has uniqueness aspect oil spilling agent processing oil spilling.
Surfactant is one type can significantly reduce the capillary material of solvent, and the past is generally obtained by chemical synthesis.The surfactant of chemical synthesis comprises cationic surfactant, anion surfactant, amphoteric surfactant, non-ionic surface active agent etc.The molecular structure of these surfactants has hydrophilic and characteristics oleophylic simultaneously, all has certain permeance property, wettability, emulsifiability, dispersive property and foam performance etc.And biosurfactant is to obtain by biotechnology is synthetic; Compare with synthetic surfactant; Except both have many similarities on performance, a distinguishing feature of biosurfactant is exactly can be by the microbial degradation of occurring in nature, and all as safe as a house to man and nature.Simultaneously, its structure is also more complicated than synthetic surfactant, and molecular weight is higher, has more functional group, has some better infiltrations, wetting, emulsification and dispersing characteristic.In view of these characteristics of biosurfactant, and the continuous enhancing of people's environmental consciousness, the demand to biosurfactant in industrial application constantly strengthens, and substituting traditional synthetic surfactant simultaneously gradually also becomes a kind of trend.And the topmost source of biosurfactant is exactly the microorganism from degraded oil.
The preparation of bion oil-spill dispersant of the present invention divided for five steps: 1) clean material-compound tank: prepare before the bion oil-spill dispersant for the first time, must the material-compound tank water be removed clean.2) preparation host: each component of host poured in the material-compound tank in proportion stir; 3) add assistant agent: each component of assistant agent is directly joined in the host after the dilution in proportion.4) microorganism of adding degraded oil spilling: the microorganism of treated various degraded oil spillings is directly joined in the treatment fluid that had before prepared in proportion.Above component add finish after, stir and get final product.
Bion oil-spill dispersant of the present invention can host, assistant agent adds microorganism and uses together, can host add microorganism and use, and can also dilute use.The dilution ratio wide range of dispersant, the concentrate that need not dilute from direct use is to all can by 1: 100 dilution proportion with water.These depend primarily on different applications, different oil spilling oil removing modes, different factors such as greasy dirt amount.Such as complicated to some textural anomalies, under the big heavily contaminated situation of oil spillage, also can directly use host to add the microorganism concentrate or add assistant agent again, need not dilution and use.
Beneficial effect of the present invention: the present invention is directed to the present situation that existing oil spilling greasy dirt is handled; Successfully developed the new bio type oil-spill dispersant that contains kinds of surface activating agent and degraded oil spilling microorganism fungus kind first; Thereby a kind of possess quick emulsification oil spilling and the biological renovation method that decomposes the greasy dirt dual-use function are provided; Has remarkable advantages such as efficiently subtracting dirty and environmental protection; Realization has reduced operating procedure with the emulsification and the purpose of decomposing as a PROCESS FOR TREATMENT of oil spilling, is the progress of a great revolution property in this field.Bion oil-spill dispersant of the present invention is applied to the emergency treatment under the oil spill situation, compares with existing chemical oil spilling agent, and the product emulsibility is better; Dispersive property is stronger, and oil can be diluted in the water more quickly, and in emulsification and dilution; Microorganism is just started working, degraded oil gradually, particularly wherein some main toxic components; Like the arene compound of benzene class, these all are strong carcinogenic substances.At short notice, they will be degraded and become some avirulences or hypotoxic organic molecule, can not cause huge pollution to environment again.
A few strain bacterium of the present invention is respectively bacillus (Bacillus sp.) WB1, bacillus (Bacillus sp.) WB2 and saccharomycete (Saccharomyces sp.) MTH-8.The culture presevation of bacillus WB1 number is CGMCC No.3669; The culture presevation of bacillus WB2 number is CGMCC No.3670, and two strain bacterium preservation times were on March 19th, 2010; The culture presevation of saccharomycete MTH-8 number is CGMCC No.0525, and the preservation time is on December 27th, 2000; The depositary institution of three strain bacteriums is China Committee for Culture Collection of Microorganisms common micro-organisms center.Wherein bacillus WB1 separates the earth from China's Daqing oil field, and its bacterium colony is coarse, and is opaque, do not glisten, and is white; Cell is oval to shaft-like, gemma is arranged, gram-positive bacteria; Growth pH value scope is 6.0-8.0, the righttest 7.0; Temperature range 20-50 ℃, the righttest 35 ℃; Another bacillus WB2 separates the earth from China's Shengli Oil Field, and its bacterium colony is coarse, half moistening transparent, do not glisten, be dirty white; Cell is oval to shaft-like, gemma is arranged, gram-positive bacteria; Growth pH value scope is 6.0-8.0, the righttest 7.0; Temperature range 20-50 ℃, the righttest 37 ℃; Saccharomycete MTH-8 separates the earth from China Liaohe Oil Field, its bacterium colony milky, glossy, more smooth, neat in edge; Cell is circle, ellipse or cylindricality, no gemma, gram-positive bacteria; Growth pH value scope is 5.0-7.5, the righttest 6.5; Temperature range 20-50 ℃, the righttest 30 ℃.
The specific embodiment
Embodiment 1:
The preparation of bion oil-spill dispersant: the bion oil-spill dispersant is by host in the present embodiment, and assistant agent and microorganism are formed, and it is following that its weight is formed proportioning; Contain rhamnolipid 5%, APEO sorbitan oleate 5%, sorbitan oleate 5%, bacillus WB1 1%; Bacillus WB2 1%, saccharomycete MTH-81%, vitamin B1 0.1%; Isopropyl alcohol 2%, butyl glycol ether 2%, water 77.9%.
Earlier material-compound tank is cleaned up with distilled water during preparation; Then to wherein adding the pure distilled water of 779 grams; According to rhamnolipid 50 grams, APEO sorbitan oleate 50 grams, the host component ratio of sorbitan oleate 50 grams joins in the material-compound tank and stirs subsequently; Add vitamin B1 1 gram, isopropyl alcohol 20 grams, butyl glycol ether 20 grams wait assistant agent component proportion of composing directly in the host after dilute by weight.Microorganism bacillus WB1 10 grams that add treated degraded oil spilling, bacillus WB2 10 grams, saccharomycete MTH-810 restrains in the treatment fluid that had before prepared.Above component add finish after, stir and get final product.
Embodiment 2:
The preparation of bion oil-spill dispersant: the bion oil-spill dispersant is made up of host, assistant agent and microorganism in the present embodiment, and it is following that its weight is formed proportioning, contains alkyl glucoside 10%; APEO sorbitan oleate 2%, polyoxyethylene oleate 2%, sorbitan oleate 2%, bacillus WB1 1%; Bacillus WB2 1%, dusty yeast 0.1%, urea 0.2%; Phosphatidyl glycerol 0.2%, butyl glycol ether 5%, water 76.5%.
Earlier material-compound tank is cleaned up with distilled water during preparation; Then to wherein adding the pure distilled water of 4225 grams; According to alkyl glucoside 500 grams, APEO sorbitan oleate 100 grams, the host component ratio of polyoxyethylene oleate 100 grams, sorbitan oleate 100 grams, butyl glycol ether 250 grams joins in the material-compound tank and stirs subsequently; Add dusty yeast 5 grams, urea 10 grams, phosphatidyl-ethanolamine 10 grams wait the assistant agent component in proportion directly in the host after dilute.Add microorganism bacillus WB1 50 grams of treated degraded oil spilling again, bacillus WB2 50 restrains in the treatment fluid that had before prepared.Above component add finish after, stir and get final product.
Embodiment 2:
The preparation of bion oil-spill dispersant: the bion oil-spill dispersant is made up of host, assistant agent and microorganism in the present embodiment, and it is following that its weight is formed proportioning, contains marine alga glycolipid 1%, polyoxyethylene oleate 2%; Sorbitan oleate 3%, bacillus WB1 2%, bacillus WB2 2%; Dusty yeast 0.1%, urea 0.2%, phosphatidyl-ethanolamine 0.2%; Polyethylene glycol 5%, water 84.5%.
Earlier material-compound tank is cleaned up with distilled water during preparation; To wherein adding the pure distilled water of 4225 grams, the host component ratio that restrains according to marine alga glycolipid 50 grams, polyoxyethylene oleate 100 grams, sorbitan oleate 150 grams, polyethylene glycol 250 subsequently joins in the material-compound tank and stirs then; Add dusty yeast 5 grams, urea 10 grams, phosphatidyl-ethanolamine 10 grams wait the assistant agent component in proportion directly in the host after dilute.Add microorganism bacillus WB1 100 grams of treated degraded oil spilling again, bacillus WB2 100 restrains in the treatment fluid that had before prepared.Above component add finish after, stir and get final product.
Embodiment 4:
The mensuration (environment temperature is controlled at 20-25 ℃ during test) of preparation bion oil-spill dispersant emulsification rate among the embodiment 2
1. the commercially available thick sea salt of 30 grams is dissolved in 1 liter of distilled water, filters the preparation that artificial seawater is accomplished in the back;
2. in 100 milliliters of separatory funnels, add 50 milliliters of artificial seawaters of people respectively with 50 milliliters of graduated cylinders, limit oil ring to be invested in the water surface in plastics.
3. extract the standard oil (through the Shengli crude of 100 ℃ of toppings) of 1 gram with 1 milliliter of syringe;, clamp-ons by electronic balance after getting on tare weight in the plastics limit oil ring in the separatory funnel; 1 milliliter of syringe with the band syringe needle extracts the biological oil-spill dispersant of 0.2 gram, and the pasta after electronic balance gets on tare weight in plastics limit oil ring evenly drips the oil-spill dispersant of amount of calculation.
4. after above-mentioned separatory funnel being vibrated 3 minutes simultaneously, take out rapidly, on vertical transitions to the separatory funnel frame, left standstill 10 minutes.This process is sure not to rock separatory funnel.
5. repeat above 2-3 step, in an other separatory funnel, add the artificial seawater of people, standard oil and oil-spill dispersant, left standstill 30 seconds after 4 vibrations set by step.
6. after step 4 and 5 liang of component liquid funnels being left standstill the stipulated time, in time respectively emit in 20 milliliters of emulsion to 20 milliliter graduated cylinders, read accurate volume to 0.1 milliliter from the bottom.
7. the emulsion of step 6 is fallen respectively in two 50 milliliters of separatory funnels of people, and add the chloroform (with the oil that adheres on the careful flushing dose barrel of chloroform) of people and emulsion equal volume with the graduated cylinder of correspondence, oscillation extraction 5 minutes leaves standstill and treated layering in 30 minutes.
8. with the about 0.2 milliliter of air of 5 milliliters of syringe pumps of band syringe needle, pass water layer rapidly and advance people's extract layer.After air is extruded in the syringe, stay a minute, extract 1 milliliter of extract, leave the water rapidly, extrude a little and clean syringe needle with filter paper.With this extract washing syringe and cuvette.Repeat aforesaid operations once.
9. 8 sampling methods set by step extract about 3 milliliters of extracts and place cuvette, and are to be measured.
10. production standard curve.Accurately take by weighing 500 milligrams of standard oils, be dissolved in 25 milliliters of chloroforms, obtain 20000 mg/litre stostes.Prepare the test oil-chloroform soln of series concentration as required, for example, get 1,2,3,4,5 milliliter of stoste respectively, be diluted to 10 milliliters, preparation series standard solution, respective concentration is respectively 2000,4000,6000,8000,10000 mg/litre.Under 650 nano wave lengths, measure the series standard solution absorbency with 0.5 centimetre of cuvette, draw the calibration curve of oil concentration and absorbance, or carry out regression Calculation, obtain coefficient correlation, slope and intercept.
11. the result calculates, the result of the test of biological oil-spill dispersant 30 seconds and 10 minutes emulsification rates is represented with percentage, is respectively 82% and 45%, all apparently higher than the emulsification rate 60% of oil-spill dispersant product national requirements and 20% index standard.
Attach: the emulsification rate computing formula:
In the formula: T-emulsification rate, %;
The concentration of oil that C-is checked in or calculates according to regression coefficient from calibration curve by the extract absorbance, mg/litre;
A-extract extension rate;
51.2-the numerical value of artificial seawater, oil and conventional type dispersant volume sum
Embodiment 5
The bion oil-spill dispersant oily ability test falls: with the bion oil-spill dispersant that is made in the present embodiment 1; Join for 0.4 milliliter in 100 milliliters of artificial seawaters that contain 2 gram Shengli crudes according to the amount that adds former weight of oil 20%; Place on 35 ℃ of shaking tables and cultivated 12-24 hour, rotating speed is 150~250rpm.With what add distilled water is blank.Cultivate when finishing; In nutrient solution, add benzinum, the centrifugal O/w emulsion of breaking, organic facies is placed in the beaker of constant weight in advance with the granular anhydrous sodium sulphate filtering means dehydration; Room temperature nitrogen stripping adopts Residual oil content in gravimetric method and the gas chromatography determination nutrient solution respectively to constant weight.Formula calculates the biological degradation rate (A) of petroleum hydrocarbon below adopting:
A=w
0-w
1/w
0×100
In the formula: W
0Be Residual oil content in the blank seawater liquid; W
1Be Residual oil content in the seawater liquid that adds the bion oil-spill dispersant.
Experimental result shows: cultivate after 24 hours, the degradation rate A that adds the seawater liquid PetroChina Company Limited. hydrocarbon of bion oil-spill dispersant reaches 70.3%.Former oil residue has been carried out the gc analysis test, and the content of various compositions significantly reduces in the total petroleum hydrocarbon, and wherein short chain alkanes has reduced 95%, and long chain alkane has reduced 72%, and aromatic hydrocarbon has reduced 64%.
Description of drawings
Fig. 1 is for adding the preceding gas chromatographic detection result to the petroleum component in the sample seawater of bion oil-spill dispersant;
Fig. 2 is 24 hours gas chromatographic detection results to the petroleum component in the sample seawater behind the adding bion oil-spill dispersant.