阅读说明：本技术 溢油修复剂及其制备方法、溢油的原位修复方法 (Oil spill repairing agent, preparation method thereof and oil spill in-situ repairing method ) 是由 王恒伟 于 2019-10-10 设计创作，主要内容包括：本发明涉及溢油修复剂及其制备方法、溢油的原位修复方法,所述溢油修复剂的制备方法包括：提供第一载体,第一载体为具有多孔结构的木质纤维载体；提供微生物菌剂悬液,将第一载体与微生物菌剂悬液混合,以使第一载体吸附有微生物,得到第二载体；提供含琼脂和表面活性剂的水溶液,将第二载体与水溶液在容器中混合,使琼脂包裹第二载体形成中间物,使容器中的中间物分散并形成颗粒,通过气流吹散,得到溢油修复剂。本发明制备方法得到的溢油修复剂密度小于水,能分散并漂浮于水面,且随着琼脂在水环境中的逐步破碎和降解,木质纤维载体吸附的微生物逐步释放并与水面的油污充分接触,具有良好的原位修复作用。(The invention relates to an oil spill repairing agent, a preparation method thereof and an in-situ repairing method of oil spill, wherein the preparation method of the oil spill repairing agent comprises the following steps: providing a first carrier, wherein the first carrier is a wood fiber carrier with a porous structure; providing a microbial agent suspension, and mixing a first carrier with the microbial agent suspension to enable the first carrier to adsorb microorganisms to obtain a second carrier; providing an aqueous solution containing agar and a surfactant, mixing the second carrier and the aqueous solution in a container, enabling the agar to wrap the second carrier to form an intermediate, enabling the intermediate in the container to be dispersed and formed into particles, and blowing away through air flow to obtain the oil spill repairing agent. The density of the spilled oil repairing agent prepared by the preparation method is less than that of water, the spilled oil repairing agent can be dispersed and float on the water surface, and along with the gradual crushing and degradation of agar in a water environment, microorganisms adsorbed by the wood fiber carrier are gradually released and fully contacted with oil stains on the water surface, so that the spilled oil repairing agent has a good in-situ repairing effect.)

1. A preparation method of an oil spill repairing agent is characterized by comprising the following steps:

Providing a first carrier, wherein the first carrier is a wood fiber carrier with a porous structure;

Providing a microbial agent suspension, and mixing the first carrier with the microbial agent suspension to enable the first carrier to adsorb microorganisms to obtain a second carrier;

Providing an aqueous solution containing agar and a surfactant, mixing the second carrier and the aqueous solution in a container, enabling the agar to wrap the second carrier to form an intermediate, enabling the intermediate in the container to be dispersed and form particles, and blowing away through air flow to obtain the oil spill repairing agent, wherein the density of the oil spill repairing agent is less than that of water.

2. the method for preparing an oil spill repairing agent according to claim 1, wherein the particle size of the first carrier is 1mm to 20 mm.

3. the method for preparing the oil spill repairing agent according to claim 1, wherein the time for mixing the first carrier and the microbial agent suspension is 10min to 72 h.

4. The method for preparing the oil spill repairing agent according to claim 1, wherein the temperature of the aqueous solution is 35 ℃ to 65 ℃, the concentration of agar in the aqueous solution is 10g/L to 30g/L, and the concentration of the surfactant is 0.01g/L to 2.0 g/L.

5. the method for preparing the oil spill repairing agent according to claim 1, wherein the surfactant comprises one or more of soap powder, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, disodium lauryl sulfosuccinate monoester, Tween-20, Tween-60, Tween-80, polyoxyethylene octylphenol ether-100, polyoxyethylene octylphenol ether-45, sophorolipid, ethoxylated alkyl sodium sulfate, disodium cocomonoethanolamide sulfosuccinate monoester, monolauryl phosphate, lauryl alcohol ether phosphate, potassium monododecyl phosphate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, and polyoxyethylene fatty acid ester.

6. The preparation method of the oil spill repairing agent according to claim 1, characterized in that the oil spill repairing agent is prepared by mixing, by mass, 1: 0.1-2, mixing the aqueous solution and the second carrier, wherein the parameters of the mixing operation are as follows: the temperature is 35-65 ℃, the stirring speed is 50-1000 rpm, and the duration is 10-120 s.

7. The method for preparing an oil spill repairing agent according to claim 1, wherein the speed of the air flow is 2m/s to 30 m/s.

8. The oil spill repairing agent obtained by the preparation method according to any one of claims 1 to 7, wherein the oil spill repairing agent comprises a first carrier, microorganisms and agar, the first carrier is a wood fiber carrier with a porous structure, the microorganisms are adsorbed on the first carrier, the agar seals the surface of the first carrier, and the density of the oil spill repairing agent is less than that of water.

9. A method for repairing spilled oil in situ, comprising dispersing the agent of claim 8 on the surface of an oil reservoir to treat the spilled oil.

10. An in-situ repair method of oil spill is characterized by comprising the following steps:

Providing a first carrier, wherein the first carrier is a wood fiber carrier with a porous structure;

Providing a microbial agent suspension, and mixing the first carrier with the microbial agent suspension to enable the first carrier to adsorb microorganisms to obtain a second carrier;

Providing an aqueous solution containing agar and a surfactant, mixing the second carrier and the aqueous solution in a container, enabling the agar to wrap the second carrier to form an intermediate, enabling the intermediate in the container to be dispersed and form particles, and blowing the particles to the surface of an oil layer through a gas flow so that the surface of the oil layer is accumulated with an oil spill repairing agent to treat the oil spill.

Technical Field

the invention relates to the technical field of ecological restoration, in particular to an oil spill restoration agent, a preparation method thereof and an in-situ restoration method of oil spill.

Background

Oil spill remediation for oceans or river channelsthere are many related studies, such as: the invention patent CN201611121360.2 relates to an immobilized microorganism oil spill repairing agent which is sodium alginate-CaCl₂The bio-based activated carbon is prepared by embedding microorganisms into a carrier. The invention patent CN201410190244.0 relates to an immobilized microorganism oil spill repair agent, the carrier component of which comprises mussel shell, sodium alginate and CaCl₂. The invention patent CN201310016703.9 relates to an immobilized microorganism oil spill repairing agent which is sodium alginate-CaCl₂Embedding peanut shell-based activated carbon as a carrier to obtain the immobilized microbial microspheres. The invention patent CN201110299829.2 relates to an immobilized microorganism particle for degrading petroleum in water, which consists of an embedding material and activated sludge, wherein the embedding material consists of a carrier and SiO₂The carrier is polyvinyl alcohol and sodium alginate, and the surfactant is Tween-80 and/or rhamnolipid. The invention patent CN201710238737.0 relates to a biodegradable microorganism sustained-release agent, which comprises microorganism bacterium powder, a carbon source sustained-release body and a hydrogel-like bacterium agent carrier, wherein the microorganism bacterium powder and the carbon source sustained-release body are suspended in the hydrogel-like bacterium agent carrier, and waste of a carbon source caused by water flow can be effectively avoided through the sustained release of the carbon source, so that the utilization efficiency of the carbon source by the microorganism is improved, and the denitrification efficiency of the microorganism is improved.

Most of the spilled oil in the ocean or river is dispersed and floated on the water surface and is dispersed along with the waves. This requires that the microbes that are directed to the oil spilled on the water surface can float and disperse enough to be in full contact with the oil droplets on the water surface, thereby performing the oil-reducing function. None of the above patents mention immobilized particles of water surface floating type microorganism degrading bacteria. At present, the oil spill repairing agent slow release particles of the water surface floating type petroleum degrading microorganisms are few.

Disclosure of Invention

In view of the above, it is necessary to provide an oil spill repairing agent, a preparation method thereof, and an in-situ oil spill repairing method; the density of the spilled oil repairing agent obtained by the preparation method is less than that of water, the spilled oil repairing agent can be dispersed and float on the water surface, and along with the gradual crushing and degradation of agar in a water environment, microorganisms adsorbed by the wood fiber carrier are gradually released and fully contact with oil stains on the water surface, so that the oil stains are degraded, and the spilled oil repairing agent has a good in-situ repairing effect.

in a first aspect of the present invention, a method for preparing an oil spill repairing agent is provided, which comprises:

S1, providing a first carrier, wherein the first carrier is a wood fiber carrier with a porous structure;

S2, providing a microbial agent suspension, and mixing the first carrier with the microbial agent suspension to enable the first carrier to adsorb microorganisms to obtain a second carrier;

And S3, providing an aqueous solution containing agar and a surfactant, mixing the second carrier and the aqueous solution in a container, wrapping the agar on the second carrier to form an intermediate, dispersing the intermediate in the container and forming granules, and blowing away by air flow to obtain the oil spill repairing agent, wherein the density of the oil spill repairing agent is less than that of water.

in step S1, the first carrier is obtained by pulverizing wood fibers of plants such as corn stalks, corn cobs, sorghum stalks, rice stalks, cotton stalks and the like, and is biodegradable and environment-friendly. In addition, the first carrier obtained by crushing the plant wood fiber has a porous structure, so that microorganisms can be adsorbed on the surface and in the pore channels of the first carrier.

Furthermore, in order to obtain the oil spill repairing agent with low density and small particles, the oil spill repairing agent is convenient to disperse on the surface of an oil layer, and the particle size of the first carrier is 1-20 mm.

In step S2, the microbial agent suspension is commercially available, wherein the microorganism is a microorganism capable of degrading petroleum.

The mixing mode of the first carrier and the microbial agent suspension comprises mixing, stirring or standing and soaking, wherein the mixing, stirring or standing and soaking time is 10 min-72 h, so that the microorganisms are adsorbed on the surface and in the pore channels of the first carrier to obtain a second carrier.

In step S3, the agar is a temperature sensitive material with good mechanical strength and degradability, and is used to seal the second carrier to obtain the spilled oil repairing agent, which has good mechanical properties, and after contacting with water, the agar can gradually release microorganisms in the process of gradual breaking and degradation, thereby playing a role of slowly releasing microorganisms, so that the microorganisms can continuously degrade petroleum to achieve the purpose of in-situ repairing.

Further, firstly, the agar is melted by water or steam with the temperature higher than 90 ℃, then water is added for stirring, the temperature is regulated to be reduced to 35-65 ℃, then the surfactant is added, and the aqueous solution containing the agar and the surfactant is obtained, wherein the concentration of the agar in the aqueous solution is 10-30 g/L, and the concentration of the surfactant is 0.01-2.0 g/L.

further, the surfactant has good foaming performance, so that the dispersion of the intermediate solution is facilitated, the foam is formed, and the oil spill repairing agent can be obtained by blowing through air flow. Specifically, the surfactant comprises one or more of soap powder, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, disodium lauryl sulfosuccinate monoester, Tween-20, Tween-60, Tween-80, polyoxyethylene octylphenol ether-100, polyoxyethylene octylphenol ether-45, sophorolipid, ethoxylated alkyl sodium sulfate, disodium cocomonoethanolamide sulfosuccinate monoester, monolauryl phosphate, lauryl alcohol ether phosphate, potassium monododecyl phosphate, fatty alcohol polyoxyethylene ether, polyoxyethylene alkylphenol ether and polyoxyethylene fatty acid ester.

further, the weight ratio of 1: 0.1-2 mixing the aqueous solution with the second carrier. In order to ensure that the second carrier is fully and uniformly mixed with the aqueous solution and the activity of microorganisms, the parameters of the mixing operation are as follows: the temperature is 35-65 ℃, the stirring speed is 50-1000 rpm, and the duration is 10-120 s.

Further, the intermediate is dispersed and formed into granules having a bulk density of 200kg/m³～900kg/m³The speed of the air flow is 2 m/s-30 m/s, preferably 5 m/s-15 m/s, after the air flow is blown out from the outlet of the container at the speed, the intermediate can be naturally cooled in the air, so that the agar seals the second carrier to obtain the spilled oil repairing agent.

In a second aspect of the present invention, an oil spill repairing agent is provided, which is obtained by the above preparation method, and includes a first carrier, a microorganism and agar, wherein the first carrier is a wood fiber carrier with a porous structure, the microorganism is adsorbed on the first carrier, the agar seals the surface of the first carrier, and the density of the oil spill repairing agent is less than that of water.

it will be understood that the agar may be completely closed to the surface of the first carrier, or may be partially closed to the surface and pore channels of the first carrier, although, in view of the effect, it is preferred that the agar completely closes the surface of the first carrier.

in a third aspect of the present invention, an in-situ oil spill remediation method is provided, in which the oil spill remediation agent is dispersed on the surface of an oil layer to treat oil spill.

The density of the spilled oil repairing agent is less than that of water, so that when the spilled oil repairing agent is dispersed on the surface of spilled oil layers such as oceans and riverways, the spilled oil repairing agent can be dispersed and floated on the water surface and is more fully contacted with the oil layer. And then, the agar is gradually crushed and degraded in a water environment, and the microorganisms adsorbed on the first carrier are gradually released and contact with the oil layer to continuously degrade the spilled oil, so that the effect of in-situ remediation is achieved.

In a fourth aspect of the present invention, there is provided an in-situ oil spill repairing method, including:

Providing a first carrier, wherein the first carrier is a wood fiber carrier with a porous structure;

Providing a microbial agent suspension, and mixing the first carrier with the microbial agent suspension to enable the first carrier to adsorb microorganisms to obtain a second carrier;

Providing an aqueous solution containing agar and a surfactant, mixing the second carrier and the aqueous solution in a container, enabling the agar to wrap the second carrier to form an intermediate, enabling the intermediate in the container to be dispersed and form particles, and blowing the particles to the surface of an oil layer through a gas flow so that the surface of the oil layer is accumulated with an oil spill repairing agent to treat the oil spill.

in the in-situ oil spill repairing method, the prepared oil spill repairing agent is directly blown off to the surface of an oil layer through airflow, so that the oil spill repairing agent can be scattered and floated on the water surface to contact with the oil layer, the oil spill repairing agent does not need to be prepared in advance, and the method is simple and efficient to use.

Compared with the prior art, the invention has the following beneficial effects:

First, the density of the spilled oil repairing agent is less than that of water, and the spilled oil repairing agent can be dispersed and floated on the water surface instead of being immersed under the water surface, so that the spilled oil repairing agent can be fully contacted with the spilled oil floated on the water surface, and the in-situ repairing of the spilled oil is realized.

Secondly, the first carrier is mixed with the microbial agent suspension, and the mixture is sealed by the temperature sensitive agar, and then the microorganisms can be gradually released along with the gradual degradation of the agar in the marine environment, so that the aim of slow release is fulfilled, the oil spill can be continuously degraded, and the effect is good.

thirdly, the invention can disperse the oil spilling repairing agent on the surface of the oil layer while preparing the raw materials such as agar, the first carrier, microorganism and the like into the oil spilling repairing agent, and does not need to be prepared in advance.

Fourthly, the materials used in the method are all natural degradable materials, and after the oil spill repairing agent is degraded in situ, the oil spill repairing agent dispersed on the water surface does not need to be recovered, and can be naturally degraded.

Drawings

FIG. 1 is a graph showing the sizes (A to D) of the oil spill repairing agents, the weight ratio (E) of the particles, and the floating state of the particles of the oil spill repairing agents in example 1 on the water surface (F);

FIG. 2 is a graph showing the effect of the repairing agent for oil spill on the degradation of oil stain on water surface in example 1, wherein the type of petroleum is diesel oil, and the density of petroleum on water surface is 5000mg/m²；

FIG. 3 is a diagram showing the case where the oil spill repairing agent of example 2 floats on the water surface;

FIG. 4 is a graph showing the effect of the repairing agent in example 2 on the degradation of oil stains on water, wherein the type of petroleum is diesel oil, and the density of the petroleum on the water is 6500mg/m²。

Detailed Description

Hereinafter, the oil spill repairing agent, the preparation method thereof, and the in-situ repairing method of oil spill will be further described by the following specific examples.