KR970006135B1 - Gel for sea effluence oil treatment - Google Patents

Abstract

An oil gellation agent and solidifier for treatment of outflow of oil on the sea are manufactured by compounding surface active agents such as sodium oletate, saturated fatty acids and alkyl sulfates, together with latex, sometimes aqueous ammonia being added thereon. The oil gellation agent and solidifier manufactured in this way absorbs ocean pollutants to produce elastic solid material of floating.

Description

Eugelizing agent for offshore oil solidification and offshore oil solidification

The present invention relates to a marine pollutant treatment agent and a method for treating marine pollutants, and to a process for solidifying oil spills and marine effluents for the solidification of marine effluents.

Recently, oil and toxic chemicals have been spilled out of the world frequently, and more than 200 spills occur every year in the coastal waters of Korea. Since such spill accidents destroy marine ecosystems and cause severe damage to fisheries resources, the importance of marine pollution control techniques including oil spill accident handling at sea is increasing day by day.

One of the conventional oil pollution treatment agents for the treatment of oil spills in the sea is a liquid oil dispersion treatment agent, and the oil pollution treatment method using this oil dispersion treatment agent reacts the oil dispersion treatment agent with the spilled oil to make oil of fine oil droplets. It is a method of making water into a state of water dispersion, essentially removing oil, and inducing long-term natural decomposition by microorganisms. Therefore, the use of the dispersant has the disadvantage that not only marine pollution due to the toxicity of the dispersant itself, but also secondary pollution, such as the dispersed oil damages the aquatic life. Therefore, the minimum amount of oil dispersant should be used, and if it is necessary to treat the spilled oil with an excessive amount of oil dispersant, it may be considered that it is possible to reduce the environmental damage if it is left untreated.

Another conventional oil pollution treatment agent includes a gelling agent or a solidifying agent which collects spilled oil by gelling or solidifying the oil, and the method of removing the oil spill using the gelling agent is as described above. There is an advantage that can solve the fundamental problem of oil dispersant, and can be greatly reduced environmental damage if used in proper circumstances. In particular, when there is a large amount of oil released at the beginning of the accident or the oil can be trapped in the oil fence, the gelling agent can be used for effective control in a short time. Using the gelling agent can solidify the oil instantaneously, thereby preventing the oil from spreading, and has the advantage of being advantageous compared to other methods in terms of cost. These gelling agents are those in the form of powders or particulate solids (hereinafter referred to as powder type gelling agents) and in liquid form.

The powdered eugelating agent is composed of various plastic powders such as polyethylene, polypropylene, and polyurethane, and the method of treating effluent oil using the same is to solidify by spraying the powdery eugelizing agent into the contaminated water, absorbing oil, and then tangling it. . The difference between the effluent oil treatment method using the powdered oil gelling agent and the effluent oil treatment method using the powdered oil sorbent which is one of the other oil pollution treatment agents is that the oil sorbent does not solidify the oil to solidify and absorb the oil. Or only adsorption. However, although the powdered eugelating agent has an advantage of being advantageous for storage, there is a difficulty in spraying, and since the high molecular compound is a main component, if it is not collected after being sprayed at sea, secondary side effects such as plastic contamination are likely to occur. Plastic pollution is one of the recent marine debris pollution, and since it is not decomposed, it remains in the marine environment for a long time and causes various damages to the ecosystem. Thus, powdered adsorbents and gelling agents are used for small scale spillage treatment on land, but are rarely used at sea.

On the other hand, conventional liquid eugelating agents include amino acid derivatives as main components, sorbitol-based gelling agents and the like. The method of treating effluent oil using a liquid eugelizing agent is a method in which the gelling agent or oil is entangled with each other and the gelling or solidifying is collected with a skimmer. Such liquid gelling agent is easy to spray on the sea and excellent in performance, but the gelling oil is weak due to the degree of gelation or solidification characteristics, and the oil is difficult to collect because it is difficult to collect.

As an example of a method for removing contaminants using such liquid gelling agents. U.S. Patent No. 4,497,663, published by Robert G. Fisher et al. According to Fischer et al., Functional groups such as carboxylic acids that are easily miscible with the contaminating organic substances in order to solidify and remove contaminating organic substances such as hydrocarbon, organo phosphate, and silicon. A cross-linking agent comprising a liquid polymer containing a functional group and a complementary funtional group, which is also easily miscible with the contaminating organic substance and includes a primary or secondary amino group, and the like. By reacting with contaminating organics and reacting them, they form a three-dimensional solid that contains the contaminating organics solidified within about 1 hour at room temperature, and is harmless and easy to handle. That is, by using a liquid eugelizing agent mixed with a polymer having a functional group and a crosslinking agent having a compensating functional group, the contaminating organic substance such as oil is entangled with the poly-solid by the crosslinking action of the crosslinking agent to remove the contaminating organic substance. . Fischer's liquid gelling agent and the method of removing effluent oil using the same are unlike any other liquid gelling agent, and since solidified oil is not easily broken and has elasticity like rubber, it is easy to collect. It is evaluated. However, the fibrinating agent by Fischer et al. Was found to be able to solidify oil only by spraying about 40% of the volume of effluent oil in a sea trial (Fingas, MF, R. Stoodley and N. Laroche. 1990, Effectiveness testing of spill treating agent, Oil and Chemical Pollusion 7: 336-348). In addition, the production of this gelling agent requires a polymer having a special functional group and a crosslinking agent having a functional group complementary thereto, and thus has a disadvantage in that the production cost is very expensive. It is proving that the product, which is a product of the gelling agent of Rigidoil, which is a product of the gelling agent of the product, is in a state of being stopped since 1992 because of its excellent performance and no price competitiveness.

As a result of many years of research, the inventors added a surfactant to latex, which is a raw material of natural rubber, and stabilized the latex, and when it was administered to seawater, it solidified immediately, and when there were marine pollutants such as oil on the surface of the seawater. It was found to absorb this to form an elastic floating solid.

Latex refers to the latex collected from the bark of rubber trees, and its specific gravity is about 0.98, and the composition is composed of 60% water, 36% bear, 2% protein, 1% sugar fatty acid, 1% soap fatty acid, 0.4% mineral and enzymes. It is. Natural rubber particles wrapped in protein layer float in water and precipitate and solidify rubber particles below pH4.8. The diameter of natural rubber particles is mostly 0.5 to 1 micron and isoprene is polymerized {(C ₅ H ₈ ) _X }, but there is no orthodoxy regarding molecular weight and chemical structure. Latex is an emulsion of polymer and water when harvested from wood, and is highly unstable and solidifies itself in the air. Therefore, ammonia water is usually added to keep the liquid state after harvesting from the tree. Although isoprene and ammonia do not have any relationship, the protective cladding surrounding isoprene does not stabilize the emulsion permanently because of the ammonia itself. It gradually solidifies. The reason for using ammonia water is that ammonia is highly volatile and easily heated when heated, and can be stored in other alkaline solutions. However, in this case, the ammonia water is expensive and cannot be easily removed.

We added a surfactant to stabilize the latex. The surfactant may be added instead of adding ammonia water immediately after harvesting from the tree, or may be added to the latex to which the ammonia water is added. Since ammonia smells, when surfactant is added after adding ammonia water, the ammonia is stabilized with a surfactant and then heated while shaking to remove ammonia. Since latex is a mixture of polymer and water in a colloidal state, a surfactant, which is a bipolar material, is present between the polymer and water to stabilize the latex.

After the latex has stabilized with the addition of surfactants, it is known that the emulsion is unbalanced when the electrolyte is added, physically agitated, cooled or the addition of an organic solvent.

As described above, the present inventors found that, first, a surfactant is added to latex to stabilize the latex, and then, when it is administered to seawater, it solidifies immediately. Second, if there is oil on the surface of the seawater, latex Can be summed up in two ways as it solidifies and absorbs it to form an elastic floating solid. Among these, the principle of the phenomenon that the latex is stabilized by the addition of a surfactant, which is the first characteristic, and then solidified immediately upon administration to seawater is the case where the electrolyte is added in the above several cases where the balance of the emulsion stabilized by the addition of the surfactant is broken. It is similar to the mechanism of phenomena occurring in.

The mechanism when the electrolyte is added is as follows. When surfactant is present at the interface between the natural rubber particles and the aqueous solution to stabilize them, electrostatic charges are generated by various mechanisms at this interface. The potential difference of the surface of natural rubber particles becomes zero from the particle surface toward the aqueous solution. When an electrolyte is added thereto, the electric double layer shrinks and condenses while the surfactant loses its role.

Since seawater is rich in electrolytes, in the state where surfactant is added to the latex and stabilized, when it comes into contact with seawater, the emulsion is rapidly broken in accordance with the above-described mechanism at the moment of contact with seawater. However, after the surfactant is added to the latex, the cause of rapid solidification upon contact with seawater may be a complex phenomenon with a mechanism other than the aforementioned mechanism.

As a result of the inventor's investigation, no literature has been found that applies this principle in relation to seawater. Moreover, we are the first to apply this principle with regard to the treatment of marine pollutants, especially the offshore oil treatment.

The second characteristic of the inventors' discovery is that when there is marine pollutants such as oil on the surface of the seawater, the latex solidifies and absorbs it to form an elastic floating solid. When applied to, it is possible to have completely different characteristics from the conventional eugelizing agent and the offshore oil treatment method using the same. That is, unlike the conventional liquid gelling agent including the aforementioned method of Fischer and the like, the polymer and oil are entangled and solidified by the crosslinking action of the crosslinking agent. In the present invention, the gelling agent itself is not used without the reaction by the crosslinking agent. As the gelling agent absorbs and solidifies the oil immediately in the presence of seawater, the absorption mechanism of the oil depends on the adsorption and absorption like the powdered gelling agent or oil absorbent, but is liquid and has a great advantage in spraying. It can be said adsorption absorption type liquid gelling agent.

It is an object of the present invention to provide a method for treating various marine pollutants, including effluent oil, using the gelling agent and its gelling agent which can be widely used due to the low production cost.

Another object of the present invention is to facilitate the collection of offshore oil, the oil of the oil and the oil of the oil outflow oil using the gelling agent and the gelling agent that can make a solid that is not broken and elastic like rubber, even when contacted To provide a treatment method.

It is another object of the present invention to provide a gelling agent having a very low toxicity to marine life does not cause secondary pollution and a method for treating marine pollutants using the gelling agent.

In order to achieve the object of the present invention, the present invention provides a gelling agent for the offshore oil solidification treatment consisting of a mixture of latex and surfactant.

In order to achieve the other object of the present invention, the present invention,

Adding a surfactant to the latex;

Administering the result to sea water;

Reacting the resultant with seawater to form a floating solid; And adsorbing or absorbing contaminants at the same time as or after forming the suspended solids to form a suspended solid containing the contaminants.

The oil gelling agent and the method for treating offshore oil using the oil gelling agent according to the present invention have various advantages as follows. First, even if the eugelating agent according to the present invention is put on the surface of oil-free seawater, the gelling agent solidifies itself and becomes floating without being mixed into the seawater, so there is no secondary toxicity. Easily identified and easy to collect. Second, since the gelling agent absorbs oil and solidifies as the gelling agent itself gels immediately in the presence of seawater without using a reaction by a crosslinking agent, the solidification rate is much faster than that by the conventional method. Third, since the solids in the state of absorbing contaminants such as oil is elastic and oil does not appear, it is very easy to collect the sea. Fourth, the absorption mechanism of oil is dependent on the adsorption and absorption, like the powder-type gelling agent or sorbent, but since it is a liquid, it is possible to spray off the sea with a nozzle or a hose, which has a great advantage in spreading. Fifth, since it is easy to manufacture a cheap latex as the main raw material, the production price of the gelling agent is much cheaper than the conventional gelling agent. Sixth, since it absorbs not only oil but also other toxic chemicals to form solids, it is applicable to marine spills of other chemicals.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example

First, the manufacturing method of the gelling agent which concerns on this invention is demonstrated to an example.

The simplest process is to add a surfactant to the latex. Here, as an surfactant, an anionic surfactant is preferable. Nonionic surfactants may also be used but are difficult to use alone without anionic surfactants and are less capable of producing stable emulsions than anionic surfactants. Cationic surfactants may also be used but are also less capable of producing stable emulsions than anionic surfactants. The anionic surfactant is, for example, sodium oleate, saturated fatty acids, alkyl sulfates, alkyl sulfonates, alkyl benzene sulfonates Ether alcohol sulfates, polyoxyethylene nonyl phenyl ethers, and the like. Although only one type of surfactant may be used, two or more types may be used in combination.

In the case of adding sodium uriate as the anionic surfactant, for example, 5% to 10% aqueous sodium oleate solution is added to the latex. At this time, the amount of the aqueous sodium uriate solution added is such that the content of sodium uriate is 0.5% -4% relative to the total moisture content of the final solution after the aqueous solution is added.

As described above, since the latex is a state in which the polymer and the water are mixed in the colloidal state, the surfactant, which is a bipolar material, is present between the polymer and the water to stabilize the latex.

As mentioned above, ammonia water is usually added to maintain the liquid state after harvesting from the tree. Therefore, most of the commercially available latex can be said to be ammonia added product. In the case of latex added with ammonia water, a step of removing ammonia is necessary to remove odor. This step is enough to shake or heat until the ammonia odor after the surfactant addition step. Of course, heating while shaking is more efficient.

The eugel haze according to the present invention, which can be prepared by the method described above, for example, maintains a stable emulsion state as a substance in which latex and a surfactant are mixed. Here, the surfactant is preferably an anionic surfactant, and examples thereof include sodium uriate, saturated fatty acid, alkyl sulfate, alkyl sulfonate, alkyl benzene sulfonate, ether alcohol sulfate, polyoxyethylene nonylphenyl ethyr, and the like. Can be. Although one type may be sufficient as surfactant, two or more types may be mixed.

When the anionic surfactant is sodium oleate, the content of sodium uriate is about 0.5% -4% based on the total moisture content of the latex and sodium uriate mixed. In addition, the gelling agent according to the present invention may contain a small amount of a substance other than latex and surfactant, for example, ammonia water. In the eugelating agent according to the invention, the surfactant serves to stabilize the latex to keep the latex in an emulsion state.

Next, an example of the offshore oil solidification treatment method using the gelling agent according to the present invention will be described.

First, the gelling agent is prepared according to the method for producing the gelling agent described above. That is, surfactant is added to latex. Here, the surfactant is preferably an anionic surfactant, and the anionic surfactant is, for example, sodium uriate, saturated fatty acid, alkyl sulfate, alkyl sulfonate, alkyl benzene sulfonate, ether alcohol sulfate, polyoxyethylene nonyl phenyl Ethir. One type of surfactant may be used, but two or more types may be used.

In the case of adding sodium uriate as the anionic surfactant, for example, 5% to 10% aqueous sodium oleate solution is added to the latex. At this time, the amount of the aqueous sodium uriate solution added is such that the content of sodium uriate is 0.5% -4% relative to the total moisture content of the final solution after the aqueous solution is added.

In the case of latex to which ammonia water is added, a step of shaking or heating may be further added after the surfactant addition step until the ammonia odor is removed to remove the odor.

The resulting product is then administered to seawater. Since the resultant is a liquid phase, it is possible to easily spray off the sea with a nozzle or a hose.

The resultant reacts with the seawater as soon as it is introduced into the seawater and solidifies itself to form a floating solid. Solids solidified by reacting the resultant with seawater without absorbing contaminants, such as oil, have a white color so that they can be easily identified at sea and are easily collected, and do not mix into the seawater.

On the other hand, if there are contaminants such as oil in the sea water, they are absorbed or adsorbed to form floating solids including the contaminants. The step of absorbing or adsorbing the contaminants may occur simultaneously with the step of solidifying the resultant itself in the presence of seawater or after the step of solidifying itself. In addition, absorbable contaminants are all harmful substances that can be absorbed by conventional adsorbents such as various types of organic solvents as well as oils. For example, fuel oils such as gasoline, diesel and jet fuel, crude oil, organic chlorine compounds, and benzene , Toluene and the like. The suspended solids formed as described above are elastic and do not have contaminants such as oil, and are easily collected by a net or a skimmer.

The oil gelling agent and the method for treating offshore oil using the oil gelling agent according to the present invention have various advantages as follows. First, even if the eugelating agent according to the present invention is put on the surface of oil-free seawater, the gelling agent solidifies itself and becomes floating without being mixed into the seawater, so there is no secondary toxicity. Easily identified and easy to collect. Second, since the gelling agent absorbs oil and solidifies as the gelling agent itself gels immediately in the presence of seawater without using a reaction by a crosslinking agent, the solidification rate is much faster than that by the conventional method. Third, since the solids in the state of absorbing contaminants such as oil is elastic and oil does not appear, it is very easy to collect the sea. Fourth, the absorption mechanism of oil is dependent on the adsorption and absorption, like the powder-type gelling agent or sorbent, but since it is a liquid, it is possible to spray off the sea with a nozzle or a hose, which has a great advantage in spreading. Fifth, since it is easy to manufacture a cheap latex as the main raw material, the production price of the gelling agent is much cheaper than the conventional gelling agent. Sixth, since it absorbs not only oil but also other toxic chemicals to form solids, it is applicable to marine spills of other chemicals.

As mentioned above, although this invention was demonstrated to the Example, this invention is not limited to this, A person with ordinary knowledge in this field can easily understand that a various deformation | transformation is possible within the range of the technical idea on which this invention is based. Could be.

Claims (8)

Eugelizer for offshore oil solidification treatment consisting of a mixture of latex and surfactant. The eugelating agent for the offshore oil solidifying treatment according to claim 1, wherein the surfactant is an anionic surfactant. The method of claim 2, wherein the anionic surfactant is sodium oleate, saturated fatty acids, alkyl sulfates, alkyl sulfonates, alkyl benzene sulfonates Eugel for marine effluent solidification treatment, characterized in that any one selected from the group consisting of sulfonates, ether alcohol sulfates, polyoxyethylen nonyl phenyl ethers and mixtures thereof. issue. According to claim 3, wherein the content of sodium uriate is the gelling agent for the marine effluent oil solidification treatment, characterized in that 0.5% -4% to the total water content of the mixture of latex and sodium uriate . Adding a surfactant to the latex; Administering the result to sea water; Reacting the resultant with seawater to form a floating solid; And adsorbing or absorbing contaminants at the same time as or after the forming of the suspended solids to form the suspended solids containing the contaminants. The method of claim 5, further comprising adding ammonia water to the latex, before adding the surfactant to the latex, and after adding the surfactant to the latex, shaking or heating the resultant. The marine effluent solidification treatment method further comprising the step. The said marine outflow oil solidification method of Claim 5 or 6 whose said surfactant is an anionic surfactant. The method of claim 7, wherein the anionic surfactant is any one selected from the group consisting of sodium uriate, saturated fatty acid, alkyl sulfate, alkyl sulfonate, alkyl benzene sulfonate, ether alcohol sulfate and polyoxyethylene nonyl phenyl ether. The marine effluent oil solidification treatment method characterized in that.