JPH0322918B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a spilled oil flocculant that is easy to use, highly efficient, and causes little harm to aquatic animals and plants, and more specifically, an olefin polymer having a true specific gravity of 1 or less; A lipophilic powder such as a 2-norbornene polymer is suspended in an aqueous solution of a hydrophilic organic solvent whose true specific gravity is similar to that of the powder, or a surfactant and/or alkali soap at a concentration close to the critical micelle concentration is added during the treatment. This invention relates to a spilled oil flocculant characterized in that it contains a hard water resistant ionic surfactant such as.

In recent years, crude oil, heavy oil, light oil, etc. that have spilled into the sea and land water systems due to tanker accidents, oil depots, factory accidents, etc. are causing so-called pollution that not only causes coastal pollution but also causes serious losses to the fish farming industry. It's a big factor.

In addition to the simple operation of enclosing oil in an oil fence and mechanically sucking up the spilled oil, there is also a method of collecting the spilled oil by installing so-called adsorption mats made of polymers such as polyolefin and allowing the oil to be absorbed by these mats. , a method of spraying a so-called spilled oil treatment agent containing an emulsifier as a main ingredient to emulsify and disperse it, amino acid derivatives and sorbitol derivatives,
A well-known method is to spray a coagulated oil such as a 2-norbornene polymer or a gelling agent and recover the spilled oil as a coagulated oil or a gelled product.

All of these methods are effective or the only possible method under certain conditions and are selectively implemented depending on the situation of the oil spill accident, but oil spill dispersants whose main agent is a liquid product With the exception of , all of the others have solid or powdered base agents, making it difficult to spread and spread over a wide area of oil. As a solution to this problem, the base agent is dissolved in a lipophilic solvent that can dissolve the solid component of the base agent to create a liquid product that can be sprayed with a pump.
Conventionally known methods include using a surfactant to create a product that is dispersed in water, or using a combination of a lipophilic solvent and a surfactant to create a liquid product that dissolves and disperses the main ingredient.

However, the method of dissolving the base solid component in a lipophilic solvent to make a liquid product still has problems, such as the toxicity of the solvent used, which causes secondary pollution. Since this method uses an expensive, low-toxicity special solvent, it has the disadvantage that in practice, the treatment agent must be several times more expensive than the spilled oil. In addition, the method of suspending the main solid powder in water with a surfactant is a stable product as a suspension, which also has high dispersion and emulsification properties when sprayed on seawater or land water, and emulsification of spilled oil. Although it meets the purpose as a dispersant, in products intended for agglomeration and gelation, the loss of the main agent is extremely large, and although the unit price of the product is low, the efficiency is significantly reduced, so the overall economic efficiency is extremely disadvantageous. Moreover, on the surface of the main agent particles, the lipophilic groups of the surfactant are arranged on the main agent particle side and the hydrophilic groups are arranged on the aqueous phase side, which deteriorates the essential affinity with spilled oil and increases the aggregation and gelation time. It has significant drawbacks.

The present invention solves the problems remaining in the above-mentioned methods for liquefying flocculation and gelling agents, and provides a stable, easy-to-use, highly efficient, fast-acting, low-pollution, and inexpensive flocculation and gelling agent for spilled oil. This is what we provide.

That is, the characteristics of the present invention are that polyolefins such as polyethylene and polypropylene, oil-curing properties such as 2-norbornene polymers having a true specific gravity of 1 or less;
While making the oil-absorbing substance into as fine particles as possible, water is added to lower alcohols such as methanol, ethanol, propanol, isopropanol, butanol, and other hydrophilic solvents with a specific gravity of 1 or less to form a solution with the same specific gravity as the fine particulate base material. The above-mentioned fine particulate main ingredient is added to this, and the mixture is thoroughly stirred using a homomixer or the like to form a liquid suspension-type aggregation and gelling agent.

The main component is preferably a 2-norbornene polymer (molecular weight of 2 million or more), which has particularly excellent flocculation performance against oil. Commercially available 2-norbornene polymer [poly(1,3-cyclopentylene vinylene)] already has a particle size of 1 mm or less, so it can be used as is, but it can also be re-pulverized to obtain an even smaller particle size. good.

As the alcohol, it is preferable to use ethanol, isopropanol, etc., taking comprehensive consideration from the viewpoints of toxicity, pollution, price, affinity with oil, diffusibility, and specific gravity.

Normally, the true specific gravity of the main ingredient particles is about 0.90 to 0.98, so if you make a 10 to 35% aqueous solution of the alcohol with a specific gravity of about 0.78 to 0.81, the specific gravity will be 0.96 to 0.98.
This becomes equal to the true specific gravity of the base agent, and the dispersion and suspension stability of the base agent therein becomes extremely good. To further improve stability, trace amounts of surfactants can also be added. In this case, the additive concentration is the critical micelle concentration (CMC) of the surfactant.
When sprayed on sea or land water, the concentration of the surfactant immediately exceeds the CMC due to the dilution effect.
It is preferable to reduce the effect. Further, the surfactant is an ionic surfactant, particularly an anionic surfactant such as a fatty acid alkali soap, and the metal ion content thereof is preferably an alkali metal such as sodium, potassium, lithium, or ammonium ion. The metals undergo ion exchange with alkaline earth metals such as calcium and magnesium, especially in seawater, resulting in a loss of surface activity.

The suspension concentration of the main agent fine particles in the organic solvent aqueous solution can be adjusted freely, but its stability and handling
It is preferably about 10 to 30% by weight in consideration of transportation, storage properties, etc.

When spraying at sea, etc., this suspension product can be sucked up with a pump or pumped up with seawater using a ventilator method, and then diluted to less than a few percent and sprayed on the spilled oil surface extremely efficiently. It is something.

The ability to aggregate oil after spraying can be achieved in terms of oil collection amount, oil collection speed, and oil condensate hardness that are approximately the same as in the case of powder spraying, and recovery by conventional methods is possible.

The present invention will be explained in more detail below based on examples.

Example 1 Poly 2-norbornene (molecular weight 2 million or more, average particle size 0.3 to 0.4 mm, true specific gravity 0.96) 20 was weighed out,
Mixed aqueous solution of isopropanol (specific gravity 0.7862/20℃) 28.3 and distilled water 71.7 (specific gravity 0.9585/27℃)
After charging to 100 ml, homomixer at room temperature
Suspension 121 was produced by stirring at 2000 r.p.m. for 15 minutes. Add 15 parts of this suspension to 50 parts of seawater and 10 parts of B heavy oil.
When the mixture was sprinkled onto the two-layer solution and stirred for about 3 seconds, heavy oil B was almost completely coagulated into poly-2-norbornene after about 20 seconds, forming a plate-shaped solid that could be collected using a net or the like.

In addition, the suspension is stable even if left for one week,
After standing for 2 weeks, a separated liquid was observed in the upper layer, but a complete suspension was restored with slight stirring.

Example 2 The same poly-2-norbornene 20 as in Example 1 was weighed out and mixed with a mixed aqueous solution (specific gravity 0.960/25°C) of ethanol (specific gravity 0.7937/15.6°C) 29 and distilled water 71 (specific gravity 0.960/25°C) 100%.
The same procedure as in Example 1 was carried out to produce suspension 121. Add 15% of this suspension to seawater
It was sprayed on a two-phase oil-water solution containing 10 parts of colored kerosene and 50 parts of colored kerosene, and stirred for about 3 seconds. After about 15 seconds, the kerosene was almost completely coagulated into poly-2-norbornene, forming a plate-shaped solid that could be collected with a net, etc. .

Although a slight amount of water separation was observed in the lower layer of the suspension after about 3 days, a complete suspension state was restored by slight shaking.

Example 3 Isotactic polypropylene (molecular weight approximately 40
30,000, specific gravity 0.90, average particle size 400-500 mμ) 30, and isopropanol (specific gravity 0.7862/20℃) 57
and distilled water 43 (specific gravity 0.90/25
After charging at 100 °C, a suspension was prepared in the same manner as in Example 1. This suspension (35%) was sprayed onto a two-layer oil-water solution containing 50% seawater and 8% colored kerosene.
After about 15 seconds of stirring, the kerosene completely coagulated into isotactic polypropylene and became amorphous lumps with a particle size of about 1 cm, which could be collected using a net or the like.

Although this suspension had slightly lower static stability than those of Examples 1 and 2, it recovered to a suspension with mild stirring.

Example 4 In the method described in Example 2, 400 g of fatty acid alkaline soap was added and stirred. The obtained suspension showed the same cohesive strength against colored kerosene as in Example 2, and had static stability for more than half a year.

Claims (1)

[Claims] 1. True specific gravity is 0.90 to 0.98 and average particle size is 1.0 to 0.5 mm.
A spilled oil flocculant characterized in that it is made by suspending an oil coagulating and oil absorbing powder such as an olefin polymer or a 2-norbornene polymer in a 10 to 35% aqueous solution of a lower alcohol having a specific gravity of 0.78 to 0.81. 2. Claims characterized in that a surfactant with a concentration close to the critical micelle concentration and/or an ionic surfactant with low resistance to hard water such as alkaline soap is present in the aqueous solution of the lower alcohol. Spilled oil flocculant according to paragraph 1.