JP2621003B2 - Oil adsorption / coagulant - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention rapidly adsorbs and coagulates oils such as mineral oil leaked to the surface of seawater, rivers and lakes, or mineral oil leaked out of a management system at a factory or a wastewater treatment plant. And a coagulant for use.

[0002]

2. Description of the Related Art Conventionally, synthetic fibers such as natural fibers, polyester fibers, and polypropylene fibers, woven fabrics, nonwoven fabrics, pulp, and foams have been widely used as treatment materials for oils such as mineral oils. Although there are absorbents such as plastics, these absorbents are lipophilic, so they absorb mineral oils and other oils, but their holding power is still insufficient, and the oils of the absorbed mineral oils are not affected by external forces. However, there is a disadvantage that it leaks from the absorbent. In addition, when using these absorbents to collect oils such as mineral oil that has flown into the sea, rivers, and lakes, water is also absorbed at the same time. There was a problem with the formulation of the absorbent.

[0003] As a treating agent for dispersing oils such as mineral oil spilled to the sea or the like to reduce the direct adverse effects of the oil itself on the mineral oil, surfactants such as fatty acid esters are known. However, this treating agent may emulsify and disperse oils such as spilled mineral oil over a wide range, resulting in deterioration of water quality and adversely affecting seafood and seaweeds. It is impossible to treat the spilled oil in a short time from the aspect of properties, and it is generally unsuitable as a treatment agent for the spilled oil.

[0004] Therefore, an adsorbent / coagulant for oils such as mineral oil has been developed. As the adsorbent / coagulant, N-acyl amino acid esters, dibenzylidene sorbitol and the like are known. However, these adsorption and
When an oil such as mineral oil is adsorbed and coagulated with a coagulant, a solvent is required, and the solidification of the coagulated body is poor, so that it is difficult to collect the coagulated body.

[0005] An adsorption / coagulant using a styrene / butadiene block copolymer is also known. However, this treatment agent is limited in the type of oil to be coagulated, and the time required for coagulation is 5 hours to 24 hours. Since it takes time, it is inefficient and unsuitable for urgently treating oil spills caused by accidents and the like.

Further, an adsorbent / coagulant using polynorbornene is also known. This treating agent shortens the time required for coagulation to 30 minutes to 2 hours, but the strength of the coagulated material after oil adsorption is reduced. Solids of sufficient hardness that are weak and easily disposable are not obtained. Furthermore, many problems remain in the ability to process a halogen-based solvent (trichloroethane, chlorofluorocarbon, etc.), which has become a particular problem in recent years.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned drawbacks, and has the advantage that only oil is well absorbed and solidified without absorbing water, and oil is not leaked by an external force. It is an object of the present invention to provide an adsorbent / coagulant which solidifies and aggregates firmly without any adverse effect on the product and which can be easily collected.

[0008]

DISCLOSURE OF THE INVENTION In view of the above situation, the present invention relates to a powder of a block copolymer comprising a polystyrene block and a polybutadiene block and bicyclo (2,
(2) An oil adsorbent / coagulant comprising: powder of polynorbornene, which is a ring-opening polymer of heptene-2 or a derivative thereof.

The block copolymer comprising a polystyrene block and a polybutadiene block used in the present invention includes a block copolymer in which polystyrene blocks and polybutadiene blocks are alternately arranged, and a block copolymer in a branched or radial form. And the molecular weight is 1
Desirably, the range is from 100,000 to 400,000, particularly from 150,000 to 300,000. It is desirable that the material softens at 100 ° C. and completely flows at 180 ° C. As for the ratio of the polystyrene block and the polybutadiene block, it is desirable that the polystyrene block is small, and the proportion is preferably 20 to 50%, particularly 35 to 45%.
% Is desirable.

The block copolymer composed of a polystyrene block and a polybutadiene block is used in the form of a powder.
01 to 1 mm is desirable.

The polynorbornene used in the present invention is a ring-opened polymer of bicyclo (2,2,1) heptene-2 or a derivative thereof, wherein the derivative is, for example, an alkyl group such as methyl or ethyl, or a methoxy group. , Ethoxy or the like, a carboxylic acid ester group, a cyano group, a halogen group, a vinyl group or the like. The molecular weight of polynorbornene is between 300,000 and 400
It is desirable, but not limited to this. The apparent specific gravity is 0.2
To 0.35. Polynorbornene is also used as a powder, but preferably has a particle size of about 0.001 to 1 mm.

The mixing ratio of the block copolymer composed of polystyrene block and polybutadiene block to polynorbornene varies depending on the characteristics of oils to be adsorbed and coagulated, or 50 to 200 parts by weight based on 100 parts by weight of the copolymer.
It is preferably about parts by weight.

The amount of the adsorbent / coagulant of the present invention added to oils depends on their properties and cannot be specified. However, in ordinary use, the amount may be about 5 to 30 parts by weight per 100 parts by weight of oil. May be appropriately adjusted according to the viscosity of the resin.

When adding the adsorbent / coagulant of the present invention, a sufficient adsorbent / coagulant can be obtained even if the oil is added at room temperature, as described above. When added at the same time, the adsorption / coagulation effect and the solidification effect can be further promoted as compared with the case of normal temperature.

The adsorptive / coagulant of the present invention includes mineral oils such as kerosene, light oil, gasoline, spindle oil, heavy oil A, heavy oil B, aromatic hydrocarbons, linear hydrocarbons, halogenated hydrocarbons, ethers and the like. It is effective for solvents.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments.

Example 1 A block copolymer comprising a polystyrene block and a polybutadiene block (weight ratio: 30 to 70) (molecular weight: about 2
7.5 million parts by weight of powder (20,000 mesh) and 7.5 of polynorbornene (molecular weight 2,000,000 to 3,000,000)
An adsorption / coagulant composed of parts by weight was prepared. When 15 parts by weight of this adsorbent / coagulant was added to 100 parts by weight of No. 1 spindle oil (Nippon Oil Co., Ltd.) at room temperature, the spindle oil was adsorbed by the adsorbent / coagulant in 1 minute as shown in Table 1. In 15 minutes, it became agar-like, and in 30 minutes, it became a single sticky and durable elastic rubber-like mass. The oil did not seep out when pressure was applied to it.

Comparative Example 1 A block copolymer comprising a polystyrene block and a polybutadiene block (weight ratio: 30 to 70) (molecular weight: about 2
100,000) Adsorption consisting of a single powder (particle size 20 mesh)
When 15 parts by weight of the coagulant was added at room temperature to 100 parts by weight of the spindle oil, the spindle oil did not change in 1 minute, thickened in 15 minutes and became agar in 30 minutes as shown in Table 1. However, it did not become an elastic rubber-like mass, and when pressure was applied, oil bleed out.

Comparative Example 2 When 15 parts by weight of an adsorbent / coagulant consisting of polynorbornene (molecular weight 2,000,000 to 3,000,000) alone was added at room temperature to 100 parts by weight of spindle oil, the spindle oil is shown in Table 1. As described above, there was no change in 1 minute, the viscosity increased in 15 minutes, and the mixture became agar in 30 minutes. However, it did not form an elastic rubber-like mass, and when pressure was applied, oil bleed out.

Example 2 15 parts by weight of the same adsorbent / coagulant as used in Example 1 were mixed with heavy oil A (J
IS K2205-1980) When added at room temperature to 100 parts by weight, Heavy Oil A thickened in 1 minute, became agar in 15 minutes, and had one non-sticky strength in 30 minutes as shown in Table 2. It became an elastic rubber-like mass. The oil did not seep out when pressure was applied to it.

Comparative Example 3 A block copolymer comprising a polystyrene block and a polybutadiene block (weight ratio: 30 to 70) (molecular weight: about 2
100,000) Adsorption consisting of a single powder (particle size 20 mesh)
When 15 parts by weight of the coagulant was added at room temperature to 100 parts by weight of Fuel Oil A, Fuel Oil A did not change in 1 minute as shown in Table 1, thickened in 15 minutes, and became agar in 30 minutes. However, it did not become an elastic rubber-like lump, and when pressure was applied, oil bleed out.

Comparative Example 4 15 parts by weight of an adsorbent / coagulant consisting of polynorbornene (molecular weight: 2,000,000 to 3,000,000) alone was added to A heavy oil 10
When added at room temperature to 0 parts by weight, fuel oil A
As shown in the figure, there was no change in 1 minute, the viscosity increased in 15 minutes, and 3
It became agar-like at 0 minutes, but did not become an elastic rubber-like lump, and when pressure was applied, oil bleed out.

Example 3 When 10 parts by weight of the same adsorbent and coagulant as in Example 1 were added at room temperature to 100 parts by weight of the halogen-based solvent shown in Table 3, the halogen-based solvents were all added as shown in Table 3. Gelation starts at the same time as the addition of the solvent, and trichloroethylene, 1,1,1 trichloroethane, methylene chloride, and fluorocarbon 113 take 5 minutes, and chloroform and methacrylate take 30 minutes. It became a strong elastic rubber-like mass.
The oil did not seep out when pressure was applied to it.

Comparative Example 5 A block copolymer comprising a polystyrene block and a polybutadiene block (weight ratio: 30:70) (molecular weight: about 2
100,000) Adsorption consisting of a single powder (particle size 20 mesh)
When 10 parts by weight of the coagulant was added at room temperature to 100 parts by weight of the halogen-based solvent shown in Table 3, all of the coagulants did not solidify and did not form an elastic rubber-like mass.

COMPARATIVE EXAMPLE 6 10 parts by weight of an adsorbent / coagulant consisting of polynorbornene (molecular weight: 2,000,000 to 3,000,000) alone was added to 100 parts by weight of a halogen-based solvent shown in Table 3 at room temperature. It did not become an elastic rubber-like mass.

Example 4 When 10 parts by weight of the same adsorbent and coagulant as in Example 1 were added at room temperature to 100 parts by weight of the mineral oil shown in Table 4, the mineral oil was 5 to 15 parts as shown in Table 4. In a minute, it solidified into one durable, elastic rubber-like mass. The oil did not seep out when pressure was applied to it.

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

[Table 3]

[0030]

[Table 4]

[0031]

The adsorbent / coagulant of the present invention does not dissolve in water but dissolves only in oil. Therefore, when used for oil suspended or dispersed in water, it does not absorb water and only absorbs oil. Satisfactorily absorbs, solidifies and floats, so that the oil can be efficiently coagulated and separated without any adverse effect on water quality. Also, once solidified, it becomes a very solidified state, oil does not leak even when pressure is applied, and the solidified body surface has no oil-specific fluff, so it hardly adheres to other objects and the environment It is very advantageous for hygiene, and since it is in the form of an elastic rubber, it is extremely easy to handle disposal.

Claims (1)

(57) [Claims] 1. A powder of a block copolymer comprising a polystyrene block and a polybutadiene block and a powder of polynorbornene which is a ring-opened polymer of bicyclo (2,2,1) heptene-2 or a derivative thereof. Oil adsorption / coagulant characterized by the following.