KR20010016273A - A method of suface water-repelling treatment of porous material and an oil-absorbent material prepared thereby - Google Patents

Abstract

PURPOSE: Provided are a method for processing the surface of porous matter to have water repellency and an oil absorbent manufactured thereof. The oil absorbent can absorb selectively only oil spilled at a river or a sea. The absorbent is demanding as follows: oil absorbency; lipophilic property for adsorbing with oil; hydrophobic property and water repellency; no settling down in water after adsorbing oil; no generating for any pollutants through incineration or any treatment; long storable; and mass production at low cost. CONSTITUTION: The method proceeds to the following steps: (i) to spread on the surface of porous matter in a bowl with an adhesive such as acrylic acid resin-hexane solution or acrylic monomer aqueous solution; (ii) to rotate the bowl for uniform application; (iii) to adsorb the pieces of silicon dioxide (10-20g for 100g of the porous matter) onto the surface of the porous matter in a bowl; (iv) to remove the silicon dioxide fixed on the surface of the porous matter by using a sieve; and (v) to heat the former porous matter at 250-300 deg.C for 5-8 minutes and to make silicon dioxide fixed firmly onto the porous matter by the carbonized adhesive. The porous matter is composed of perlite, vermiculite, pumice or firing soil not transmuted at the high temperature of 300 deg.C or more.

Description

A method of suface water-repelling treatment of porous material and an oil-absorbent material prepared according to the water-repellent treatment method of the porous structure

The present invention relates to a method for water repellent treatment of the surface of a porous structure and a water-repellent and oil-repellent porous structure produced thereby, in order to provide an oil absorption material for selectively absorbing only oils such as waste oil spilled into rivers and seas.

The ocean occupies more than 70% of the earth's total surface area and is rich in biomass and mineral resources, making it the last report of humankind's expectations. Today, the ocean is a large industrial complex located within the coastal region. In addition to the causes of pollution from the land, such as inflow of industrial wastewater and domestic wastewater discharged from large cities, fertilizers and contaminated groundwater and surface water from agricultural and livestock activities, oil spills from large tanker accidents, washing water from ships, etc. It is rapidly devastated by the causes of pollution, such as wastewater and various wastes discharged from marine facilities, and is in a serious pollution state that has a huge impact on the entire ecosystem.

In particular, oil spilled from ships due to accidents, not only in the early stages of the accident, but also causes massive damage to the ecosystem, causing massive deaths of algae and asphyxiation of fish and shellfish over the months and decades after the accident. have.

The spilled oil may be partially removed through the control and purification operations, but most of the oil remains in the environment during the complex weathering process and continuously affects various marine organisms. This is a challenge that must be addressed in terms of protection or in the prevention of damage to the marine industry such as aquaculture.

When oil spills, oil fences are first installed to prevent oil from spreading and to recover oil.

Oil recovery technology uses a waste oil removal device that sucks oil by mechanical force such as centrifugal or vacuum type, uses a chemical that treats oil spilled at sea by chemical and biochemical methods, incineration A method of removing effluent oil or a method of using an oil absorption material for adsorbing and recovering oil is used.

However, the method of inhaling the oil strip of the waste oil on the sea surface by the mechanical device is not only difficult to remove the oil strip effectively because water is also sucked when the waste oil is inhaled, and the oil strip of the vast area such as the sea is removed. In order to take a lot of time, there is a disadvantage that can not be a quick oil control operation.

In addition, even when the waste oil on the surface is removed by using chemicals, even though the waste oil from the sea level is removed since the chemical solidifies with the waste oil, the sedimented waste oil causes secondary environmental pollution. In addition, the method of controlling waste oil by incineration is not a suitable method considering that toxic substances are generated during incineration.

Because of these problems, technology is focused on the development of an effective oil absorbent that absorbs only waste oil.

Oil absorbers are currently made of petroleum polymers and are made of synthetic materials that are hydrophobic so that they can be absorbed from low viscosity oils to high viscosity, or organic materials such as plant fibers, pulp, and coal packed in nets. Oil absorbents made of special materials are used to have water repellency, but such oil absorbents are generally expensive or have a problem in that toxic gases are generated during incineration after adsorbing oil.

Therefore, a method of using minerals having a porous structure such as perlite, vermiculite, pumice, and calcined earth has been proposed. These minerals have a porous structure, so they have good absorption or adsorption to liquids, but do not absorb oil by preferentially absorbing water when used in a mixture of water and oil, such as in seawater with oil spills. Since it becomes impossible, it has a limit to use as an oil absorption material. Therefore, various methods for absorbing only oil by providing water repellency to these minerals have been researched and developed.

Among them, a method of treating a surface of the porous structure with a water-repellent chemical component such as epoxy vinyl chloride has been proposed.However, the water-repellent chemical component can absorb the pores of the porous structure by filling capillary pores in the porous structure or closing the inlet during the surface attachment process of the porous structure. The problem has been raised that even loss.

A method of attaching a water repellent material only to the surface of the porous structure by using an adhesive in a method of water repellent treatment of the surface of the porous structure In addition, as in the case of directly attaching the water repellent material, the adhesive material fills or blocks the capillary pores of the porous structure. Therefore, there have been various difficulties in producing an oil absorption porous structure by surface water repellent treatment.

Therefore, the present inventors should have (1) oil absorbency, which is a property of absorbing oil, which is a requirement for oil absorbents, (2) have lipophilic properties of adsorption power to oil attracting oil, and (3) water. Has hydrophobic and water repellent properties that do not absorb, (4) does not sink in water even after adsorbing oil, (5) no environmental pollutants will be generated during other processing such as incineration after adsorbing oil The present invention was completed after efforts to develop a new oil absorbent material having conditions such as (6) long-term storage, (7) low cost, and mass production.

Accordingly, an object of the present invention is to provide an excellent oil-absorbing porous structure having the above-mentioned requirements as an oil absorbent through an effective water repellent treatment, and a method of manufacturing the same.

1 is a view showing a process of fixing the silicon dioxide particles as a water repellent material on the surface of the porous structure by the method of the present invention, Figure 1a is a view showing a porous structure surface-treated with a pressure-sensitive adhesive and silicon dioxide particles before heating 1B is a view showing a porous structure in which silicon dioxide particles are fixed on a surface by an adhesive after heating.

2 is a photomicrograph of the cross section of the state in which silicon dioxide as a water repellent is fixed to the surface of the porous structure according to the present invention.

Explanation of symbols on the main parts of the drawings

1: porous structure

2: adhesive material

3: silicon dioxide particles

4: carbonized adhesive

The porous structure water repellent treatment method of the present invention for achieving the above object is characterized by consisting of the following steps:

(1) dispersing the adhesive material of the acrylic resin-hexane solution or the acrylic monomer aqueous solution on the surface of the porous structure in a container including the porous structure,

(2) stirring the container so that the adhesive solution is evenly applied onto the porous structure surface,

(3) transferring the porous structure coated with the pressure-sensitive adhesive material to a container containing silicon dioxide in a powder state, and then stirring to ensure that the silicon dioxide particles are evenly attached onto the surface of the porous structure coated with the pressure-sensitive adhesive material,

(4) removing excess silicon dioxide particles attached to the surface of the porous structure using a sieve,

(5) gradually heating the porous structure at a temperature of 250 ° C. to 300 ° C. for 5 to 8 minutes to allow the silicon dioxide particles to adhere onto the surface of the porous structure by a carbonized adhesive.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of water repellent treatment of a surface in order to provide oil absorption to absorb only oil to an absorbent gas having a porous structure.

The present invention also relates to a water-repellent and oil-absorbing porous structure produced by the above method.

In the present invention, silicon dioxide is used as the water repellent.

Silicon compound has a very good water repellency and lipophilic property with low surface tension, and it is an inorganic material widely used as a water repellent and a waterproofing agent together with a fluorine compound, of which silicon dioxide exists as a white fine powder in nature. Therefore, it has been difficult to attach to the absorbent gas having a porous structure.

However, in the present invention, by using an acrylic resin-hexane solution or an acrylic monomer aqueous solution as an adhesive material for attaching silicon dioxide powder to the porous structure, by heating it at a high temperature of 250 ℃ to 300 ℃, evaporation of unnecessary adhesive material and thus Along with the shrinkage phenomenon, the silicon dioxide is fixed on the surface of the porous structure by adhesive carbonization.

That is, according to the water-repellent treatment method according to the present invention, the silicon dioxide is pressed on the surface of the porous structure due to the shrinkage of the adhesive layer that occurs in the process of evaporating the unnecessary adhesive material by the high temperature heating, and the remaining part on the silicon dioxide-attached portion Since the adhesive material is carbonized to serve as a crosslinking role for the silicon dioxide to be fixed on the surface of the porous structure, as in the conventional method, capillary pores of the porous structure are filled or closed by the adhesive material, resulting in loss of oil absorption. It doesn't work.

In addition, as a water absorbing gas, it is possible to use a variety of materials having a porous structure, such as perlite, vermiculite, pumice, calcined earth, etc., which is economic in terms of manufacturing cost, and toxic gas in the incineration process after oil adsorption Does not occur, so it is very advantageous from an environmental point of view.

Hereinafter, the method of the present invention will be described in more detail step by step.

In step (1), the adhesive material of the acrylic resin-hexane solution or the acrylic monomer aqueous solution is sprayed onto the surface of the porous structure by spraying the porous structure in a rotating container.

In this case, the amount of the acrylic resin-hexane solution or the acrylic monomer aqueous solution adhesive is used in an amount such that the surface of the porous structure can be sufficiently coated, that is, in an amount of 7/100 to 8/100 of the gas volume.

Thereafter, step (2) is performed to stir the vessel for 2 to 3 minutes at a low speed of 20 to 30 revolutions per minute so that the pressure-sensitive adhesive solution is evenly applied on the surface of the porous structure. As a result of step (2), the entire surface of the porous structure is in a state of being coated with the pressure-sensitive adhesive solution.

In step (3), the porous structure coated with the adhesive material is transferred to a container containing silicon dioxide, and then stirred well so that the silicon dioxide particles are evenly attached onto the surface of the porous structure coated with the adhesive material.

At this time, the silicon dioxide is attached to the surface of the porous structure by a pressure-sensitive adhesive layer formed on the surface of the porous structure through the step (2) in a white fine powder state.

Silicon dioxide is used in an amount of about 10 to 20 g, preferably 15 g based on 100 g of the porous structure.

In step (4), excess silicon dioxide particles adhering to the surface of the porous structure are removed by sieving or the like.

A diagram showing the porous structure with the adhesive and silicon dioxide attached is shown in FIG. 1A.

As can be seen from this figure, the pressure-sensitive adhesive material applied to the porous structure fills or closes not only the surface of the porous structure but also the micropores, so that the porous structure loses absorbency in this state.

Thereafter, a step (5) of removing the adhesive blocking the micropores and performing heat treatment on the porous structure to fix silicon dioxide more firmly on the surface of the porous structure is performed.

When the porous structure is slowly heated at a temperature of 250 ° C. to 300 ° C. for 5 to 8 minutes through the heat treatment step of step (5), most of the adhesive material evaporates and shrinkage of the adhesive layer causes silicon dioxide particles to form the surface of the porous structure. In close contact with the phase, some of the pressure-sensitive adhesive remaining between the silicon dioxide and the porous structure is carbonized to serve as a crosslinking layer to further adhere the silicon dioxide onto the porous structure surface.

In this heating process, the porous structure is gradually heated at a temperature of 250 ° C. to 300 ° C. over 5 minutes to 8 minutes, wherein the heat source is directly in contact with the surface of the workpiece or when the heating temperature exceeds 300 ° C. When the used acrylic component ignites, no shrinkage is achieved, and the fastening effect is not realized. Even when rapid heating is performed within 5 minutes, the fastening effect is also insufficient and the fastening effect is reduced. In addition, if the heating rate is too slow or the heating temperature is lower than 250 ° C., some of the acrylic components used as the adhesive may be cured before evaporation, and thus capillary pores of the porous structure may be blocked. Particular attention should be paid to control.

After heating, the adhesives filling the micropores are evaporated, and a diagram showing the state of the porous structure in which silicon dioxide particles are fixed on the surface by the carbonized adhesive is shown in FIG. 1B.

As a result of step (5), oil absorption and hydrophobic porous structures surface-treated with water-repellent silicon dioxide are produced.

The porous structure produced by the method of the present invention exhibits almost complete water repellency without degrading oil absorption due to the properties of the water-repellent silicon dioxide and the water-absorbing porous structure, and the fine particles of silicon dioxide are used for the surface of the porous structure. By being evenly distributed, it is an excellent oil absorption material material which combines the conditions of the oil adsorption material mentioned above.

Hereinafter, the experimental procedure and results for the absorption (water repellency) and oil absorption performance of the porous structure treated with the water repellent surface by the method of the present invention will be described as examples.

The following examples are provided to illustrate the invention and to demonstrate the associated efficacy and should not be considered as limiting or limiting the scope of the invention.

Example 1

An oil-absorbing porous structure was prepared by the water repellent treatment method according to the present invention using a calcined soil for soil improvement as a porous structure, and an acrylic resin-hexane solution as an adhesive and silicon dioxide as a water repellent.

First, a calcined earth having a particle size of 8 to 12 mm was placed in a container, and a commercial acrylic resin-hexane solution was sprayed to the extent that the surface of the calcined earth was sufficiently covered and dispersed on the calcined earth surface.

The container is rotated so that the pressure-sensitive adhesive solution is evenly applied on the surface of the calcined earth, and the silicon dioxide particles are placed on the surface of the calcined earth to which the pressure-sensitive adhesive is applied by placing it in a heat resistant container containing 88.01% of commercially available silicon dioxide in a white powder state. Evenly attached.

After the use of a sieve to remove excess silicon dioxide particles, it was slowly heated over a period of about 7 minutes at a temperature of 250 ° C. to 300 ° C. to evaporate unnecessary adhesives and allow the silicon dioxide particles to stick on the calcined earth surface. .

After measuring the weight of the oil-absorbing calcined soil thus prepared, it was allowed to stand on water surface at 20 ° C. for 5 minutes, transferred to a wire mesh and left for 5 minutes, and then the weight was measured to measure the increase in weight. The test was carried out (December 52 of the Ministry of Transport, Transport, and Transport, No. 52).

In addition, the same amount of calcined soil was allowed to stand on the oil surface at 20 ° C. for 5 minutes, transferred to a wire mesh, and left for 5 minutes, and then the weight was measured to measure the increase in weight to test the oil absorption performance. Chief Master-Dol-Hun 52. 2. 1).

Finally, the same amount of calcined soil was placed on the surface of water at 20 ° C. with oil (oil) for 5 minutes, transferred to a wire mesh and left for 5 minutes, and then the weight was measured to measure the increase in weight. Was tested against.

Example 2

An oil-repellent porous structure was prepared by the same method as in Example 1, using dry bread pieces having a thickness of 10 to 15 mm as the porous structure, and commercially available acrylic monomer aqueous solution as the adhesive and 88.01% of commercial silicon dioxide as the water repellent material. It was.

In the same manner as in Example 1, a test on water repellent performance, oil absorption performance, and mixed oil absorption performance was performed on the prepared oil absorbent bread.

Test results of Examples 1 and 2 are shown in Table 1 below.

Absorption test Oil absorption test Mixed oil absorption test Example 1 2.80 g / ℓ 320 g / ℓ 333 g / ℓ Example 2 2.75 g / ℓ 473 g / ℓ 487 g / ℓ

As can be seen from the above test results, the porous structures produced by the method of the present invention were found to have an extremely small amount of water absorption compared to the oil absorption, and have excellent water repellency along with oil absorption.

In the case of the mixed oil absorption test, the increase in total absorption slightly from the oil absorption test is considered to be an increase in the weight due to water buried with oil.

According to the method of the present invention, since the silicon dioxide having water repellency can be effectively fixed on the surface of the porous structure without the side effect of closing the micropores by the adhesive, the porous structure having excellent water repellency and oil absorption can be obtained. Can provide.

In addition, the oil absorbing material manufactured by the present invention uses a porous structure as a gas, so that it does not go into water even after adsorbing oil, and does not generate environmental pollutants during incineration or the like after oil adsorption, and can be stored for a long time. In addition, while the conventional oil absorbent is a product of a special material manufactured to have a water repellency in the material itself, the porous structure of the present invention is a water-repellent treatment of the surface to a general material, there is no great restriction on the material and various materials of low cost Since it can be used, there is an advantage that mass production is possible even at low manufacturing cost.

Claims (5)

(1) dispersing the adhesive material of the acrylic resin-hexane solution or the acrylic monomer aqueous solution on the surface of the porous structure in a container including the porous structure, (2) stirring the container so that the adhesive solution is evenly applied onto the porous structure surface, (3) transferring the porous structure coated with the pressure-sensitive adhesive material to a container containing silicon dioxide in a powder state, and then stirring to ensure that the silicon dioxide particles are evenly attached onto the surface of the porous structure coated with the pressure-sensitive adhesive material, (4) removing excess silicon dioxide particles attached to the surface of the porous structure using a sieve, (5) the porous structure is gradually heated at a temperature of 250 ° C. to 300 ° C. for 5 to 8 minutes to allow the silicon dioxide particles to adhere onto the surface of the porous structure by a carbonized adhesive. Water repellent surface treatment method. The method of claim 1, Method for using silicon dioxide in an amount of 10 to 20g per 100g of the porous structure. A water and oil repellent porous structure produced by the method of claim 1. The method of claim 3, wherein The porous structure, characterized in that the porous structure is made of a material that is not deformed at a high temperature of 300 ℃ or more. The method of claim 4, wherein The porous structure is a porous structure, characterized in that the perlite, vermiculite, pumice or calcined soil.