JPH10273650A - Treatment of oil to be treated and solid fuel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for treating an oil to be treated by adding a specific oil absorbing agent to a recovered spillage oil, etc., discharging water admixed in the spillage oil, etc., and dehydrating. SOLUTION: An oil absorbing agent containing an oil-absorbing polymer, etc., is added to a recovered slurried oil to be treated discharged to the ocean, stirred and mixed. The oil-absorbing agent is absorbed in the oil to be treated and water admixed in the oil to be treated is discharged to give a solid material having low tackiness. The mixture containing the discharged oil absorbing agent containing water is dehydrated by filtration under pressure, centrifuging, pressing, etc., and water is taken out of the system to give a lump having a low water content and no tackiness. A polymer obtained by polymerizing bicyclo [2.2.1]heptene-2 is especially preferable as the oil-absorbing polymer. The lump has no tackiness, is readily handled and is easily subjected to waste treatment such as reclamation and incineration. The lump can be used as a solid fuel.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a process for absorbing oil to be treated mixed with water by an oil absorbing agent, efficiently discharging water mixed in the oil to be treated, and dehydrating if necessary. The present invention relates to a method for treating oil to be treated for removing water from the system. In the treatment method of the present invention, the oil-absorbing agent absorbs the oil to be treated, the mixed water is discharged, and the treatment residue with low tackiness and easy handling can be obtained. In particular, water discharged from the oil to be treated and taken into the oil absorbing agent can be easily removed from the system by pressure filtration, centrifugation, or the like. The residue after dehydration is very easy to handle as a solid mass having almost no tackiness. Furthermore, the present invention relates to a solid fuel containing an oil absorbing agent, an oil to be treated, and water, wherein water mixed into the oil to be treated is reduced to a certain amount or less.

[0002]

2. Description of the Related Art In recent years, recovery of oil spills in the oceans, rivers, and the like or treatment of oil in drainage has become a major problem in environmental conservation. As an effective means for collecting and treating such spilled oil and oil components in wastewater, a method of absorbing oil with an oil absorbing agent or an oil treating material obtained by storing the oil absorbing agent in an appropriate packaging container or the like has conventionally been used. More adopted. Various oil absorbing agents are used depending on the properties of the oils, the processing environment, and the like. However, especially when a large amount of oil spills in the ocean, etc., it is not easy to perform on-site treatment work. First, oil floating on the site or oil floating on the coast is collected and then absorbed. It is often treated with agents.

[0003] However, in the case of oil to be treated mixed in a large amount of water, such as in the case of a spill of crude oil from an oil tanker in the ocean, a considerable amount of water is mixed in the recovered oil to be treated. And, depending on the type of heavy oil or the like, the oil to be treated is a slurry having a high viscosity and is often very difficult to handle. For example, it is extremely difficult to collect the spilled oil that has arrived on a coastal reef or the like. Also,
Collect spilled oil floating on the sea surface, bucket, drum can, etc.
Even when stored in an appropriate container, it is not easy to bury them, take them out of the container for incineration, etc., or transfer them to another container. Furthermore, it is difficult to incinerate an oil absorbing agent mixed with a large amount of water together with the oil to be treated, and it is necessary to separate and remove water. However, the removal of the water is not easy, and the treatment of the oil-absorbing agent containing the oil to be treated and the water after the collection is a new problem.

[0004] After the oil absorbing agent that has absorbed the oils is collected, some treatment such as landfilling or incineration is usually required. In the case of landfill, there is a problem of land for that purpose. In particular, as described above, the landfill operation is not easy with the oil absorbing agent that has absorbed the oil to be treated in a slurry state containing a considerable amount of water. Further, the oil absorbent that has absorbed the oil to be treated is often incinerated and disposed of. However, at the time of incineration, toxic gases such as sulfur compounds such as sulfur oxides and hydrogen sulfide or chlorine compounds such as hydrogen chloride are generated from sulfur content contained in the oil to be treated or chlorine content mixed into the oil absorbing agent from seawater. Therefore, there is a concern about the effects on the human body or environmental pollution.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems, and provides an oil absorbing agent containing an oil absorbing polymer.
If necessary, the oil to be treated is absorbed by the oil-absorbing agent by being stored in a water-soluble packaging container, etc., and the water mixed in the oil to be treated is easily discharged and dehydrated. It is an object of the present invention to provide a processing method. Also, the present invention
By using an oil-absorbing agent containing a specific oil-absorbing polymer and making the amount of water contained in the oil-absorbing agent after absorbing the oil to be treated a certain amount or less, the tackiness is low, the handling is easy, and the It is an object to provide a solid fuel that can be burned.

[0006]

According to a first aspect of the present invention, there is provided a method for treating an oil to be treated, wherein an oil-absorbing agent containing an oil-absorbing polymer is mixed with the oil to be treated or water containing water, and water is mixed. The oil to be treated is absorbed by the oil absorbing agent, and at least a part of the water mixed in the oil to be treated is discharged.

The above-mentioned "oil-absorbing agent" contains the above-mentioned "oil-absorbing polymer" as a main component. This oil-absorbing polymer has an oil absorbing agent of 10
0% by weight (hereinafter simply referred to as “%”),
It is preferably at least 50%, particularly preferably at least 60%, more preferably at least 70%. Examples of the oil-absorbing polymer include bicyclo [2.2.1] heptene # 2, 1-hexene,
And octene, isooctene, 1-nonene, 1-decene and 1-dodecene. Further, a polymer composed of an alicyclic vinyl compound such as vinylcyclohexane, or an allyl ether having a hydrocarbon group such as dodecyl allyl ether can also be used.

Further, at least one kind of alkyl (meth) acrylate having at least one aliphatic hydrocarbon group having 3 to 30 carbon atoms, alkylaryl (meth) acrylate, aliphatic vinyl ester, alkylstyrene and the like. A polymer composed of a saturated compound can also be used. These polymers may be copolymers composed of two or more appropriate monomers. As the oil-absorbing polymer, only one of these polymers and copolymers may be used, or two or more thereof may be used in combination.

As the oil absorbing polymer, a polymer of "bicyclo [2.2.1] heptene # 2 (hereinafter referred to as" norbornene ")" is particularly preferable as in the second invention. This norbornene can be subjected to ring-opening polymerization in the presence of a noble metal compound and a reducing agent such as alcohol.
However, a polymer obtained by such a method is not preferable as an oil-absorbing polymer because it becomes a dense mass.

On the other hand, a catalyst system comprising ruthenium trichloride dissolved in n-butanol or tungsten hexachloride;
In the presence of a catalyst system consisting of an alkylaluminum and an aromatic solvent, monomers undergo incomplete ring-opening polymerization at a pressure above atmospheric pressure, and then polymerize by a method of rapidly reducing the pressure at a temperature above the boiling point of the reaction product. You can also. The polymer obtained by this method is granular and suitable for use as an oil-absorbing polymer. The norbornene may be a “substituted derivative” in which one or two or more hydrogen atoms at an appropriate position are substituted by a short-chain alkyl group or the like, as long as the ring-opening polymerization is not particularly hindered.

The particle size of the oil absorbing polymer is 10 to 1000 μm.
m, especially 50-800 μm, and even 100-600 μm
The degree is preferred. When the particle size is less than 10 μm, the particles tend to aggregate. When treating oils having low viscosity, only the surface layer of the polymer particles that is in contact with the oils adsorbs the oils in a short time and swells. Therefore, the flow of oils between the particles is hindered, and furthermore, the water absorption between the particles is not discharged to the outside. If the particle size exceeds 1000 μm, the surface layer of the polymer particles comes into contact with oils and swells, and the oils hardly penetrate beyond the surface layer and into the inside of the particles, and the oil absorption decreases. Not preferred.

The above-mentioned “oil to be treated containing water”
It refers to oils to be treated which are collected in a relatively large amount of water, such as the ocean and rivers, collect spilled oil and the like which are floating, etc., and are contained in appropriate containers and the like with little mixed water. This contamination refers to a state in which the oil to be treated is taken in the lump,
In the present invention, it is said that water that exists independently of this lump is mixed. Further, the above-mentioned “oil to be treated which is mixed with water and mixed with water” means that, in addition to the mixed water, the mixed water is present in a large amount exceeding the volume of the oil to be treated. Oil to be treated. In addition, the oil to be treated mixed in this water is also the oil to be treated collected in some container or the like,
It is usually difficult to apply the method of the present invention to a site such as an ocean or a river from which oils or the like have flowed out. Also,
The oil to be treated which is crashed to the shore or the like and is attached to a rock reef or the like also corresponds to the oil to be treated in the present invention in which water is mixed.

[0013] Such an oil to be treated is often in the form of a slurry having a high tackiness except for water mixed therein.
After the oil to be treated is absorbed by contacting the oil to be treated with an oil absorbing agent containing an oil-absorbing polymer and a part of the mixed water is discharged, the oil absorbing agent, the oil to be treated and the discharged water are removed. The resulting mixture becomes solid and less sticky. Therefore, the mixture becomes very easy to handle, and it is easy to take out this mixture from a container or the like when performing landfill processing. However, if the water discharged by the oil absorbing agent absorbing the oil to be treated is taken in a large amount in the oil absorbing agent, this mixture has too much water, and even if mixed water is removed, It is difficult to incinerate as it is.

The method of causing the oil absorbing agent to "absorb" the oil to be treated is not specified. Even if the oil-absorbing agent is sprayed on the oil-to-be-treated and thrown in and left as it is, the oil-to-be-absorbed gradually absorbs with time. However, in this case, the oil absorbing agent and the oil to be treated cannot be quickly and sufficiently brought into "contact" and absorbed, so that the oil is usually stirred by appropriate means,
Mixing promotes contact between the oil absorbing agent and the oil to be treated and absorption of the oil to be treated by the oil absorbing agent. The stirring and mixing may be performed manually, but it is not easy to sufficiently stir and mix the slurry-like oil to be treated with high viscosity by manual power.
Therefore, an oil absorbing agent is sprayed on the oil to be treated collected in a container or the like,
After insertion, an impeller or the like may be inserted and rotated by some power.

The oil-absorbing agent absorbs the oil to be treated, and the water mixed in the oil to be treated is "discharged", and the oil to be treated in the form of slurry gradually loses its tackiness and becomes solid. It changes. As the properties change in this way, the mixture containing the oil absorbing agent, the oil to be treated, and water is hardly attached to the wall surface of the container or the impeller, and does not stick,
It becomes easy to handle. Further, water contained in this mixture can be removed from the system by "dehydrating" the mixture as in the third invention. As a result, the mixture can be made into a lump consisting essentially of solids. In addition, water that has been taken in the oil absorbing agent after being discharged from the oil to be treated can be easily removed by pressure filtration, centrifugation, or the like.

The method of dehydration is not particularly limited.
Dehydration can be performed by various methods such as a filter press such as a squeezing filter press, a belt press, a screw press, and a centrifugal separation such as centrifugal sedimentation and concentration.

In addition to the method of dehydrating using the specific device as described above, the mixture can be pressed to perform dehydration. As long as the oil to be treated is collected in a suitable container such as a drum can or the like, a person can ride on the above mixture and press down with his / her feet, or may press down with any tool. If water cannot be sufficiently removed by human power, appropriate mechanical power may be used. For example, a disk-shaped plate-like body having a shape similar to the cross section of a container such as a drum can and having a slightly smaller area may be pressed, and this may be pressed by hydraulic pressure or the like. The water that emerges from the upper portion due to the pressing can be removed by flowing out from a through hole for drainage provided at an appropriate position on the side surface of the container or the like. The mixture dehydrated in this way becomes a solid mass with little tackiness.

Further, the oil-absorbing agent absorbs the oil to be treated by stirring and mixing, the water is discharged, and the mixture having reduced adhesiveness is placed on a suitable wire mesh or the like, and the mixture is pressed from above. It is also possible to dehydrate and remove water out of the system. Further, the mixture can be passed between a pair of rolls at appropriate intervals and pressed to remove water. Such as the above filter press and the method of using this roll,
If the method uses a full-fledged machine or equipment, the process of spraying and introducing the oil absorbing agent to the collected oil to be treated, stirring and mixing to absorb the oil to be absorbed into the oil absorbing agent and mixing the water The step of discharging water and the step of dewatering and removing water to the outside of the system are mechanized to provide a continuous treatment apparatus, so that the oil to be treated can be treated more efficiently.

Incidentally, if such a series of processing devices are provided on a ship of a processing vessel for collecting spilled oil, etc., (1) collection of spilled oil, (2) spraying and charging of an oil absorbing agent, and (3) stirring Absorption of the oil to be treated by mixing, draining of water, (4) removal of water out of the system by dehydration, and (5) collection of hardly sticky lump, etc. should be carried out continuously on a ship, etc. You can also In addition, the discharged and removed water is appropriately provided if necessary.
After cleaning, it can be returned to the sea. If a series of processes are performed on the processing boat in this way, the lump collected at the port of call can be easily loaded on a truck or the like, and post-processing is extremely easy regardless of whether it is landfilled or incinerated.

[0020] The magnitude of the force applied to the mixture containing the oil absorbing agent, the oil to be treated and water during the dehydration is not particularly limited. However, it is preferable that the pressure is increased to such an extent that 50% or more of the mixed water, particularly 60% or more, and further, as in the fourth invention, "70% or more" is dehydrated. The water to be dehydrated can be 80% or more. The greater the applied pressure, the more water is removed, and a more difficult to adhere and easier-to-handle mass is formed. This lump is also easy to incinerate.

The less water remaining in the mass, the more
It becomes more difficult to adhere to other objects, and it becomes very easy to treat it, whether it is landfilled or incinerated. This water is discharged and the dehydrated lump can be used as a solid fuel as in the fifth invention. In addition, in the case of the above-mentioned mixture which is only dewatered and not dewatered, at least 10% or more, especially 20% of water mixed in the oil to be treated.
As described above, it is generally assumed that about 25 to 35% is discharged.

The weight ratio between the oil to be treated and the oil absorbing agent mixed with water is not particularly limited. It is not necessary to use an excess amount of the oil absorbing agent with respect to the oil to be treated, but it is preferable to use an amount of the oil to be treated as much as possible, preferably such that all the oils to be treated are absorbed by the oil absorbing agent. preferable. When the amount of the oil to be treated is 100 parts by weight (hereinafter, referred to as “parts”), the oil absorbing agent is preferably at least 20 parts, particularly preferably at least 30 parts. Further, 30 to 70 parts, especially 40 to 6 parts of the oil absorbing agent is used.
It is particularly preferable to use 0 parts. If the amount is within this range, the oil to be treated is quickly and reliably absorbed by the oil absorbing agent, and the mixture containing the oil absorbing agent, the oil to be treated, and water has an adhesive property. It is low and easy to handle. In addition, if necessary, water can be easily removed from the system by dehydration to form a lump having little tackiness and being easier to handle.

The solid fuel according to the fifth invention is a solid fuel containing an oil-absorbing agent containing an oil-absorbing polymer, the oil to be treated absorbed by the oil-absorbing agent, and water, wherein the oil to be treated is mixed with water. Or, the oil absorbing agent is brought into contact with the oil to be treated which is mixed with water and the water is mixed therein, the oil to be treated is absorbed by the oil absorbing agent, and at least a part of the water which is mixed into the oil to be treated And then a mixture containing the oil absorbing agent, the oil to be treated, and water discharged from the oil to be treated is obtained by dehydration.

The oil absorbing polymer according to the fifth invention includes:
The same one as in the first invention can be used. The oil to be treated is, for example, oil recovered from the ocean, river, or the like in an appropriate container or the like as in the first invention. In addition, the "water contained in the solid fuel" is obtained by absorbing the oil to be treated into the oil absorbing agent, discharging the mixed water, and further dehydrating by pressure filtration, centrifugation, pressing and the like. If the mixed water is 100 parts, it can be reduced to 30 parts or less. This water is particularly preferably at most 15 parts, more preferably at most 10 parts.

As described above, when the amount of water is small, the solid fuel is less sticky, does not adhere to or stick to other materials, is easy to handle, and is very easy to use as a fuel. This solid fuel can be used as it is as the main fuel, especially when the amount ratio of water is lower. Even when water is close to the upper limit of 15 parts of the preferred range, it can be used at least sufficiently as an auxiliary fuel for other fuels. The solid fuel of the present invention is particularly suitable as a fuel in industries requiring a large amount of inexpensive fuel, such as steel, thermal power generation, and cement production.

The oil absorbent used in the present invention is often incinerated after treating the oil to be treated. in this case,
By mixing and using a specific basic inorganic salt in the oil absorbing agent, at the same time as incineration, without requiring any other operation,
The sulfur content in the oil to be treated can be desulfurized and treated.
In addition, when the oil to be treated is processed and the oil is recovered from the oil absorbing agent, the same operation and effect can be obtained. When the component of the oil absorbing agent itself, such as an oil absorbing polymer, contains sulfur in addition to the sulfur in the oil to be treated, the sulfur can also be desulfurized and treated. In particular, in the solid fuel of the fifth invention, it is preferable to blend this "basic inorganic salt" as in the sixth invention.

As the basic inorganic salt, it can be blended with an oil-absorbing polymer to be dispersed and mixed. When the used oil-absorbing agent is incinerated, the sulfurous acid gas generated from the sulfur content in the oil to be treated is used. And the like which can react with SO _x , H ₂ S, etc., and convert it into a sulfate or the like. As the basic inorganic salt, it is particularly possible to use at least one of an alkali metal carbonate, an alkali metal hydroxide, an alkaline earth metal carbonate and an alkaline earth metal hydroxide. preferable.

As the above-mentioned carbonate, any of normal salt, hydrogen carbonate and carbonate hydroxide can be used.
Further, any of alkali metals and alkaline earth metals constituting the salt may be used, but sodium, potassium, calcium, magnesium, barium and zinc are more common in terms of cost, availability, and the like. It is. Furthermore,
In the case of hydroxides, calcium hydroxide, magnesium hydroxide, barium hydroxide and the like are usually used.

The particle size of the basic inorganic salt is not particularly limited, but is 0.01 to 900 μm, particularly 0.05 to 900 μm.
It is preferably about 300 μm, more preferably about 0.5 to 100 μm. If the particle size is less than 0.05 μm, especially less than 0.01 μm, the particles of the basic inorganic salt aggregate and are difficult to handle. In addition, workability when dispersing and mixing with the oil absorbing polymer is poor, which is not preferable. On the other hand, when the particle size exceeds 900 μm, the reactivity with SO _x or the like generated during incineration of the oil absorbing agent is reduced, and a part of the SO _x or the like may be released to the atmosphere as it is, which is preferable. Absent.

The amount of the basic inorganic salt to be incorporated into the oil-absorbing polymer such as a polymer composed of norbornene or the like is not particularly limited as long as it can be appropriately uniformly dispersed and mixed. However, it is not necessary to mix a basic inorganic salt in an amount more than a required amount, and an appropriate mixing amount may be determined depending on the type and properties of the oil to be treated. This blending amount is 1 to 20%, especially 2 to 15%, and more preferably 3 to 10% with respect to 100% of the oil absorbing polymer.
%, The oil absorbing properties and oil retaining properties inherent to the oil absorbing polymer are not impaired. In addition, with such a blending amount, uniform dispersion and mixing can be achieved, and a uniform oil absorbing agent can be obtained.

The oil absorbing polymer used in the present invention,
Particularly, in the case of a polymer having a large molecular weight such as a polymer made of norbornene or the like, an appropriate amount of a softening agent may be added. This softener facilitates blending of other additives, granulation of the polymer, and the like. As the softener, various plasticizers, surfactants, and the like can be used. As a plasticizer,
Phosphoric esters, phthalic esters, oxyacid esters and the like can be used. In addition, as a surfactant,
In addition to anionic surfactants such as carboxylate, sulfonate, sulfate ester salt and phosphate ester salt, various surfactants such as cation surfactant and nonionic surfactant can be used.

In the polymer composed of norbornene or the like, the softener is preferably a salt of a fatty acid having 12 to 18 carbon atoms. As the fatty acid, lauric acid, myristic acid, palmitic acid, stearic acid, and the like, which are saturated acids, and oleic acid, which is an unsaturated acid, are generally used. Further, the salt is usually an alkali metal salt and an alkaline earth metal salt, and examples thereof include a sodium salt, a potassium salt, a calcium salt and a magnesium salt. Among these salts, calcium stearate is particularly preferable, and addition of this salt facilitates compounding of various additives and facilitates granulation of the polymer, which is preferable.

The amount of the above softener is 1 to 30%, especially 3 to 20%, more preferably 5 to 15%, when the oil absorbing polymer such as a polymer composed of norbornene or the like is 100%.
The degree is preferred. When the softening agent has an oil absorbing property, the addition amount may be determined in consideration of the property. Further, when the softening agent is water-soluble, the softening agent may dissolve in water mixed with the oil to be treated and flow out. Further, the softener may be discharged from the mixture containing the oil absorbing agent, the oil to be treated and water, dissolved in the water to be dehydrated, and flow out to the ocean, river, or the like. Therefore, care must be taken not to add more than the required amount.

The oil absorbing polymer can be prepared by blending various additives which are usually added to resins, rubbers and the like to the oil absorbing polymer. Such additives include antioxidants, ultraviolet absorbers, lubricants, antistatic agents and the like. Further, if necessary, a pigment such as a fluorescent pigment may be added to color the oil absorbing agent in an appropriate color tone. In addition, the oil absorbing agent used in the present invention may be considerably heated when a basic inorganic salt, a softening agent and the like are mixed and added to an oil absorbing polymer such as a polymer composed of norbornene or the like. Therefore, especially in order to prevent thermal deterioration in such a process, for example, when a phenolic antioxidant such as dibutylhydroxytoluene is used in an oil-absorbing polymer of 100%, 0.5 to 7%, especially 1-5
%, More preferably about 2 to 4%.

The method of adding a softener or the like to an oil-absorbing polymer such as a polymer composed of norbornene is not particularly limited. For example, a softener or the like can be adhered to the surface of the oil-absorbing polymer particles by mixing with a mixer such as a Henschel mixer or a turbo mixer. However, since the softening agent and the like may not act sufficiently only when they are simply adhered, it is preferable that the mixture is further melted and kneaded by extrusion molding or the like, and then granulated.

The method of blending the basic inorganic salt with the oil absorbing polymer is not particularly limited. For example, the particles of the basic inorganic salt and the oil-absorbing polymer may be simply mixed, or after mixing, vibration may be applied, and the basic inorganic salt may be adhered and fixed to the surface of the oil-absorbing polymer by static electricity. Good.
The adhesion and fixation are performed by mixing a basic inorganic salt with the oil-absorbing polymer, and heating the oil-absorbing polymer to a temperature near the softening point of the oil-absorbing polymer or a high temperature below the decomposition temperature to bond the surface of the oil-absorbing polymer. It can be implemented by making it possible.
Furthermore, the basic inorganic salt can be adhered and fixed on the surface by heating the basic inorganic salt to about 800 ° C. in the case of, for example, calcium carbonate and mixing it with the oil-absorbing polymer.

In the present invention, the oil to be treated is not used directly for oil spills floating in the ocean or the like, but is used for oil to be treated recovered by some method. Therefore, it is not necessary to pay much attention to the scattering of the oil absorbing agent due to wind, waves, or the like, or the injection of the oil absorbing agent into a predetermined location. Therefore, the granular oil absorbing agent may be directly sprayed, charged, mixed and dispersed in the oil to be treated. However, especially when the oil to be treated is collected in a container having a large capacity, an appropriate amount of the oil absorbing agent is stored in a packaging container of an appropriate size to form an oil treatment material. Good.

As a packaging container, immediately dissolve in water,
Further, those made of a material that hardly absorbs oil are preferable. Further, the shape and the like of the packaging container are not particularly limited, but it is preferable to use a bag-like container made of a film having such a strength that it is not easily damaged during transportation, storage and handling.

As a material soluble in water, natural polymers such as proteins and starch can be used. Further, synthetic polymers such as polyvinyl alcohol, polyethylene oxide, polyacrylamide, and polyvinylpyrrolidone can also be used. As the material that dissolves in water, polyvinyl alcohol that dissolves promptly in water and does not generate insoluble components is preferable. In addition, the water-soluble paper is slightly inferior in the absorption rate of water and contains insoluble components, so that the whole amount is insoluble in water. However, in the present invention, it can be used without any problem.

In the method for treating an oil to be treated according to the first aspect of the present invention, the water contained in the oil to be treated can be easily discharged by making the oil absorbing agent absorb the oil to be treated. In addition, water can be easily removed from the system by a very simple method of dehydrating a mixture containing an oil absorbing agent, an oil to be treated, and discharged water by pressure filtration, centrifugation, or the like. Dehydration can be performed more effectively in proportion to the strength of the force applied in pressure filtration, centrifugation, etc., and the stickiness of the formed lump becomes lower, sticking to the wall of the collection container, etc. And handling becomes extremely easy. The water thus sufficiently discharged and the dehydrated mass can be easily burned. Mixtures and lumps, especially lumps with lower water content, are also very advantageous in terms of transportation during disposal, such as landfilling and incineration.

When an oil absorbing agent containing a specific basic inorganic salt is used, sulfur contained in the oil to be treated is oxidized and generated during incineration or oil recovery. A harmful gas such as sulfurous acid gas reacts with the basic inorganic salt to become a solid and is not released into the atmosphere.
Further, even when salt in seawater is taken into the oil absorbing agent, harmful gas such as hydrogen chloride generated by oxidation becomes solid chloride and is not released into the atmosphere. Further, in the method for treating oil to be treated of the present invention, sulfur contained in the oil absorbing agent itself is treated in the same manner, and is not released into the atmosphere.

The method for treating oil to be treated of the present invention,
It is particularly useful for treating oil spills collected during an oil spill accident in the ocean or the like. When not only oils such as gasoline, kerosene, light oil, and heavy oil, but also various organic solvents such as benzene, xylene, toluene, ether, ketone, and ester are mixed with water, apply them to the absorption and treatment of them. Can also.

[0043]

BEST MODE FOR CARRYING OUT THE INVENTION

(1) Addition of softener and antioxidant to polynorbornene 88.1% of granular polynorbornene and 8.9% of calcium stearate were charged into a turbo mixer, and stirred and mixed in a dry state. Thereafter, the mixture of polynorbornene and calcium stearate and 3.0% of a phenolic antioxidant (dibutylhydroxytoluene) were added.
After being melted and kneaded by an extruder, the mixture was granulated, classified by a sieve, and those having a particle size of 100 to 600 μm were selected. Those having a particle size of less than 100 μm and those having a particle size of more than 600 μm were returned to the extrusion step and reused. In addition, the thing which deviated from this particle size may be used for another use.

(2) Preparation of Oil Absorbing Agent 10% of calcium carbonate is blended with 100% of polynorbornene containing calcium stearate and antioxidant prepared as described above, and uniformly mixed in a dry state by a turbo mixer. Thus, an oil absorbing agent containing an oil absorbing polymer was prepared. Oil-absorbing paper having a high oil-absorbing rate obtained by subjecting the fibers of the paper pulp to a water-repellent treatment or by subjecting the water-repellent treated paper to a cotton-opening process was used for comparison.

(3) Performance Evaluation of Oil Absorbent The oil to be treated which spilled into the ocean and drifted on the shore (including heavy fuel oil C, such as gravel, sand, and other contaminants and water; It is estimated that the amount of water is several percent or less, and the amount of water is about 60% of the total amount.)
40 g of each type of oil absorbing agent was charged. The oil to be treated was a slurry having a considerably high viscosity, but in the case of an oil absorbing agent containing an oil absorbing polymer, the oil absorbing agent was absorbed by the oil to be treated by stirring and mixing with a glass rod. The mixed water was discharged and the tackiness was gradually lost.

Further, when the upper surface of the oil-absorbing agent which has absorbed the oil to be treated is pressed by a glass disk-shaped plate slightly smaller than the cross-sectional area of the beaker, the oil-absorbing agent is discharged from the oil to be treated and taken into the oil absorbing agent. The water was easily dehydrated from the oil absorbent and emerged at the top. This water was discarded, and when pressed further, it could be easily dewatered again. As a result, water was discharged, and the dehydrated residue became a solid mass having almost no tackiness, did not adhere to the wall surface of the beaker at all, and became very easy to handle.

On the other hand, in the comparative oil absorbing agent, it was observed that the oil to be treated was absorbed by the oil absorbing agent and integrated. However, there was almost no change in the properties of the slurry, the viscosity was high, and the slurry adhered and adhered to the glass rod. Thereafter, pressing was similarly performed using a glass disk-shaped plate, but the oil absorbing agent that absorbed the oil to be treated adhered to the entire pressing surface of the disk. Also, although water may have been discharged, everything is taken up by the oil absorbing agent, and the appearance of the mixture is almost the same as that of the original oil to be treated, and the oil absorbing agent containing the oil absorbing polymer The behavior was completely different from the case.

The present invention is not limited to the specific embodiments described above, but may be variously modified within the scope of the present invention in accordance with the purpose and application. For example, the oil absorbing agent containing an oil absorbing polymer includes rice hulls, straw, pulp, cotton, porous lime, porous silica, porous pearlite, polypropylene fiber, conventionally known oil absorbing agents and fillers such as urethane foam. They can be used in combination.

[0049]

According to the first aspect of the present invention, the water mixed in the oil to be treated is easily discharged, and a low-stick, solid mixture containing an oil absorbing agent or the like that has absorbed the oil to be treated is produced. The mixture can be easily dehydrated by a very simple method such as pressure filtration, centrifugation or pressing. As a result, the mixture becomes a lump having almost no tackiness, and does not adhere to or stick to other things such as the wall surface of the collection container, and is very easy to handle. Also,
According to the fifth invention, a solid fuel that is low in water content and easy to handle can be obtained, and particularly useful solid fuel is obtained in industries requiring a large amount of inexpensive fuel such as steel, thermal power generation, and cement production. be able to.

Claims (6)

[Claims] 1. An oil-absorbing agent containing an oil-absorbing polymer is brought into contact with an oil-to-be-processed oil or an oil-to-be-processed oil which is mixed with water and mixed with water. A method for treating an oil to be treated, wherein the oil is absorbed and at least a part of the water mixed in the oil to be treated is discharged. 2. The oil absorbing polymer according to claim 1, wherein said oil absorbing polymer is bicyclo [2.
2.1] The method for treating an oil to be treated according to claim 1, which is a polymer of at least one of heptene-2 and a substituted derivative thereof. 3. The method for treating an oil to be treated according to claim 1, wherein a mixture containing the oil absorbing agent, the oil to be treated, and the water discharged from the oil to be treated is dehydrated. 4. The method according to claim 1, wherein the water mixed in the oil to be treated is 1
The method for treating an oil to be treated according to any one of claims 1 to 3, wherein 70% by weight or more of the oil is discharged and dewatered when the amount is 00% by weight. 5. An oil-absorbing agent containing an oil-absorbing polymer, a solid fuel containing water to be treated and water absorbed by the oil-absorbing agent, wherein the solid fuel contains water and is mixed with the oil or water to be treated. The oil absorbing agent is brought into contact with the oil to be treated in which water is mixed, the oil to be treated is absorbed by the oil absorbing agent, and at least a part of the water mixed in the oil to be treated is discharged. A solid fuel obtained by dehydrating a mixture containing the oil absorbing agent, the oil to be treated, and water discharged from the oil to be treated. 6. The solid fuel according to claim 5, wherein the oil absorbing agent contains a basic inorganic salt.