JPH07178391A - Method for removing contaminated portion of organic liquid - Google Patents

Abstract

PURPOSE: To highly effectively remove org. liq. contaminants from an aq. soln. in which the contaminants are captured by passing the aq. soln. through a contact region contg. fixed beds of at least one of granular thermoplastic elastomeric linear diblock, triblock and branched diblock copolymers.

CONSTITUTION: An aq. soln. in which org. liq. contaminants are captured is passed through a contact region contg. fixed beds 12, 14 of at least one of granular thermoplastic elastomeric linear diblock, triblock and branched diblock copolymers which are granular thermoplastic elastomeric block copolymers comprising monovinyl arom. polymer blocks bonded to elastomeric conjugated diene polymer blocks and/or monovinyl arom. polymer blocks bonded to elastomeric monolefin polymer blocks. A water stream substantially freed of the contaminants is drawn out of the contact region.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an organic liquid substance and crude oil,
Petroleum products, including refined petroleum distillates, are used in water, soil, water streams,
It relates to methods for removing bottom sewage and solid surfaces such as garages, store floors and steel decks.

[0002]

BACKGROUND OF THE INVENTION Various techniques have been proposed for treating petroleum pollutant spills. Various substances containing large amounts of straw, clay, silica and diatomaceous earth particles have been suggested as absorbents for oil spills. It has also been proposed to use foamed polymeric materials such as porous polystyrene particles and porous polyethylene fibers, either alone or with additives such as other solid mineral fillers.

In US Pat. No. 3,518,183, a large area monovinylarene-conjugated diene block copolymer is applied to the oil to contact the oil slick and the oil spill, and the oil is absorbed into the block copolymer to form an oil. Separating the impregnated block copolymer from water is disclosed. The block copolymer can be loaded into a tubular net in the form of a collar surrounding an offshore drilling platform. The block copolymer may also be incorporated into a boom or embankment to prevent oil slicks from spilling out to the harbor entrance or along the shoreline.

US Pat. No. 4,941,978 discloses treating oil spills on the surface of water with a particulate elastomer composition consisting of a block copolymer of styrene and an ethylene / butadiene copolymer elastomer.

[0005]

SUMMARY OF THE INVENTION The present invention relates to the recovery of oil and other liquid contaminants from soil and water with granular thermoplastic elastomer block copolymers. In one of its aspects, the present invention is a method of removing organic liquid contaminants from an aqueous solution in which it is entrapped by passing the solution through a contact area containing a fixed bed of particulate thermoplastic elastomer block copolymer. Concerning the method consisting of. The thermoplastic elastomer copolymer comprises linear diblock copolymers, triblock copolymers or branched diblock copolymers. Further, the granular thermoplastic elastomer block copolymer consists of a monovinyl aromatic polymer block bonded to an elastomer conjugated diene polymer block, or a monovinyl aromatic polymer block bonded to an elastomer monoolefin polymer block. After passing the aqueous solution through a fixed bed of granular block copolymer, a substantially contaminant-free water stream is recovered from the contact area. If desired, this aqueous solution can be treated with one or more of ozone, UV irradiation and activated carbon and also passed through an air stripper.

The elastomeric polymer block and / or the monovinyl aromatic polymer block may be partially or wholly hydrogenated. Preferably, the thermoplastic elastomer copolymer comprises polystyrene-polybutadiene-polystyrene block copolymer or polystyrene-ethylene / butylene copolymer-polystyrene block copolymer.

Further, by coating a thermoplastic rubber selected from the group consisting of monovinyl allene-conjugated diene block copolymers, monovinyl allene-monoolefin block copolymers and hydrogenated derivatives of these block copolymers with a small amount of hydrophobic silica, It was found that the oil spill absorption time can be dramatically reduced and the amount of polymer required can be dramatically reduced. According to the present invention, a hydrocarbon spill is contacted with the composition of the present invention to encapsulate the hydrocarbon. When the spill is a crude or refined petroleum product spill on water, the composition containing the encapsulated oil of the present invention floats on the surface of the water and can be easily picked up and recovered. When the spill is on a solid surface, such as a garage floor, the composition of the present invention encapsulates the spilled liquid and the spilled liquid can be easily wiped with almost no trace.

The present invention also relates to a method of removing organic liquid contaminants from soil, the first step being to combine the soil contaminated with organic liquid with one of the thermoplastic elastomer block copolymers described above. Next, the soil contaminated with the organic liquid and the thermoplastic elastomer copolymer are mixed to form a homogeneous mixture. The homogeneous mixture is then mixed with water, the organic liquid contaminants encapsulated with the copolymer are removed from the homogeneous mixture, and the contaminant-free soil is recovered from the rest of the mixture.

In one aspect of the invention, the contaminated soil is first washed with water, preferably under pressure, and the water extract is then treated with the contaminated liquor in a fixed bed of granular thermoplastic elastomer block copolymer in the manner described above. It can be processed by passing it through the contact area containing it.

The organic liquid contaminants, optionally encapsulated with the copolymer, are dissolved in an organic solvent such as petroleum naphtha, gasoline, diesel fuel or fresh crude oil and recovered from the homogeneous mixture before the organic liquid contaminants-elastomer. -It may be adapted to form a liquid composition of petroleum, and the resulting liquid composition may be used as fuel for furnaces, engines and the like. Also, soil contaminated with organic liquids is typically excavated prior to mixing it with the thermoplastic elastomer block copolymer.

The present invention also provides a method for removing an organic liquid film from a solid surface, wherein the thermoplastic elastomer block copolymer is evenly distributed on the organic liquid film, and the organic liquid-encapsulated copolymer is provided on the solid surface. A method consisting of removing from. The amount of block copolymer applied is typically from about 0.1 to about 1 pound per gallon of organic liquid, depending on the surface area of the spill and the viscosity of the organic liquid and the length of time the organic liquid has been dwelling. Is the range. For example, the larger the surface area, the more viscous the organic liquid, the longer the organic liquid stayed,
Larger amounts of polymer will be required to encapsulate the organic liquid.

In yet another aspect, the present invention relates to a method of utilizing a hydrocarbon fluid recovered from water by encapsulating the hydrocarbon fluid with one of the above thermoplastic elastomer block copolymers. This method uses a hydrocarbon fluid encapsulated in a thermoplastic rubber as a petroleum naphtha,
It comprises the steps of dissolving in a solvent such as gasoline, diesel fuel and crude oil to form a liquid composition of thermoplastic rubber-hydrocarbon fluid-petroleum suitable for use as a fuel in furnaces, engines and the like. Thus, the method also includes the step of burning the thermoplastic rubber-hydrocarbon fluid-petroleum liquid composition in a furnace. Suitably, the solvent is heated during the dissolution process to facilitate dissolution.

The present invention further relates to a method of removing organic liquid contaminants from soil, wherein soil contaminated with organic liquid matter is thoroughly mixed with water to leach organic liquid contaminants from the soil, A mixture is obtained. This soil / liquid mixture is then filtered to obtain washed soil and an aqueous filtrate containing organic liquid contaminants. The aqueous filtrate is then sent to a contact area containing a fixed bed of one of the particulate thermoplastic elastomer block copolymers described above, and a substantially contaminated water stream is recovered from this contact area.

The present invention further relates to a method of preventing organic contaminants from leaching from an underground fuel tank into the underlying soil. This method comprises mixing an initial amount of soil with the thermoplastic elastomer block copolymer to form a soil / block copolymer mixture, which is placed at the bottom of a hole dug in the base soil. Positioning the underground fuel tank above the soil / block copolymer mixture, and making a second
Consisting of the steps of filling the soil with an amount of. The soil / block copolymer mixture absorbs the fluid leaking from the fuel tank and escaping down, thus preventing the fluid from seeping into the base soil.

The present invention also relates to a method of preventing organic contaminants leaking or spilling from an oil well from seeping into the surrounding substrate soil. In this method, an initial amount of soil is mixed with one of the thermoplastic elastomer block copolymers to produce a soil / block copolymer mixture,
This soil / block copolymer mixture is placed on the ground around the well. The soil / block copolymer mixture absorbs organic contaminants that are leaking or spilling from the well, thus preventing organic contaminants from seeping into the base soil.

[0016]

EXAMPLES The composition used in the present invention is a thermoplastic elastomer block copolymer. The thermoplastic elastomer block copolymer used in the practice of the present invention is
(1) A block polymer segment of a vinyl aromatic monomer and a conjugated diene, wherein at least one monovinyl aromatic polymer block is attached to a conjugated diene polymer block, or (2) at least one monovinyl aromatic polymer block is attached to a monoolefin polymer block. Block polymer segment of vinyl aromatic monomer and monoolefin monomer, or (3)
It consists of hydrogenated derivatives of these block copolymers.
Each polymer or block segment may be 100 or more individual monomer units joined together.

More particularly, the block copolymer used in the present invention is a thermoplastic elastomeric linear diblock, triblock or branched copolymer, wherein the monovinylaromatic polymer block is an elastomeric conjugated diene or an elastomeric monoblock. Included are olefin polymer blocks, as well as hydrogenated derivatives of such polymer blocks. The general structure of thermoplastic elastomer block copolymers can be linear ABA triblock, radial or branched AB diblock, and linear AB diblock. In such a structure, "A" represents a monovinyl aromatic polymer block, some or all of which may be hydrogenated, and "B" is an elastomeric conjugated diene, hydrogenated diene or monoolefin. Or represents a hydrogenated monoolefin polymer block.

The ABA triblock structure has the elastomeric block B as the middle block and the polymer block A as the end block. Radial or branched A
-B diblock copolymer is a common hub where multiple A polymer blocks are joined at their first ends.
Is formed. Second of each A polymer block
The terminals extend radially from the common center in various directions. Each of the second terminals is attached to a B-polymer block, which generally extends radially outward from the common center.

The monovinylaromatic polymer block is either a homopolymer or a copolymer, with the monovinylaromatic monomer predominating as the major polymerisable unit in general. The conjugated diene and hydrogenated monoolefin polymer blocks and the monoolefin and hydrogenated monoolefin polymer blocks can be either homopolymers or copolymers. The essential feature is that they are of such composition that they are characterized by their elastomeric properties.

Blocks "A" and "B" may be partially or wholly hydrogenated. If the hydrogenation is only partial, it is preferred that block "B", the conjugated diene polymer block, be hydrogenated to improve its oxidation resistance. Thus, the polymer can be an unhydrogenated, partially hydrogenated, or fully hydrogenated polymer block.

Monovinyl aromatic monomers that can be used to form the thermoplastic elastomer block copolymers of the present invention include styrene, alpha-methyl styrene, and cycloalkylated styrenes. These are polymerized with each other or with a small amount of conjugated dienes to form block "A".
To form. Conjugated dienes that can be utilized to form block "B" or as a minor component of block "A" include:
A conjugated diene, preferably having 4 to 8 carbon atoms per molecule,
Among these are butadiene and isoprene. Block "B"
The monoolefins which can be used for the formation of OH have preferably 2 to 8 carbon atoms, especially ethylene, propylene and butylene. The presently preferred monoolefin "B" block consists of an ethylene / propylene and ethylene / butylene copolymer.

Typical thermoplastic elastomer block copolymer forms are polystyrene-polybutadiene-polystyrene, polystyrene-polyisoprene-polystyrene, and polystyrene-poly (ethylene / butylene)-.
Polystyrene ABA triblock copolymers; polystyrene-polybutadiene and polystyrene-polyisoprene radial or branched AB diblock copolymers; and polystyrene-polybutadiene, polystyrene-poly (ethylene / propylene), and polystyrene-poly It is a linear AB diblock copolymer of (ethylene / butylene). The presently preferred thermoplastic elastomer block copolymer is polystyrene-polybutadiene-
Polystyrene and polystyrene-poly (ethylene / butylene) -polystyrene linear ABA triblock copolymers.

Thermoplastic rubbers particularly suitable for use in the present invention are available on the market today from Micro Invilonal Incorporated of Grand Rapids, Mich. Under trade designations PS320 and PS3400.
The PS3200 product is a polystyrene-polybutadiene-polystyrene block copolymer and the PS3400 product is a polystyrene-poly (ethylene / butylene) -polystyrene block copolymer. The most suitable materials are available from the above manufacturers as particulate material in either pellet or powder form. It is preferred to use the powder form, since at present the powder form exhibits a larger surface area due to absorption and / or adsorption (“encapsulation”) than pellets. Preferably, the thermoplastic elastomer (rubber) block copolymer particles have a particle size of 100 to 300 microns, with 180 to 220 microns being most preferred.

In some cases, it is desirable to uniformly coat the thermoplastic elastomer copolymer particles with a small amount of hydrophobic silica to increase fluidity and increase hydrocarbon uptake. Hydrophobic silicas that can be used are disclosed in the patent and technical literature and are readily available commercially.
Hydrophobic silica includes silica, diatomite, kieselguhr, and diatomaceous earth treated to render other substances hydrophobic.
Silica materials such as earth) may be included. A particularly preferred silica is the hydrophobic amorphous fumed silica, available from Aerosil R-972, R-972V, R-97 from Degussa Corporation of Richfield Park, NJ.
4, available under the designations R-974V and R-976.
The hydrophobic silica is from 0.1 to 2.5% by weight, most preferably 0.1% by weight, based on the weight of the thermoplastic elastomer block copolymer.
It can be used at 5% by weight.

The hydrophobic silica can be easily mixed with the thermoplastic elastomer block copolymer by conventional blending techniques, the block copolymer having its surface coated with a substantially uniform hydrophobic silica.

The amount of treated block copolymer utilized depends, in part, on the thickness of the oil film to be absorbed, the time required for economical collection of the oil, and the water from which the oil should be removed when treating the oil slick. Depends on the agitation method and similar physical factors. It is preferred to apply the milled block copolymer in an amount of 3 to 7 pounds per gallon of breakthrough when the breakthrough is a film less than about 0.5 inch thick. The time required to encapsulate the oil with the block copolymer will depend on the temperature, the degree of agitation, the elastomer spill to block copolymer ratio, the viscosity of the liquid, and the surface area of the block copolymer utilized.

The coated block copolymer encapsulant of the present invention begins encapsulating the hydrocarbon spill in seconds when the new encapsulant is contacted with the liquid spill. The overall time required to clean a spill of 0.5 inch or less is typically several minutes. Large spills, such as when a tanker runs aground, can take a long time because continuously providing a surface of new encapsulant is a function of time depending on the amount of spill and the area spread. It will cost. Generally, treatment of the spill with the encapsulating agent of the present invention is preferably initiated within about 4 hours of the spill. Very large leaks may require more than one treatment with the composition of the present invention.

Surprisingly, even if the block copolymer is treated with a small amount of hydrophobic silica (eg 1 to 2.5% by volume), the block copolymer's volumetric absorption is from about 3 oil volumes / block copolymer volume to about. 4 oil volume / block copolymer volume. further,
Encapsulation of spilled oil with treated block copolymer is about 25% compared to oil absorption with untreated polymer
Also takes less time.

The breakthrough is substantially completely encapsulated within the body of the treated block copolymer and the surface of the block copolymer encapsulating agent is dry and non-toxic. This allows the collection of the encapsulated liquid and the block copolymer to be facilitated by such means as moving a rake, boom or net onto a surface such as water. When the spill is on a solid surface, such as a steel deck, wooden deck, concrete floor, etc., the encapsulated liquid polymer can be wiped off with a broom or the like.

Application of the compositions of the present invention to liquid spills can be accomplished by a variety of methods. Preferably, it is desirable to distribute the composition of the present invention relatively evenly over the contaminated area, or over the portion to be treated. The compositions of the present invention may be dispensed by aerial spraying or otherwise on and / or in the leak. This can be done in a variety of ways. Liquid spills, such as on concrete surfaces, can be absorbed by manually sprinkling or otherwise spraying the composition of the invention onto the spill. Small amounts of spillage above water can be treated by spraying, spraying or sprinkling the composition of the invention on a small boat. For large spills, it may be necessary to use several surface containers. If the oil appears to be spread over a large area, the substance can be easily sprayed over the oil slick with a regular airplane. If the spill is intended to continue spreading to the shoreline or beach, it can be contained by using a water-permeable boom in which the encapsulating agent of the composition of the invention is enclosed in a porous mesh cover. These booms are water permeable, but the oil is impermeable by encapsulation.

The composition of the invention may also be used for cleaning bilge tanks, either directly or by dispersing with a pillow or bilge bag. Bilge bags consist of a closed mesh cloth filled with the porous encapsulating composition of the present invention.

The present invention also relates to a method of removing organic liquid contaminants such as hydrocarbons, which are dispersed or trapped in water streams such as effluents from chemical treatment processes. In this method, a stream of water contaminated with organic liquid is passed through a fixed bed of thermoplastic elastomer copolymer absorbent particles. The water stream to be treated contains organic liquid pollutants such as fuels, methyl, ethyl ketone, toluene, ethylbenzene, xylene and benzene, and even metals such as iron. As an example, referring to FIG.
The copolymer processing unit 11, which constitutes a processing system for removing trapped organic liquid contaminants from the ship's bottom, comprises:
It has a bilge pump 10 connected by suitable pipes downstream of two co-polymer absorbent beds 12,14. The contaminated organic liquid stream is pumped out of the bilge 18 of the contaminated liquid container or other storage tank to the bilge removal pipe 16 and by the three-way valve 24 the treatment unit intake pipe 20.
Or sent to 22. The pressure of the contaminated organic liquid in the take-out pipe 16 can be measured by the pressure gauge 23.

When the three-way valve 24 is directing a contaminated stream to the intake pipe 20, the contaminated liquid is passed through the copolymer absorbent bed 12 by the pump 10, the bed comprising a fixed bed of thermoplastic elastomer block copolymer particles. There is. The treated aqueous liquid, which is substantially free of contaminants, exits the copolymer absorbent bed 12, enters the processing unit removal pipe 26, and flows through the three-way valve 28 into the reservoir intake pipe 30. The pressure gauge 32 measures the pressure of the treated liquid flowing through the storage tank intake pipe 30. The pump 10 transfers the treated liquid from the pipe 30 to the treated liquid storage tank 34,
Or return to bilge 18.

Copolymer absorbent bed 14 as is usual in liquid treatment systems having juxtaposed treatment units.
Is in a standby state for use when the first absorbent bed 12 is regenerated. Each copolymer absorbent bed 12, 14 is filled with a quantity of block copolymer-encapsulated particles sufficient to encapsulate about 2.5 quarts (about 2.3 liters) of liquid organic contaminants. Pressure gauge 23 and pressure gauge 3
The difference in pressure measured at 2 and 2 indicates the amount of pressure drop across the copolymer absorbent bed 12. When this pressure drop corresponds to an encapsulation of about 2 quarts (about 1.89 liters) of contaminants, an appropriate alarm is issued to the operator, thus activating the second copolymer absorbent bed 14, The fixed bed of the copolymer absorbent bed 12 of is regenerated. The second bed of copolymer absorbent 14 is operated by turning the three-way valve 24 to allow contaminated organic liquid to flow to the processing unit intake pipe 22. The treated liquid from the copolymer absorbent bed 14 enters the withdrawal pipe 36. The three-way valve 28 must be turned to direct this treated liquid to the reservoir intake pipe 30.

Thus operating the bilge filtration system over a period of several months substantially prevents leakage of contaminants to the environment. However, if the particle fixed bed of the copolymer absorbent bed in use is not regenerated in a reasonable amount of time, the absorbent bed will be under pressure of the treated liquid in the reservoir intake pipe 30 to maintain proper operation of the bilge pump 10. Will continue to work until they are insufficient.
Such operation will cause significant cavitation in the bilge pump 10.

Initial test data showed that a large number of copolymer processing units 11 similar to those shown in FIG. 1 could be placed in series to achieve a continuous high degree of contaminant removal. In contrast to this, FIG. 2 shows a combined system, which comprises one or more copolymer processing units 11, one or more air strippers 40, 1.
One or more ozone treatment units 42, one or more UV irradiation treatment units 44, and one or more activated carbon treatment units 46, which are arranged in series. Remove
It can be used to generate a contaminant-free stream 50. Of course, it is not necessary for the combination system to include all of these units, and any combination of elements may be used. For example, killing or harvesting bacteria 48
When removing metal from the ozone treatment unit 4
2 is preferably used. The ultraviolet irradiation processing unit 44 is also effective in killing bacteria. The decision to use another form of combination system or to use a series of polymer absorption columns depends on the nature of the contaminants, the degree of removal required, and the cost of removal. For example, if the water stream is predominantly contaminated with less volatile compounds such as xylene, then a polymer-only approach may be attractive from a technical and economic standpoint.

If it is intended to treat a gasoline contaminated water stream using a combined system, pretreating the water stream with a copolymer treatment unit prior to use of the air stripper unit will result in substantial amounts of benzene and toluene and low levels of toluene. It is possible to remove essentially all of the volatiles such as xylene. This reduces the load on the column containing activated carbon, thereby increasing the life of the activated carbon. The combinatorial processing approach will result in lower overall processing costs, as a significant reduction in carbon costs can be realized.

Further, in today's commercial treatment systems, activated carbon treatment units are typically used. The activated carbon treatment unit is an approved filter medium. However, activated carbon beds have to be regenerated on a daily basis at a considerable cost. However, by placing the copolymer treatment unit in series before the activated carbon treatment unit, the activated carbon of the activated carbon treatment unit need only be regenerated approximately every other day or every two days. In the use of this combination treatment unit, the copolymer of the copolymer treatment unit may be regenerated approximately every 3 or 4 days, which is lower than the regeneration cost of the activated carbon bed.

The present invention also relates to a method of utilizing hydrocarbon recovered from water by encapsulating a hydrocarbon fluid with a thermoplastic rubber block copolymer. In this method, a thermoplastic rubber encapsulated hydrocarbon fluid is dissolved in a solvent such as petroleum naphtha, gasoline, diesel oil and crude oil to form a thermoplastic rubber-hydrocarbon fluid-petroleum liquid composition. , It is suitable for use as fuel in furnaces, engines, etc. In other words, the thermoplastic rubber also dissolves in the solvent during this melting step. The thermoplastic rubber-hydrocarbon fluid-petroleum liquid composition can then be combusted in a furnace or used as a fuel in an engine. Preferably the solvent is heated during the dissolution process to facilitate dissolution of the thermoplastic gum encapsulated hydrocarbon fluid.

The present invention also relates to two methods for recovering organic liquids, especially hydrocarbons, that have penetrated into the soil. Referring to FIG. 3, this first method is shown in which soil contaminated with spilled liquid is excavated and loaded into a mixer such as a ribbon blender. Next, one of the block copolymer encapsulating agents as described above is added to the contaminated soil in the blender in a weight ratio of about 1:10 to about 1: 1, preferably 1: 1. It may be advantageous to add a certain amount of new hydrocarbons to the soil and encapsulant in the blender to activate organic liquid contaminants.

Third, the contaminated soil and the block copolymer encapsulating agent are mixed in the blender for a sufficient time,
The contaminant is adsorbed or absorbed by the block copolymer. The mixing time can be 30 seconds to 2 hours or more, depending on the nature of the contaminant and the time the contaminant was in the soil,
Currently, 1 to 10 minutes is suitable. The homogeneous mixture of soil-encapsulated copolymer and soil is then poured into a holding tank. The contaminant-encapsulated copolymers can be powdery or large agglomerates, depending on the form of block copolymer used.

Fourth, the copolymer-encapsulated contaminants are leached from the soil by mixing the intimate mixture with water. Since a large mass of encapsulated contaminants floats on the surface of the water, the scooping leaves water and soil substantially free of organic liquid contaminants. Preferably the mass is recovered from the water using a 0.125 to 1 inch (0.3 to 2.54 cm) net. The water and soil are then filtered to obtain substantially dry soil and extracted water, each free of organic contaminants.

The organic liquid contaminants encapsulated with the copolymer can be economically utilized in subsequent steps. For example, block copolymer-encapsulated contaminated masses can be mixed with various organic solvents such as petroleum naphtha, gasoline, diesel oil,
Alternatively, it can be liquefied with crude oil or the like. The resulting organic contaminant-elastomer-organic solvent liquid composition can be used as a fuel source in industrial furnaces, engines, and the like. Alternatively, the solid contaminant encapsulation copolymer can be used as a solid fuel.

In the second method for recovering the organic liquid substance that has soaked into the soil, the soil contaminated with the spilled organic liquid is dug out and mixed well with water in a blender or other mixing device to remove the contaminated material. Leach from. The mixture is then filtered to obtain a washed soil and an aqueous filtrate (containing captured or dispersed organic liquid). The filtrate is then passed through a fixed bed of thermoplastic elastomer copolymer absorbent particles, such as copolymer treatment unit 11 shown in FIG. 1, to remove organic contaminants from the aqueous stream. If desired, the washed soil may be further treated by further treating it according to the above-mentioned first method (method for removing contaminants from soil).

The present invention also relates to a method of applying a thermoplastic elastomer block copolymer to a spilled liquid material on a solid surface such as a steel deck, a wooden deck, a concrete floor, etc., which is on the surface of the spilled liquid. By manually or otherwise applying the block copolymer encapsulating agent evenly.

The amount of block copolymer utilized depends, in part, on the thickness of the organic liquid film to be absorbed or adsorbed and the time required to collect the liquid economically. If the spilled film is no thicker than about 0.5 inch (about 1.3 cm), block copolymer is spilled at about 0.1 per gallon.
It is preferably applied to the block copolymer in an amount of ~ 1 lb (about 0.045-0.45 kg). The time required to encapsulate the organic liquid with the block copolymer is
It depends on the temperature, the ratio of organic liquid to the block copolymer, the viscosity of the organic liquid, the surface area of the block copolymer utilized, and the length of time the organic liquid has been in or on the soil.

The block copolymer encapsulating agent will spill (hydrocarbon) within a few seconds after initial contact with the spill.
Start to encapsulate. The total time required to clear a spill that is 0.5 inches thick or less is typically a few minutes. Spilled organic or petroleum-based liquids are virtually completely encapsulated inside the block copolymer body, and the surface of the encapsulating agent is essentially dry (non-oil).
Non-viscous and non-toxic in the state. Therefore, the encapsulated organic liquid and the block copolymer can be easily collected by rake, wiping, and the like.

Referring to FIG. 4, the present invention also relates to a method of preventing organic contaminants from seeping out from an underground fuel tank into the underlying soil. In this method, the soil / block copolymer mixture 60 is prepared by thoroughly mixing an initial quantity of soil with one of the block copolymers described above. Next, the soil / block copolymer mixture 60 is placed in the bottom of the hole 62 dug in the base soil 63. An underground fuel tank 64 is then positioned over the soil / block copolymer mixture 60 and a second amount of soil 66 is filled into the dug hole 62.

If the organic liquid 68 leaks from the tank 64, the liquid will escape downwards through the second amount of soil 66 and is absorbed or adsorbed by the block copolymer in the soil / block copolymer mixture 60. It If desired, the soil / block copolymer mixture 60 can be placed directly under the tank 64 so that the spilled organic liquor is directly mixed with this mixture 6.
You may make it escape to 0. Thus, in this method, the organic liquid 68 is transferred from the underground tank 64 to the base soil 63 below it.
Prevent it from bleeding inside.

Similarly referring to FIG. 5, the present invention relates to a method for preventing organic contaminants leaking or spilling from a spring source portion 72 of an oil well 70 from seeping into the surrounding soil. In this method, the source portion 72 is surrounded by a ring 74 of the soil / block copolymer mixture described above. Oil and other organic contaminants from oil wells are absorbed or adsorbed by the block copolymers of the soil / block copolymer mixture and collected. In this way, the leaching of contaminants into the soil around the oil well 72 is prevented. If desired, the well 72 may be drilled down to the required depth and filled with the soil / block copolymer mixture. That is, the ring 74 can be of any desired depth.

The invention will be further described by the following examples. Example 1 Powdered P on a single 0.5 inch diameter fixed bed absorption column
S3200 absorbent (volume of about 100 mL) (micro
About 30 inches (about 76.2c) of block copolymer sold by INVIRONMENTAL INC.
It was packed to the depth of m). Then, water contaminated with gasoline (about 0.6 g of Amoco Silver grade unleaded gasoline per liter of solution) was passed through this column at a rate of 12 bed volumes (BV) per hour (where BV is the block in the column). A volume equal to the volume of the copolymer (ie 100
mL)).

1 hour and 40 minutes after column operation, 3 hours and 20 minutes
% Of component removal of treated effluent relative to untreated stream after minutes, 6 hours 40 minutes, 10 hours and 13 hours 20 minutes
Was measured according to EPA Method 602 (VOA) and is shown in the following table. Component removal% 1 hour 40 3 hours 20 6 hours 40 10 hours 3 hours 20 Contaminated matter MTBE 31.6 59.6 33.0 41.6 13.4 Benzene 99.4 93.1 76.9 81. 4 79.0 Toluene 100.0 100.0 99.5 96.6 91.7 Ethylbenzene 100.0 100.0 100.0 100.0 100.0 Xylene 100.0 100.0 100.0 100.0 100 .0

As expected, the more volatile compounds benzene and toluene broke through faster. There was no sign of a pressure drop across the column during the test. Furthermore, no dissolution or "melting" of the block copolymer (reaction of gasoline and block copolymer different from absorption and / or adsorption) was observed. This absorbent thus responded physically as it would be found in other adsorption type column systems.

Example 2 The procedure of Example 1 was repeated, except that the absorption column was packed with PS3400 absorbent (a block copolymer sold by Micro Incorporated Incorporated).
However, volatile organic compounds (benzene, toluene, ethylbenzene and xylene) were tested earlier in the effluent.
The test was terminated in 3 hours and 20 minutes, as it was shown that a breakthrough of ## STR1 ## occurred much earlier than with the PS3200 of Example 1.

The percent component removal (1 hour 40 minutes and 3 hours 20 minutes after column run) of the effluent relative to the untreated stream was measured and is shown in the table below. As the results show, PS3200 used in Example 1 was a more effective absorber than PS3400. Component Removal% 1 hour 40 minutes 3 hours 20 minutes Contaminated matter MTBE 19.0 28.8 Benzene 84.5 83.6 Toluene 93.8 94.0 Ethylbenzene 97.1 97.5 Xylene 96.7 97.1

Example 3 To determine the efficiency of PS3200 and PS3400 in removing gasoline from water in a single stage batch contact system, final adsorption and / or
Alternatively, the absorption capacity was first measured. Since these block copolymers tend to melt on contact with concentrated gasoline solutions, the following procedure was used to determine final capacity: a) Add a specific amount of gasoline to a metered excess of polymer and react for several hours. Let b) The melted block copolymer that had reacted with gasoline was removed and the unreacted block copolymer was weighed. c) The weight of unreacted block copolymer was subtracted from the total weight of block copolymer to determine the weight of reacted (melted) block copolymer.

The proficiency test was as follows. Gasoline Reacted polymer performance material (gram) (gram) ( gasoline g / polymer g ) PS3200 5.0 4.8 1.04 PS3400 5.0 4.0 1.25 PS3400 material is a specific absorbent material PS3200
Adsorbs more gasoline. During this test, PS
3400 was observed to appear to "melt" to a greater extent than PS3200. This may explain the superiority of the PS3200 in a column-type approach. In the column type, the absorbent is immobile and minimal dissolution is desired to eliminate the possibility of bed blockage and liquid passage.

After determining the final capacity of the absorbent, one-stage batch isothermal contact between the absorbent and contaminated water was made as follows. First, distilled water was contaminated with Amoco Silver grade unleaded gasoline to make two containers (2 liter solution), each having a concentration of 0.6 g of gasoline / liter of solution. Second, the first amount of absorbent (powder form) (which was calculated to be 0.6 g / L for PS3200), which corresponds to the amount required to recover all gasoline at 100% adsorption, was Added to 2 liter solution. The first amount of 2
A second amount of absorbent equal to double was added to the second 2 liter solution.

Each sample was then mixed on a tumbler for about 16 hours. After mixing, remove water samples from each container,
"BETX" contamination was analyzed by EPA Method 602 (VOA). The component removal% is shown below. Component Removal% Polymer Polymer 1st amount 2nd amount (0.6g / L) (1.2g / L) Contamination content Benzene 27.8 33.6 Toluene 46.5 50.4 Ethylbenzene 62.8 66.4 Xylene 65.5 68.5

Example 4 PS3400 absorber was used in place of PS3200 Example 3
The procedure was repeated. Similarly, the first amount of absorbent was equal to the amount required to recover 100% sorption of all gasoline (for PS3400, this was calculated to be 0.5 g / L). This was added to the first 2 liter solution of gasoline contaminated water. The second amount of absorbent equaled twice the first amount and was added to the second 2 liter solution of gasoline contaminated water. After mixing the samples, the container was removed from the mixer tumbler and analyzed for decontamination. The component removal% is shown in the table below. Second amount pollution content Ingredient dividing removed by% polymer polymer first amount (0.5g / L) (1.0g / L) benzene 20.8 24.2 toluene 37.4 43.2 Ethylbenzene 54.9 60.7 xylene 58.2 63.4

From the examination of the effectiveness of the absorbent in the one-step batch contact method in Examples 3 and 4, PS3
Both the 200 and PS3400 absorbents remove some of the polluted gasoline, but PS3200 is found to be a more efficient absorbent. Second, doubling the amount of absorbent does not result in a substantial increase in the removal of polluted gasoline. Third, the one-step batch catalytic processes of Examples 3 and 4 are clearly less effective than the column catalytic processes of Examples 1 and 2 in removing gasoline components from aqueous solutions.

The procedure of Example 1 is the modified 55 gallons (about 2
It can be scaled up by using 08 liter) drums with intake and take-out dispensing headers. This column is about 50 gallons (189 liters) of PS32
00 absorber (about 140 pounds = about 63.4 kg) can be packed. Larger flow rates (1 tested in Example 1
About 10 gallons (based on 2 BV / hour flow)
It will be 7.8 liters / minute. The expected pressure drop through the column is less than 3 psig.

Spill half a cup of unleaded gasoline onto the garage floor. Block copolymer encapsulating agent (PS34
00) on the surface of the spill. Spilled gasoline can be encapsulated within about 15 seconds.

Example 7 The procedure of Example 6 is repeated using 10-W-30 motor oil. Substantially the same results are obtained.

100 g of uncontaminated soil (infrared tested) was mixed with 10 g of # 2 diesel oil to give a contaminated soil sample. Mix 10 g of PS3200 absorber with the contaminated soil sample for 30 minutes to make a homogenous mixture. This mixture is mixed and leached with 1 liter of deionized water for 2 hours. After leaching was complete, a mass of encapsulated contaminants emerged on the surface of the water and were removed by scooping the surface of the water with a net. The rest of the sample was then filtered. The filtered extract is FI
Gas chromatograph with D detector for volatile organic contaminants (benzene, toluene, ethylbenzene and xylene)
Was analyzed. The filtered extract was found to have no detectable volatile organic contaminants. Therefore, volatile organic contaminants were not present in amounts above 10 ppb.

Example 9 The procedure of Example 8 was repeated except that the contaminated soil sample and the absorbent were mixed for 2 hours instead of 30 minutes. The same result was observed.

Example 10 20 gallons (about 75.6 liters) of topsoil contaminated with 2 gallons (about 7.56 liters) of unleaded gasoline is fed to a ribbon blender. About 3 gallons (about 11.3 liters) of the encapsulating agent of Example 1 was mixed with the contaminated topsoil to form a substantially homogeneous mixture, which was 100 gallons (about 378 liters).
L) Pour in holding tank. The intimate mixture is mixed with 50 gallons of tap water. A lump of contaminated encapsulation floats on the surface of the water in the holding tank and is removed by scooping with a leaf rake. Testing of the water and soil remaining in the tank reveals that it is essentially free of unleaded gasoline.

Example 11 In this experiment, seawater was placed in a glass container and sufficient quat crude oil was poured onto the seawater to form a 0.5 inch thick film.
A block copolymer (Kraton G-1650) treated with solid hydrophobic silica (Aerosil R974) was sprinkled onto the crude oil surface to a thickness of about 1/8 inch (about 0.3 cm) and agitated into the crude oil film. The oil is completely encapsulated by the block copolymer composition of the present invention within 1 minute,
It became a dry solid and floated on the surface of seawater. This solid was easily removed from the surface of seawater as it left no greasy residue on the hands. After separating the dry solids, the seawater was clear with no crude oil residue. Kuwait crude oil film untreated Kraton G-1
It took approximately 1.5 minutes to encapsulate the oil when similarly treated with 650 block copolymer.

Example 12 The procedure of Example 11 was repeated using fresh water instead of seawater.
Substantially the same results were obtained.

Example 13 The procedure of Example 12 was repeated substituting unleaded gasoline for the quat crude. Substantially the same results were obtained.

Example 14 The procedure of Example 12 was repeated once more using 10-W-30 lubricating oil instead of quat crude. Substantially the same results were observed, the water being completely free of contaminants after treatment with the encapsulating agent of the invention.

Example 15 The procedure of Example 12 is repeated, substituting diesel oil, heptane, seal oil, transformer oil, JP-5 jet fuel, hydraulic oil and transmission oil, respectively, in place of quat crude oil.
Substantially the same results were obtained in each case, and the water was substantially free of hydrocarbon contaminants. In all cases, the hydrocarbon was encapsulated by the composition of the invention about 25% faster than the untreated control.

Example 16 3 with a 20-30 gallon bilge tank with an inboard diesel engine
2 foot boat, about 4 inches in circumference (about 10.4c
m), a bilge bag of about 48 inches (about 122 cm) in length filled with the composition of the invention of Example 11.
This bag is effective in removing 2 quarts (about 1.89 liters) of contaminated oil before it needs to be replaced. During use, this bilge bag keeps the water in the bilge substantially free of contaminated oil.

Example 17 Diesel oil slick (area about 0.25 acre = about 1
011 square meters, about 0.25 inches thick = about 0.6 cm) were made on a small inland lake. Example 1 of the invention for individual booms
A flow-through boom filled with composition 1 was placed between the shore and the oil slick to protect the shore. The shoreline edge of the slick was treated by first spraying the composition of Example 11 of the present invention from a small boat and then from the edge to the center the composition of the present invention was applied around the slick. The treated amount was about 20% (weight) with respect to the calculated amount of slick. The encapsulated oil fragments were recovered from the water by scooping using a 1/8 inch net. Dissolved recovered fragments in petroleum naphtha and liquid diesel oil
A rubber-petroleum naphtha mixture was produced. 55 this mixture
It was packed in gallon steel drums and later used as fuel for industrial hot water reactors.

Example 18 In this example, bilge pumps are fitted with parallel filter cartridges with appropriate tubing and valves, one at a time for in-line filters to remove contaminants from bilge water. The second filter is waiting to be used while the first is being played. Each filter cartridge is filled with the encapsulating agent of Example 11 of the present invention in an amount sufficient to encapsulate about 2.5 quarts (about 2.4 liters) of contaminated hydrocarbons. When the pressure drop through the filter becomes equivalent to the encapsulation of about 2 quarts of contaminants, an appropriate alarm will be issued, so the second
Put the filter in line 1 in line and clean the first filter. If the filter is not changed in a timely manner, the filter will continue to work until the bilge pump automatically stops operating due to the pressure drop. Thus, operating the bilge pump filtration system for a period of about 6 months substantially eliminates contaminants from escaping to the environment.

The present invention thus provides a highly effective method for recovering petroleum-based liquids from organic matter from soil, water streams and solid surfaces. The block copolymers used in the method of the present invention rapidly absorb or adsorb organics or petroleum-based liquids. After organic matter or petroleum-based liquid is absorbed or adsorbed,
The organic encapsulation block copolymer was easily recovered, leaving little trace of leaked organics or petroleum-based liquids. The recovered copolymer containing organics can be further used as a solid fuel or can be dissolved in various liquid fuels into fuel oil, thus avoiding costly landfill and disposal problems. Furthermore, encapsulation of the organic liquid with a copolymer increases the flash temperature (decreases the flash point) of the organic liquid.

[Brief description of drawings]

FIG. 1 is a schematic block diagram of a bilge filtration system according to the present invention with a side-by-side copolymer processing unit containing thermoplastic elastomer block copolymer particles for removing trapped hydrocarbon contaminants from a water stream. .

FIG. 2 is a schematic block diagram of a combined treatment system including a copolymer treatment unit, an air stripper unit, an ozone treatment unit, an ultraviolet irradiation treatment unit, and an activated carbon treatment unit.

FIG. 3 is a flow chart showing the steps of the method of the present invention for removing organic liquids from soil.

FIG. 4 is a cross-sectional view of an underground fuel tank placed on top of the soil / block copolymer mixture of the present invention.

FIG. 5 is a perspective view showing a ring of the soil / block copolymer mixture of the present invention placed around an oil well.

[Explanation of symbols]

10 ... Bilge pump 11 ... Copolymer processing unit 12, 14 ... Absorbent bed 16 ... Bilge extraction pipe 18 ... Bilge 23, 32 ... Pressure gauge 24, 28 ... Three-way valve

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B09C 1/08 C02F 1/20 ZAB A 1/32 ZAB 1/40 ZAB E 1/78 ZAB

Claims (17)

[Claims] 1. A method for removing organic liquid contaminants from an aqueous solution in which it is entrapped, comprising: a monovinyl aromatic polymer block bonded to an elastomer conjugated diene polymer block; and an elastomer monoolefin polymer block. Immobilization of at least one of granular thermoplastic elastomer linear diblock copolymers, triblock copolymers and branched diblock copolymers, which is a granular thermoplastic elastomer block copolymer consisting of at least one with a monovinyl aromatic polymer block attached A method of removing organic liquid contaminants comprising passing the aqueous solution through a contact area containing a bed and removing a substantially decontaminated water stream from the contact area. 2. A method for removing organic liquid contaminants from soil, comprising a monovinyl aromatic polymer block bonded to an elastomer conjugated diene polymer block and a monovinyl aromatic polymer bonded to an elastomer monoolefin polymer block. Combining at least one of granular thermoplastic elastomer linear diblock copolymers, triblock copolymers and branched diblock copolymers, which is a granular thermoplastic elastomer block copolymer consisting of one with a block, with organic liquid contaminated soil Mixing the organic liquid contaminated soil with the thermoplastic elastomer block copolymer to form a homogeneous mixture of the thermoplastic elastomer block copolymer and the organic liquid contaminated soil, mixing the homogeneous mixture with water, blocking from the homogeneous mixture Taking out the organic liquid contaminated fraction encapsulated in polymers, and organic contaminants fraction method for removing consisting in taking out soil free of contamination fraction from the remaining mixture. 3. A method of removing an organic liquid film from a liquid or solid surface, the method comprising: a monovinyl aromatic polymer block bonded to an elastomer conjugated diene polymer block; and a monovinyl aroma bonded to an elastomer monoolefin polymer block. A granular thermoplastic elastomer block copolymer consisting of one of a linear diblock copolymer, a triblock copolymer or a branched diblock copolymer, which is composed of one of a group of polymer blocks and a weight ratio of 0. 1 to 2.5
Distributing evenly the ground thermoplastic elastomer block copolymer uniformly coated with an amount of hydrophobic silica in an amount in the range of weight percent over an organic liquid film, encapsulating the oil within said block copolymer, and organic A method for removing organic contaminants, comprising recovering a liquid-encapsulated block copolymer from a liquid or solid surface. 4. A method for removing organic pollutants from soil, comprising mixing soil contaminated with an organic liquid with water to leach organic liquid pollutants from the soil to obtain a soil / liquid mixture. Filtering the liquid mixture to obtain an aqueous filtrate containing organic liquid contaminants and washed soil, the filtrate comprising a monovinyl aromatic polymer block bonded to an elastomer-conjugated diene polymer block,
Granular thermoplastic elastomer linear diblock copolymers, triblock copolymers and branched diblock copolymers, which are granular thermoplastic elastomer block copolymers comprising at least one monovinylaromatic polymer block attached to an elastomeric monoolefin polymer block Of at least one fixed bed, and removing a substantially contaminant-free water stream from said contact region. 5. A method for preventing organic contaminants from leaching from a pollutant-containing tank or pipe into the soil under or around the tank or pipe, the monovinylaromatic being bonded to an elastomer-conjugated diene polymer block. A granular thermoplastic elastomer linear diblock copolymer which is a granular thermoplastic elastomer block copolymer consisting of at least one of a polymer block and a monovinyl aromatic polymer block bonded to the elastomer monoolefin polymer block,
Mixing a triblock copolymer and a branched diblock copolymer with an amount of soil to form a soil / block copolymer mixture, and placing the soil / block copolymer mixture in soil under or around a tank or pipe A method consisting of: 6. The method of claim 5, further comprising removing the soil and copolymer mixture from the soil after contamination with organic contaminants and separating the contaminant-containing copolymer from the soil. Method. 7. The method according to claim 1, wherein the elastomeric polymer block is at least partially hydrogenated. 8. The method according to claim 1, wherein the monovinyl aromatic polymer block is at least partially hydrogenated. 9. The method according to claim 1, wherein the thermoplastic elastomer block copolymer comprises a polystyrene-polybutadiene-polystyrene block copolymer. 10. The method according to claim 1, wherein the thermoplastic elastomer block copolymer comprises polystyrene-ethylene / butylene copolymer-polystyrene block copolymer. 11. The method according to claim 1, further comprising dissolving an organic liquid contaminant encapsulated with the block copolymer in an organic solvent to obtain an organic liquid contaminant-copolymer liquid composition. A method including making, fueling for a furnace, an engine, etc. 12. The method of claim 11, wherein
The method in which the organic solvent is selected from the group consisting of petroleum naphtha, diesel engine oil, crude oil and gasoline. 13. The method of claim 3, wherein the amount of block copolymer applied is from about 0.1 to about 1 pound per gallon of organic liquid. 14. The method of claim 1, further comprising treating the aqueous solution with ozone. 15. The method of claim 1, further comprising treating the aqueous solution with ultraviolet radiation. 16. The method of claim 1, further comprising treating the aqueous solution with activated carbon. 17. The method of claim 1, further comprising passing the aqueous solution through an air stripper.