JPH11106744A - Coating composition for promoting decomposition of petroleum and method for cleaning base material contaminated with petroleum - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which decomposes and removes a hydrocarbon such as crude oil with which rock, an artificial construction or the like is contaminated by mixing a resin vehicle with a nutrient component for organisms and an oxygen permeation accelerator. SOLUTION: This composition comprises a resin vehicle, desirably a polyester resin, a natural resin or the like (e.g. polycaprolactone), 1-90 wt.%, desirably 10-70 wt.%, based on the nonvolatiles of the composition, at least one nutrient component for microorganisms selected among nitrogenous substances, phosphorus substances, alkali (alkaline earth) metal substances, etc., (e.g. soybean cake, acetaldehyde/urea condensate, magnesia ammonium phosphate and powdered oyster shell) and desirably 0.1-80 wt.%, more desirably 2-40 wt.%, on the same basis, oxygen permeation accelerator (e.g. pulp) for example a natural polymer or a water-soluble salt. The weight ratio of the nutrient component to the resin vehicle is desirably 5/95 to 95/5, more desirably 10/90 to 80/20.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a paint composition for accelerating petroleum cracking and a method for purifying a substrate contaminated with petroleum.

[0002]

BACKGROUND OF THE INVENTION Petroleum pollution in the marine environment has been particularly increasing in recent years. In particular, spills of crude oil and fuel oil due to the Russian ship's tanker Nakhodka's ship accident, etc. caused a large amount of oil to spill at a time in a limited area, and the oil flowing along the coast was attached to rocks, artificial structures, etc. In addition to causing severe destruction of the marine environment, it has had a tremendous economic impact on fisheries such as aquaculture and tourism. On the other hand, the speed of movement of the spilled oil to the surface of the sea is extremely high, and environmental pollution has spread before the installation of an oil fence or the like, and a situation of drifting to the coast has occurred. Crude oil contains many harmful substances to living organisms, and its accumulation in edible marine products is a huge public health problem due to its high concentration in the human body through the food chain. Is also a concern. The spilled oil undergoes evaporation and volatilization (weathering), and the light components mainly composed of aliphatic hydrocarbons, that is, the readily biodegradable components, disappear quickly, but the tar components remaining after weathering have heavy, high-boiling physical properties. It is a hard-to-decompose component mainly composed of aliphatic hydrocarbons, cycloaliphatic hydrocarbons and aromatic hydrocarbons, and remains on the coastline that has drifted ashore for a long period of time, and adheres to rocks and artificial structures. The problem is compounded by public health concerns.

[0003] At a crude oil spill accident site in an actual marine environment, when removing hydrocarbon compounds such as oil spills, mechanical pumping, spraying of nutrients to improve natural purification ability by microorganisms, and high-pressure heat Measures such as washing using water and surfactants have been taken, but all of them are too costly, or conversely lead to eutrophication of the marine environment, leading to marine pollution such as red tide generation. However, it was not an effective means. As a result, most of the treatment of contaminated oceans by spilled crude oil is now either left to nature's self-cleaning power or removed manually. In particular, there has been no method of efficiently removing crude oil components adhering to coastal rocks and artificial structures, which are the most problematic.

[0004]

SUMMARY OF THE INVENTION The present invention relates to hydrocarbons,
Especially contained in crude oil attached to rocks and man-made structures, etc., straight-chain aliphatic hydrocarbons having high boiling point properties, branched-chain aliphatic hydrocarbons, cycloaliphatic hydrocarbons, cycloaliphatic hydrocarbons alkylcyclohexane and Using a method of applying a petroleum cracking promoting paint composition on a contaminated substrate to propagate microorganisms capable of broadly and satisfactorily decomposing other types of hydrocarbons such as alkylbenzenes of aromatic hydrocarbons onto rocks and artificial materials. It is intended to decompose and remove hydrocarbons such as crude oil that have contaminated structures and the like.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies on a method for decomposing petroleum components attached to rocks and man-made structures in a short period of time after drifting on the shore, and as a result, a resin vehicle, a microorganism, It is possible to efficiently purify petroleum by applying a petroleum cracking accelerating coating composition containing petroleum cracking nutrients, materials improving oxygen permeability, and, if necessary, petroleum cracking microorganisms to contaminated substrates. It turns out that it is possible and has completed the present invention. That is, the present invention
A paint composition for accelerating petroleum decomposition, comprising (a) a resin vehicle, (b) a nutrient for microorganisms, and (c) an oxygen permeation enhancer.

Further, the present invention provides (a) a resin vehicle,
A paint composition for accelerating petroleum decomposition, comprising (b) a nutrient for microorganisms, (c) an oxygen permeation promoter, and (d) a petroleum decomposition microorganism. Furthermore, the present invention is a method for purifying a petroleum-contaminated substrate, which comprises applying the above-described coating composition for promoting petroleum decomposition to a substrate contaminated with petroleum.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The petroleum cracking accelerating coating composition of the present invention,
(A) a resin vehicle component, (b) a nutrient component for microorganisms,
(C) An oxygen permeation promoter is used as a main component, and (d) a petroleum-degrading microorganism and (e) a solid substance can be blended with this as needed.

(A) Resin Vehicle The resin vehicle (a) is used to control the outflow rate of microbial nutrients eluted after the coating composition of the present invention is applied to a substrate contaminated with petroleum. Can be As the resin vehicle to be used, there are a solvent evaporative drying type, an oxidative polymerization type, and a reaction curable type resin which can form a film at room temperature or by baking and drying. Examples of these resins include a room temperature-curable or heat-curable amino resin (eg, melamine resin), a two-part curable epoxy resin, an epoxy ester resin, a two-part curable polyurethane resin, an oil-free polyester resin, and an oil-soluble phenol resin. (And a fusion product thereof with a drying oil), oil-modified low acid value alkyd resin, vinyl chloride resin, chlorinated rubber resin, chlorinated polyethylene resin, chlorinated polypropylene resin, acrylic copolymer resin, ethylene-vinyl acetate Copolymer resin, styrene-butadiene copolymer resin, vinyl chloride-vinyl isobutyl ether copolymer resin, polyolefin resin, polyester resin (eg, polylactic acid, polyhydroxybutyrate, polycaprolactone), low acid value processed natural resin (eg, rosin) Derivatives), natural resins (eg, sodium alginate) Um, rosin), and a petroleum hydrocarbon resin. These resins may be used alone or as a mixture of two or more. In addition, these resins may be liquid themselves, but in the case of solid resins, they are usually dissolved in a solvent and used in the form of a varnish.

As the paint for accelerating petroleum decomposition, it is preferable to use a biodegradable resin vehicle (a) because of its nature to be applied in a natural environment. Among the resins exemplified above, polyester resins, natural resins, and the like are preferable. Specific examples of the biodegradable resin include rosin, polylactic acid,
Examples thereof include polyhydroxybutyrate, polycaprolactone, and polyvinyl alcohol. Further, a plasticizer may be added to the resin vehicle (a) as required. The plasticizer is not particularly limited as long as it has a plasticizing effect on paints, plastics, and the like.

(B) Microbial nutrients Since the ocean and the like contain little nitrogen and phosphorus, it is necessary to add microbial nutrients to the above-mentioned resin vehicle (a). The nutrient component for microorganisms is one or more substances selected from a nitrogen-containing substance, a phosphorus-containing substance, an alkali metal-containing substance, an alkaline earth metal-containing substance, and the like. In the present invention, two or more of these substances are particularly used in combination. Is preferred. These substances also include substances containing two or more kinds of the above-mentioned atoms containing nitrogen, calcium and a trace amount of other atoms (for example, phosphorus) in combination, such as, for example, lime nitrogen, bone meal, and oyster powder. . A specific example is as follows. In addition, the nutrient component containing the above-mentioned atoms in combination is typically exemplified as a substance containing one atom for convenience.

[0011] Nitrogen-containing substances; ammonium sulfate, urea, lime nitrogen, salt ammonium, ammonium nitrate, phosphorus phosphorus, ethylenediaminetetraacetic acid (EDT
A) Metal salts, chicken dung, beef dung, amino acid salts, guanyl urea salts, oil residue, soybean residue, acetaldehyde urea condensate (CDU) powder, glymin and the like. Phosphorus-containing substances; lime superphosphate, lime heavy phosphate, lime metaphosphate, lime ammonium phosphate, soluble phosphorus fertilizer, condensed phosphate, phosphorus phosphate, and the like. Alkali metal-containing substances; potassium chloride, potassium phosphate, potassium sulfate, potassium nitrate, seaweed ash, plant ash, etc. Alkaline earth metal-containing substances; bone meal, fish meal, seaweed meal,
Such as calcium carbonate.

Each of the substances exemplified above is one end of the nutrient that can be used in the present invention, and is a fertilizer substance or a nutrient component containing the above atoms alone or in combination.
Those other than those exemplified above can be used without particular limitation. Among these substances, one, preferably two or more, nutrients selected from bone meal, scallop powder, crab powder, oily scum, soybean scum, CDU powder, and phosphorous ammonium phosphate are suitably used. The amount of the nutritional component (b) in the paint for promoting petroleum cracking of the present invention is not particularly limited, but the total weight ratio of the nutritional component (b) is 1 to 90% in the nonvolatile solid content of the paint. , Preferably 10
It is in the range of 70%.

(C) Oxygen permeation enhancer The oxygen permeation enhancer (c) is used in a coating material in order to improve the permeability of oxygen from the coating film surface to a substrate contaminated with petroleum or the like. As the oxygen permeation enhancer (c), a natural polymer or a water-soluble salt is used. The natural polymer improves the oxygen permeability of the coating film by improving the permeability of water (seawater) into the coating film. Further, the water-soluble salts are dissolved in water (seawater) after the formation of the coating film, and are dissolved out of the coating film, thereby reducing the density of the coating film and improving oxygen permeability.

The oxygen permeation enhancer (c) is not particularly limited as long as it can improve oxygen permeability into the inside of the coating film, and examples of natural polymers include cellulose, pulp, calcium alginate and the like. Newspaper, cardboard or the like may be used as the cellulose component. Examples of the water-soluble salts include sodium chloride, magnesium chloride, magnesium sulfate, sodium sulfate, rock salt, artificial seawater, and the like. As the oxygen permeation enhancer, at least one selected from the above components is suitably used. The blending amount of the oxygen permeation enhancer in the paint for promoting petroleum cracking is not particularly limited, but the total weight ratio of the oxygen permeation enhancer is 0.1 to 80%, preferably 2 to 80%, in the nonvolatile solid content of the paint. It is in the range of 40%.

(D) Petroleum-degrading microorganisms The petroleum-degrading microorganisms (d) are used as needed to increase the initial activity of cracking crude oil. Petroleum-degrading microorganisms (d)
Even if no oil is added, by promoting the growth of petroleum-degrading microorganisms (d) that are always present in the environment, crude oil components attached to rocks or artificial structures can be decomposed. ) Can decompose crude oil deposits more quickly.

Many strains of the petroleum-degrading microorganism (d) are already known. For example, Rhodococcus sp.
95879), Alkaligenes sp. (JP-A-7-95878), Agrobacterium sp. (JP-A-7-313146)
Alternatively, the genus Candida (JP-A-7-144199) can be mentioned, but the genus of the microorganism is not particularly limited.

From the viewpoint of cost and the like, the coating composition of the present invention generally does not contain the petroleum-degrading microorganisms (d). If (d) is blended, a remarkable effect can be obtained. These petroleum-degrading microorganisms (d) may be used alone or in combination of two or more. The blending amount of the petroleum-degrading microorganisms (d) in the paint for accelerating petroleum cracking is not particularly limited, but the total dry weight ratio of the microorganisms may be 0.001 to 5 in the nonvolatile solid content of the paint.
%, Preferably in the range of 0.01 to 1%.

(E) Solid substance A solid substance or the like can be blended as required for adjusting the properties of the paint. For example, metal particles such as sand, concrete particles, plastic powder, glass particles, pottery flakes, silica stone powder, and mine tails are exemplified. The petroleum cracking promoting paint of the present invention contains a resin vehicle component (a) and a microbial nutrient component (b), and the mixing ratio of the two components is a solid content weight ratio. / 5 to 5/95, more preferably 90/10 to 20/80, and the mixing of these two components may be carried out in the presence of water and / or an organic solvent.

Furthermore, the paint for promoting petroleum cracking includes the above-mentioned resin vehicle (a), nutrient component for microorganisms (b),
In addition to the oxygen permeation enhancer (c), petroleum-degrading microorganisms (d) and solid substances (e), for the purpose of adjusting paint viscosity, storage stability, coating workability, color tone, and the state of the coating film and its physical properties Known solvents, additives, curing accelerators, coloring contents, etc., which are commonly used in coatings, can also be used. Also,
The above-mentioned paint can be easily produced by mixing the above-mentioned respective components and by a known dispersion method (for example, a pebble mill, a paint shaker, a dissolver, etc.).

A method for purifying a substrate contaminated with petroleum is as follows.
By applying the petroleum cracking accelerating paint on the base material, the contaminants adhering to the surface of the base material can be efficiently decomposed. The base material that can be contaminated is not particularly limited, but is applied to concrete structures such as rocks, sand, quays, iron structures such as ship bottoms and piers, plastics such as buoys, and artificial structures. Shellfish such as a coating film, a fishing net, oysters, and mussels can be given.

As a method for applying the paint for accelerating petroleum cracking of the present invention, the shape, structure, surface condition and the like of the contaminated substrate are taken into consideration, and the coating is easily applied by a known coating method suitable for this.
The coating method includes spraying, roller coating, brush coating, flow coating, and the like, and the coating may be performed by a method selected from these. The coating film is usually dried at room temperature, but may be dried by heating (for example, 40 to 60 ° C.) depending on the properties of the resin and the type of the object to be coated.

From the coating film thus formed, nutrient components migrate to the surface of the base material and are supplied to petroleum-degrading microorganisms present on the base material contaminated with petroleum. Decomposition is promoted. Further, since nutrient components are also supplied to the periphery of the coating film, the decomposition of petroleum of the contaminated base material around the coating film is promoted. The decomposed petroleum spontaneously peels off from the substrate, but if it does not peel off, it may be removed using a scraper or the like.

[0023]

Next, the present invention will be described in detail with reference to examples. In the following, “parts” indicates “parts by weight”. [Example 1] On a 200 cm ² upper surface of a concrete block having a width of 20 cm, a depth of 10 cm, and a height of 6 cm, 1.2 g of heavy oil floating on a Russian registered tanker Nakhodka collected at Fukui Technoport on February 4, 1997. Applied. 2.4 g of a paint X for accelerating petroleum cracking (YSP-X) was spray-painted on the upper surface and air-dried.

Formulation of YSP-X 35.6 parts of 60% rosin, 6.4 parts of 25% caprolactone H-4 (manufactured by Daicel Co., Ltd.), 0.92 parts of Despalone NS (manufactured by Kusumoto Kasei Co., Ltd.), Benton # 38 (NL In
dustries Inc.) 1.4 parts, soybean waste 20 parts, acetaldehyde urea condensate (manufactured by Chisso Corporation) 20 parts, oyster powder (manufactured by Maruei Co., Ltd.) 20 parts, and Rin'an (Made Co., Ltd.) 10 parts, Pulp-03 (Gyeyang Textile Industry Co., Ltd.) 5 parts,
Xylene 12 parts, methyl isobutyl ketone 8 parts

Example 2 Heavy oil floating on concrete blocks was applied in the same manner as in Example 1. The upper surface was spray-coated with a petroleum cracking-promoting paint XM (YSP-XM) containing petroleum-degrading microorganisms, and then air-dried. A strain of Rhodococcus sp.PR4 as a petroleum-degrading microorganism, (Deposit No. FER
MP-13804). Rhodococcus PR4 strain is ZoBell-
After culturing in a 2216 medium (manufactured by Difco) at 20 ° C. for 4 days, the freeze-dried cells were used as a sample.

Blend of YSP-XM 35.6 parts of 60% rosin, 6.4 parts of 25% caprolactone H-4 (manufactured by Daicel Co., Ltd.), 0.92 parts of Desparone NS (manufactured by Kusumoto Kasei Co., Ltd.), Benton # 38 (NL In
dustries Inc.) 1.4 parts, soybean waste 20 parts, acetaldehyde urea condensate (manufactured by Chisso Corporation) 20 parts, oyster powder (manufactured by Maruei Co., Ltd.) 20 parts, and Rin'an (Made Co., Ltd.) 10 parts, Rhodococcus PR4 freeze-dried bacterial cell powder 1
Department, Pulp-03 (Gyeyang Textile Industry Co., Ltd.) 5 Department, Xylene 12
Parts, methyl isobutyl ketone 8 parts

[Example 3] The same operation as in Example 1 was performed except that YSP-Y was used instead of YSP-X in Example 1. YSP-Y formulation 60% rosin 35.6 parts, 25% caprolactone H
-4 (manufactured by Daicel Corporation) 6.4 parts, Desparon NS (manufactured by Kusumoto Kasei Co., Ltd.) 0.92 parts, Benton # 38 (NL Industries Inc.)
1.4 parts, soybean waste 20 parts, acetaldehyde urea condensate (manufactured by Chisso Corporation) 20 parts, oyster powder (Maruei Co., Ltd.)
20 parts, Rin'an Rokuan (Corp Chemical Co., Ltd.) 10
Department, Aquamarine (Senju Pharmaceutical Co., Ltd.) 15 Department, Xylene 12
Parts, methyl isobutyl ketone 8 parts

[Comparative Example 1] The same test as in Example 1 except that the heavy oil stuck on the concrete block was applied was used for the test. [Comparative Example 2] The same procedure as in Example 1 was carried out except that YSP-B was used in Example 1 except that pulp-03, which is an oxygen permeation promoter, was used. YSP-B 60% Rosin 35.6
Part, 25% caprolactone H-4 (manufactured by Daicel Corporation) 6.4
Department, Desparon NS (manufactured by Kusumoto Chemicals) 0.92 parts, Benton # 38 (manufactured by NL Industries Inc) 1.4 parts, soybean waste 20 parts,
20 parts of acetaldehyde urea condensate (manufactured by Chisso Corporation),
20 parts of oyster powder (Maruei Co., Ltd.)
10 parts, xylene 12 parts, methyl isobutyl ketone 8 parts

Test method A thermostat containing 800 ml of seawater (width 23.5 cm, depth 14.5 cm,
A concrete block coated with petroleum cracking-promoting paint was tilted so that the lower side of the upper surface was immersed in seawater with the painted surface facing up. The thermostat was reciprocated at 20 ° C. and 100 rpm. After the start of shaking, 800 ml of seawater was replaced with a new one every 12 hours. Seawater was sampled every 12 hours, and the nitrogen and phosphorus concentrations were measured. The results are shown in Table 1. In addition, the state of adhesion of heavy oil on the coating surface was observed over time, and the results are shown in Table 2.

[0030]

[Table 1]

(1) Total-N: NO ₃ , NO ₂ , NH in the sample
₄ Measure the ion concentration and calculate the total concentration of these N atoms (ppm)
showed that. (1) Total-P: Measure the PO ₄ ion concentration in the sample,
The total concentration (ppm) of these P atoms is shown. It can be seen that by applying YSP-X, YSP-XM, YSP-Y, and YSP-B, nutrients can be stably supplied outside the system. The addition of an oxygen permeation enhancer tended to slightly increase the rate of nutrient release over YSP-B.

[0032]

[Table 2]

Observation of heavy oil adhesion on the upper surface of the block: Evaluation was made by visual observation. ：: Decomposition is noticeable (block surface is visible in 70% or more of the surface). ：: Decomposition is clearly understood (block surface is visible in 40% or more of the surface). Δ: It can be seen that it was decomposed (a block surface is visible in 10% or more of the surface). ×: Almost no decomposition (block surface is not visible).

It can be seen that the application of YSP-X, YSP-XM, and YSP-Y promotes the decomposition of the attached heavy oil more than YSP-B containing no YSP-X. YSP-XM degraded the attached heavy oil even faster due to the effect of adding petroleum-degrading microorganisms.

[0035]

The present invention provides a novel paint composition for accelerating petroleum cracking and a method for purifying a substrate contaminated with petroleum. The use of the coating composition and the purification method makes it possible to efficiently remove crude oil components adhering to coastal rocks and artificial structures.

Continued on the front page (72) Inventor Toshiji Shimauchi 751-1 Hirata, Kamaishi-shi, Iwate Pref. 75-1% Kamaishi Research Center, Marine Biotechnology Institute, Ltd.

Claims (3)

[Claims] 1. A paint composition for promoting petroleum decomposition, comprising (a) a resin vehicle, (b) a nutrient for microorganisms, and (c) an oxygen permeation enhancer. 2. A paint composition for accelerating petroleum decomposition, comprising (a) a resin vehicle, (b) a nutrient for microorganisms, (c) an oxygen permeation enhancer, and (d) a petroleum decomposition microorganism. 3. A method for purifying a substrate contaminated with petroleum, comprising applying the coating composition for accelerating petroleum decomposition according to claim 1 to a substrate contaminated with petroleum.