Composition and method for hydrocarbon and lipid degradation and dispersal

Abstract

The present invention is directed toward a bioremediation product, its method of manufacture and method of use. A blend of microorganisms, cleansers and surfactants is disclosed which is non-toxic and solvent free, and which has the ability to accelerate the breaking down process of oils, materials such as benzene, toluene, and xylene (BTEX); petroleum hydrocarbon fractions F1-F4 (as defined by CCME2000), polycyclic aromatic hydrocarbons (PAH), paraffin waxes, volatile organics, molds, and the like; while simultaneously providing a biological component which is effective to reduce the total petroleum hydrocarbon levels to zero at an accelerated rate. The product is useful for bioremediation and as an oil dispersant composition useful in treating oil spills, and for cleanup of the shoreline, animals, plants, and equipment.

Claims

1. A composition useful as a petroleum hydrocarbon dispersant and remediation composition comprising in combination: 1) 7.3%-9.3% by weight of cocoamidopropyl-betaine; 2) 6.8%-8.3% by weight of tall oil fatty acid; 3) 7.9%-9.7% by weight monoethanolamine; 4) 7.9%-9.7% by weight of a Nonionic Octylphenol Ethoxylate having the formula: ##STR00011## wherein R=octyl (C.sub.8) and x=4.5 (avg); 5) 8.3%-10.4% by weight of a Nonionic Octylphenol Ethoxylate having the formula: ##STR00012## wherein R=octyl (C.sub.8) and x=9.5 (avg); 6) 8.4%-10.5% by weight of a tetrasodium salt of ethylenediaminetetraacetic acid; (7) at least one biological hydrocarbon degrader selected from aerobic and/or anaerobic microorganisms of the families Bacillus, Pseudomonas, Paenibacillus and Aspergillus, as well as environmentally modified, transitioned or evolved strains thereof in an amount effective for optimal hydrocarbon degradation; and 8) water to make 100% by weight.

2. The composition of claim 1 comprising: 1) 8.87% by weight of cocoamidopropyl-betaine; 2) 7.74% by weight of tall oil fatty acid; 3) 8.68% by weight monoethanolamine; 4) 8.87% by weight of a Nonionic Octylphenol Ethoxylate having the formula: ##STR00013## wherein R=octyl (C.sub.8) and x=4.5 (avg); 5) 9.06% by weight of a Nonionic Octylphenol Ethoxylate having the formula: ##STR00014## wherein R=octyl (C.sub.8) and x=9.5 (avg); 6) 9.15% by weight of a tetrasodium salt of ethylenediaminetetraacetic acid; and 7) 47.63% by weight water.

3. A process for the treatment of oil spills, soil remediation, degreasing and release of oil in the automotive industry, and oil dispersal and equipment clean-up in the oil transport, aerospace and food preparation industries comprising: providing a composition which includes 7.3%-9.3% by weight of cocoamidopropyl-betaine; 6.8%-8.3% by weight of tall oil fatty acid; 7.9%-9.7% by weight monoethanolamine; 7.9%-9.7% by weight of a Nonionic Octylphenol Ethoxylate having the formula: ##STR00015## wherein R=octyl (C.sub.8) and x=4.5 (avg); 8.3%-10.4% by weight of a Nonionic Octylphenol Ethoxylate having the formula: ##STR00016## wherein R=octyl (C.sub.8) and x=9.5 (avg); 8.4%-10.5% by weight of a tetrasodium salt of ethylenediaminetetraacetic acid; providing at least one biological hydrocarbon degrader selected from aerobic and/or anaerobic microorganisms of the families Bacillus, Pseudomonas, Paenibacillus and Aspergillus, as well as environmentally modified, transitioned or evolved strains thereof in an amount effective for optimal hydrocarbon degradation; providing water to make 100% by weight; and contacting an oil spill, soil in need of remediation, fats, oils and grease (FOG), automotive components requiring degreasing or release of oil, and equipment in need of clean-up from the oil transport, aerospace and food preparation industries with said composition; whereby oil spill treatment, soil remediation, degreasing and release of oil in the automotive industry, and oil dispersal and equipment clean-up in the oil transport, aerospace and food preparation industries are effected.

4. A process for the treatment of oil spills, soil remediation, degreasing and release of oil in the automotive industry, and oil dispersal and equipment clean-up in the oil transport, aerospace and food preparation industries comprising: providing a composition which includes 8.87% by weight of cocoamidopropyl-betaine; 7.74% by weight of tall oil fatty acid; 8.68% by weight monoethanolamine; 8.87% by weight of a Nonionic Octylphenol Ethoxylate having the formula: ##STR00017## wherein R=octyl (C.sub.8) and x=4.5 (avg); 9.06% by weight of a Nonionic Octylphenol Ethoxylate having the formula: ##STR00018## wherein R=octyl (C.sub.8) and x=9.5 (avg); 9.15% by weight of a tetrasodium salt of ethylenediaminetetraacetic acid; and 47.63% by weight water; and providing at least one biological hydrocarbon degrader selected from aerobic and/or anaerobic microorganisms of the families Bacillus, Pseudomonas, Paenibacillus and Aspergillus, as well as environmentally modified, transitioned or evolved strains thereof in an amount effective for optimal hydrocarbon degradation; and contacting an oil spill, soil in need of remediation, fats, oils and grease (FOG), automotive components requiring degreasing or release of oil, and equipment in need of clean-up from the oil transport, aerospace and food preparation industries with said composition; whereby oil spill treatment, soil remediation, degreasing and release of oil in the automotive industry, and oil dispersal and equipment clean-up in the oil transport, aerospace and food preparation industries are effected.

5. The composition of claim 1, wherein the nonionic octylphenol ethoxylates are replaced with like amounts of at least one alternative sugar selected from the group consisting of a Ficoll, a Sucrose, a Fructose, a Glycine, and a Glycerol.

6. The process of claim 3, wherein the nonionic octylphenol ethoxylates are replaced with like amounts of at least one alternative sugar selected from the group consisting of a Ficoll, a Sucrose, a Fructose, a Glycine, and a Glycerol.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 illustrates relative effectiveness of DXR versus modified surfactant formulations substituting alternative sugars for breakdown of paraffin;

(2) FIG. 2 illustrates use of a 1:1 blend of DXR and NLB1000 to treat hydrocarbon contamination in soil;

(3) FIG. 3 illustrates the use of the product of the present invention in a comparative analysis demonstrating the treatment of medium crude oil contamination in soil.

DETAILED DESCRIPTION OF THE INVENTION

(4) The invention is directed toward a novel composition comprised of the combination of an oil dispersant composition and a biological hydrocarbon degrader, and methods for their production and use.

(5) In its broadest context, the invention is a composition of matter including a novel oil dispersant/surfactant composition, which contains a number of ingredients, which are formulated in a particular sequence in order to arrive at the novel oil dispersant as herein disclosed and claimed; in combination with at least one biological hydrocarbon degrader selected from aerobic and/or anaerobic microorganisms of the families Bacillus, Pseudomonas, Paenibacillus and Aspergillus, as well as environmentally modified, transitioned or evolved strains thereof, in an amount effective for optimal hydrocarbon degradation.

(6) The broadly disclosed composition is formulated by providing the following ingredients within the ranges stated:

(7) 1) 7.3%-9.3% by weight of cocoamidopropyl-betaine;

(8) 2) 6.8%-8.3% by weight of tall oil fatty acid;

(9) 3) 7.9%-9.7% by weight monoethanolamine;

(10) 4) 7.9%-9.7% by weight of a Nonionic Octylphenol Ethoxylate having the formula:

(11) ##STR00005##
wherein R=octyl (C.sub.8) and x=4.5 (avg);

(12) 5) 8.3%-10.4% by weight of a Nonionic Octylphenol Ethoxylate having the formula:

(13) ##STR00006##
wherein R=octyl (C.sub.8) and x=9.5 (avg);

(14) 6) 8.4%-10.5% by weight of the tetrasodium salt of ethylenediaminetetraacetic acid; and

(15) 7) water to make 100% by weight.

(16) Cocamidopropyl betaine (CAPB) is a synthetic surfactant derived from coconut oil and dimethylaminopropylamine. It is a zwitterionic chemical compound with a quaternary ammonium cation. It is a viscous pale yellow transparent liquid and is used as a surfactant in bath products such as shampoos and hand soaps, and in cosmetics as an emulsifying agent and thickener, and to reduce irritation purely ionic surfactants would cause. It also serves as an antistatic agent in hair conditioners. CAPB is available from Spectrum Laboratories in Gardena, Calif.

(17) Tall oil fatty acid is available under the brand name SYLFAT FA2, from Arizona Chemical Company of Jacksonville, Fla. The material is an intermediate in the manufacture of soaps, dimer acids, amines, amides, imidazolines, alkyd resins, coatings, and polyesters. It is useful in areas such as specialty industrial and household cleaners, plasticizers for rubber products, textiles, and surfactants.

(18) Monoethanolamine, MEA, is an absorbent chemical employed, for example, in carbon dioxide scrubbers aboard nuclear submarines. It is available from the Sciencelab Company in Houston, Tex.

(19) A Nonionic Octylphenol Ethoxylate surfactant composition having the formula:

(20) ##STR00007##
is available as Triton X-45 from Dow Chemical Company. It is useful in defoamers, cleaners, metalworking fluids, agrochemicals, textiles, pulp and paper manufacture, oilfields, paints and coatings.

(21) A Nonionic Octyiphenol Ethoxylate surfactant composition having the formula:

(22) ##STR00008##
is available as Triton X-100 from the Dow Chemical Company. It is useful in Household and Industrial cleaners, metalworking fluids, agrochemicals, textiles, pulp and paper manufacture, oilfields, paints and coatings.

(23) The tetrasodium salt of ethylenediaminetetraacetic acid is available as VERSENE 100, from the Dow Chemical Company. VERSENE 100 is described as a chelating agent, provided as an aqueous solution of the tetrasodium salt of ethylenediaminetetraacetic acid. (Na.sub.4EDTA). It will chelate most multivalent metal ions (e.g., Fe, Cu, Mn, Ca, Mg, Zn) in a 1:1 molar ratio. VERSENE 100 is completely miscible with water, but is not soluble in organic systems. Na.sub.4EDTA is stable under widely varying conditions of temperature, acidity, alkalinity, and the presence of other chemicals. Applications include agriculture, cleaning products, metalworking, oilfield applications, personal care products, polymerization, pulp and paper, scale removal and prevention, textiles, water treatment.

(24) In a method of manufacture, the ingredients are added sequentially to a vessel, e.g. a high-density polyethylene beaker, and blended with a mixer, e.g. a Lightnin Mixer, available from the SPX Corporation in Rochester, N.Y. Each ingredient is added in sequential order, and mixing is conducted in a stepwise fashion for about 10 minutes per ingredient, or until a uniform blend is produced, before addition of the next ingredient. While in the mixing stage, some heat is produced, typically reaching a temperature of about 45 C. Upon cooling, the resultant product is a clear liquid having a slightly yellowish color. It is understood that as the batch size increases, the skilled artisan will extend the mixing time between steps so as to assure uniform blending.

(25) In another method of manufacture, the composition, designated DXR-02, is an oil dispersant supplied as a homogeneous mixture of the following ingredients, blended in sequence, for a time sufficient to provide a uniformly blended intermediate prior to addition of the next ingredient:

(26) 1) 8.87% by weight of cocoamidopropyl-betaine;

(27) 2) 7.74% by weight of tall oil fatty acid;

(28) 3) 8.68% by weight monoethanolamine;

(29) 4) 8.87% by weight of a Nonionic Octylphenol Ethoxylate having the formula:

(30) ##STR00009##
wherein R=octyl (C.sub.8) and x=4.5 (avg);

(31) 5) 9.06% by weight of a Nonionic Octylphenol Ethoxylate having the formula:

(32) ##STR00010##
wherein R=octyl (C.sub.8) and x=9.5 (avg);

(33) 6) 9.15% by weight of the tetrasodium salt of ethylenediaminetetraacetic acid; and

(34) 7) 47.63% by weight water.

(35) The composition further includes at least one biological hydrocarbon degrader selected from aerobic and/or anaerobic microorganisms of the families Bacillus, Pseudomonas, Paenibacillus and Aspergillus, as well as environmentally modified, transitioned or evolved strains thereof in an amount effective for optimal hydrocarbon degradation.

(36) In a further embodiment, it is within the purview of the present invention to substitute the nonionic octylphenol ethoxylates with equivalent amounts of an alternative sugar such as Ficoll, Sucrose, Fructose, Glycine, Glycerol, or the like, and combinations thereof.

(37) As illustrated in FIG. 1, formulations were prepared using Ficoll, Sucrose, Fructose, Glycine, and Glycerol in place of the Nonionic Octylphenol Ethoxylates. Tests were carried out to determine the percentage of paraffin wax (y-axis) versus the days of treatment (x-axis) in order to develop a comparison of effectiveness. While various of the sugar substitutions yielded compositions effective as paraffin dispersants, the DXR formulation was still superior in this regard.

(38) It has been the inventor's experience that when formulating larger batches, e.g. 1000 KG, the mixing times increase to about 30 minutes per sequence in order to assure uniformity.

(39) A study was conducted to assess the toxicity of the test substance, DXR-02, to Mysidopsis Bahia, in a 96-hour static, non-renewal test.

(40) Test concentrations were determined by a preliminary range-finding test. A definitive test was conducted using concentrations of 50, 100, 200, 400 and 800 mg/L of the test substance. Each test concentration consisted of three replicates often organisms (greater amount than the protocol requirement of 20 organisms). Organisms were randomly placed, individually, into each test container containing the appropriate concentration of test substance. Three replicates often (10) organisms were not exposed to test substance and served as controls to demonstrate the condition of the test population. At 0, 24, 48, 72 and 96 hours following dosing, each test container was examined for mortality, and the number of live shrimp was recorded. The test was terminated after 961 hours of exposure.

(41) The 96-hour median effective concentration (EC50) of DXR-02 was determined to be 475.00 mg/L with 95% confidence limits of 0.00-677.50 mg/L. The NOEC (No Observed Effect Concentration) for survival was determined to be 100 mg/L. Results presented are based on nominal concentrations.

(42) Comparisons of 48 hour toxicity with respect to various commercial products are illustrated in Table 1:

(43) TABLE-US-00001 TABLE 1 Toxicity Comparison Material Tested Species LC50 (ppm) TIME LD50 Death Test guide lines DXR-02 Mysidopsis bahia 600 48 hr OCSPP 850.1035 BIODISPERS Mysidopsis bahia 78.9 48 hr N/A COREX Mysidopsis bahia 32.23 48 hr N/A EC9500A COREXIT Mysidopsis bahia 24.14 48 hr N/A EC9527A FINASOL Mysidopsis bahia 9.37 48 hr N/A OSR 52

(44) As evidenced by the values set forth in Table 1, the LC50 in PPM of DXR-02 is between about 8 and 20 times that of the commercially available oil dispersants tested.

(45) The presences of toxic materials such as heavy metal was evaluated with respect to alternative, commercially available oil dispersants and are reported in Table 2.

(46) TABLE-US-00002 TABLE 2 Product Arsenic Cadmium Chromium Copper Lead Mercury Nickel Zinc Cyanide DXR-02 0 0 0 0 0 0 0 0 0 BIODISPERS <2.5 <0.75 <0.75 <0.5 <5.0 N/D <1.20 <0.50 3.9 COREXIT EC9500A 0.16 N/D 0.03 0.1 N/D N/D N/D N/D N/D COREXIT EC9527A <0.005 <0.01 <1.0 <0.2 <0.1 <0.003 <0.1 0.1 <0.01 FINASOL OSR 52 <10.0 <10.0 <10.0 <10.0 <10.0 <1 <10.0 <10.0 <0.4 JD-109 <10.0 <10.0 <10.0 <10.0 <1 <10.0 <10.0 <10.0 <0.5 JD-2000 <0.24 <10.0 <10.0 <10.0 <0.43 <10.0 <10.0 <0.11 <0.20 MARE CLEAN 200 <0.50 <0.10 <0.50 <0.250 <2.5 <0.0200 <2.5 0.611 <0.01 NEOS AB3000 <0.1 <0.1 0.26 <0.05 0.21 <0.001 0.076 1.1 <0.05

(47) Table 2 illustrates that DXR-02 is the only oil dispersant tested which did not contain heavy metals. This is thought to be due to the absence of any solvents in the production of the DXR-02 oil dispersant of the present invention.

(48) The dispersant properties of the composition of the invention were determined in accordance with ASTM-F2059, Laboratory Oil Spill Dispersant Effectiveness Using the Swirling Flask. The % Effectiveness is illustrated in Table 3.

(49) TABLE-US-00003 TABLE 3 Material Tested - South Louisiana Crude Oil Dispersant % Effectiveness DXR-02 74.28% BIODISPERS 63% COREX EC9500A 54.70% COREXIT EC9527A 63.4 FINASOL OSR 52 71.60%

(50) This test establishes a baseline performance parameter so that dispersants can be compared, a given dispersant can be compared for effectiveness on different oils, and at different oil weathering stages, and batches of dispersant or oils can be checked for effectiveness changes with time or other factors. Basically, the test method covers the procedure to determine the effectiveness of oil spill dispersants on various oils in the laboratory. This test method covers the use of the swirling flask test apparatus. Results obtained using this test method are intended to provide baseline effectiveness values used to compare dispersants and oil types under conditions analogous to those used in the test.

(51) Acute Oral Toxicity in Rats

(52) The test material, DXR-02, was tested in rats to assess an Acute Oral Toxicity. The test yielded the following result:

(53) In a Limit Screen, an oral 5000 mg/kg (body weight) dose of this test material, when administered to five female Sprague-Dawley rats, did not result in any mortality or abnormalities. The LD50 is thus greater than 5000 mg/kg. According to the Guide to the Globally Harmonized System for Classification and Labeling of Chemicals (GHS), the classification of chemicals, as well as Acute Oral Toxicity LD50 (mg/kg) for EPA/US/FIFRA, are classified as follows:

(54) TABLE-US-00004 LD.sub.50 (mg/kg) Toxic Category Acute Toxicity Definition 0 50 Toxicity Category I High >50 500 Toxicity Category II Hazard >500 < 5000 Toxic Category III Hazard >5000 Toxic Category IV Low

(55) The LD.sub.50 for DXR-02 was determined to be greater than 5000 mg/kg, which according to above categories, the acute toxicity of this product is low.

(56) Now referring to FIG. 2, a field test of DXR was conducted using DXR in a 1:1 ratio with a cocktail of microbes obtained from New Leaf Biologics Inc. in Manitoba, Canada, designated NLB1000. NLB1000 is a cocktail of microbes used for hydrocarbon degradation. While the 1:1 ratio represents an effective embodiment for hydrocarbon degradation, it is understood that this is a non-limiting embodiment, and that various other effective ratios are within the purview of the present invention, so long as they are effective for A 3 cubic foot sample of soil spiked with petroleum hydrocarbons was provided. The test was run in triplicate. To Piles 1, 2 and 3 the 1:1 combination of DXR and NLB1000 was added by spraying onto the piles. As can be seen in FIG. 2, the percentage of total petroleum hydrocarbons (TPH) was fully degraded by about day 30.

(57) Although the field test was conducted with NLB1000, in accordance with the present invention, suitable biological hydrocarbon degraders include, but are not limited to, aerobic and/or anaerobic microorganisms selected from the families Bacillus, Pseudomonas, Paenibacillus and Aspergillus, as well as environmentally modified, transitioned or evolved strains thereof for optimal hydrocarbon degradation in combination with the disclosed DXR oil dispersant formulation in order to maximize the efficiency of treatment. The microorganisms are selected on the basis of their suitability for degrading such materials as benzene, toluene, and xylene (BTEX), petroleum hydrocarbon fractions F1-F4 (as defined by CCME2000), and polycyclic aromatic hydrocarbons.

(58) Now referring to FIG. 3, the NLB1000/DXR 1:1 blend (designated NLB1010) was tested to compare different hydrocarbon degrading products on a medium crude oil contaminated test pile. The piles were dosed as follows:

(59) Pile 1NLB1000; Pile 2BSG2000 (Biosolv Green 2000); Pile 3NLB1010; Pile 4Open PileAutoclaved to kill off any microbes; Pile 5Normal floraan open pile containing indigenous flora; Pile 6dosed with ERE microbe blend (a competitive microbial composition).

(60) As can be seen from the graph of FIG. 3, the percentage of Total Petroleum Hydrocarbons provided by the medium crude oil contaminant was degraded at various rates. After 45 days, only the NLB1010 sample was virtually devoid of petroleum hydrocarbon contamination, showing the superiority of the instantly disclosed invention for remediating petroleum hydrocarbon contamination in soils.

(61) All patents and publications mentioned in this specification are indicative of the levels of those skilled in the art to which the invention pertains. All patents and publications are herein incorporated by reference to the same extent as if each individual publication was specifically and individually indicated to be incorporated by reference.

(62) It is to be understood that while a certain form of the invention is illustrated, it is not to be limited to the specific form or arrangement herein described and shown. It will be apparent to those skilled in the art that various changes may be made without departing from the scope of the invention and the invention is not to be considered limited to what is shown and described in the specification and any drawings/figures included herein.

(63) One skilled in the art will readily appreciate that the present invention is well adapted to carry out the objectives and obtain the ends and advantages mentioned, as well as those inherent therein. The embodiments, methods, procedures and techniques described herein are presently representative of the preferred embodiments, are intended to be exemplary and are not intended as limitations on the scope. Changes therein and other uses will occur to those skilled in the art which are encompassed within the spirit of the invention and are defined by the scope of the appended claims. Although the invention has been described in connection with specific preferred embodiments, it should be understood that the invention as claimed should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes for carrying out the invention, which are obvious to those skilled in the art, are intended to be within the scope of the following claims.