BR102015013644B1 - composition, composition preparation process, biocidal process and use - Google Patents

Abstract

COMPOUND, COMPOSITION, PROCESS, METHOD AND USES. The present invention describes compounds comprising chemical castor compounds. The present invention also relates to the composition comprising said compounds, process for preparing the composition, method and uses of the compound and the composition. The present invention is located in the fields of Agriculture, Microbiology and Chemical Engineering.

Description

Priority

[0001] This patent application claims internal priority over patent application BR 10 2014 014162-6, filed on June 11, 2014.

Field of the Invention

[0002] The present invention describes a composition comprising ricinoleic acid, castor oil and additionally an amino compound and / or a defoamer such as, for example, citric acid. The present invention also describes a process for preparing said composition, biocidal process / method which comprises the step of applying the composition and the use of said composition. The present invention is in the fields of Agriculture, Microbiology and Chemical Engineering.

Background of the invention

[0003] One of the main current challenges of the state of the art is the provision of compositions that have biocidal activity (that is, activity against different types of microorganisms, such as viruses, fungi and bacteria) and, at the same time, that are biodegradable ( that is, not generating toxic waste to the environment) and also being of low toxicity to fauna.

[0004] In one aspect of the state of the art related to the subject, there is the issue of oil fields, where, according to estimates, the volume of water produced by oil fields worldwide exceeds that of oil by a factor of three. Consequently, the produced water (or oil-producing water) represents one of the highest costs associated with companies, as, as a management strategy, it is usually pumped or transported to off-site treatment facilities, or pumped into disposal wells. . In addition, there are four main problems related to microorganisms for this Sector: (I) biocorrosion; (II) contamination of the produced water that can lead to contamination of oil fields after reinjection; (III) biological encrustation, which is the formation of biological deposits; and (IV) acidification, which is the production of hydrogen sulphide (H2S) by bacteria.

[0005] With the expectation of high growth of produced water and the resulting public pressure for regulation and control (Oliveira et al., 2012), a high growth in the demand for laboratory services (analyzes) is expected, aiming at monitoring, control and characterization, as well as new ideas that result in more efficient services.

[0006] Thus, there is a need to provide solutions to solve the problem of water contamination in regions where there is oil, without, however, presenting a high risk to the environment or to the populations in the surroundings.

[0007] The search for the state of the art has revealed some documents indicated below, but which do not reveal or suggest the present invention.

[0008] The document “In vitro evaluation of the antimicrobial activity of a oil-based castor irrigant” (Leonardo et al., J. Endod. 2001 Dec; 27 (12): 717-9.) Refers to antimicrobial activity Endoquil (castor oil detergent solution), 2% chlorhexidine gluconate solution and 0.5% NaOCl solution, against gram-positive and gram-negative bacteria. However, among other technical reasons, nothing is revealed in relation to a composition containing at least 40% ricinoleic acid, castor oil and additionally diethanolamine.

[0009] The document “Evaluation of the Antimicrobial and Phytochemical Properties of Oil from Castor Seeds (Ricinus communis Linn)” (Momoh et al., Bull. Environ. Pharmacol. Life Sci .; Volume 1 [10] September 2012: 21 - 27) refers to the antimicrobial evaluation and phytochemical properties of castor oil. However, among other technical reasons, nothing is revealed in relation to a composition that comprises at least 40% ricinoleic acid, castor oil and additionally diethanolamine and / or its biocidal applications.

[0010] BR PI 0807634 discloses biocidal compositions comprising at least one dialkylamide and at least one biocide. However, there is no disclosure in said document of a composition comprising at least 40% ricinoleic acid, castor oil and additionally diethanolamine and / or its biocidal applications.

Summary of the Invention

[0011] Thus, the present invention aims to solve the constant problems in the state of the art from a composition that comprises ricinoleic acid, castor oil and additionally in combination with an amino compound and / or a defoamer such as, for example , citric acid (although it is not limited to citric acid only), as well as a process for preparing said composition, a biocidal process / method comprising the stage of applying the composition and the use of said composition.

[0012] A composition comprising ricinoleic acid and castor oil is a first object of the present patent application.

[0013] A second object of the present invention is a process for preparing said composition comprising the step of solubilizing ricinoleic acid, castor oil, and additionally an amino compound and / or an antifoam.

[0014] A third object of the present invention is a biocidal process / biocidal method comprising contacting the biocidal composition disclosed by the present invention with at least one microorganism.

[0015] It is a fourth object of the present invention to use the composition disclosed by the present invention for the control of microorganisms.

[0016] Still, the inventive concept common to all the claimed protection contexts is the composition revealed by the present invention.

[0017] These and other objects of the invention will be immediately appreciated by those skilled in the art and by companies with interests in the segment, and will be described in sufficient detail for their reproduction in the description below.

Brief Description of the Figures

[0018] In order to better define and clarify the content of this patent application, the following figures are presented:

[0019] Figure 1 shows the experimental results obtained for the disk diffusion method for qualitative analysis of the action of biocides on anaerobic bacteria no. 3. A = biocide HAB-1; B = biocide HAB-2; Glu = glutaraldehyde, Met = methanol, A = 10 μL of the biocide HAB-1 and B = 10 μL of the biocide HAB-2, A / 2 = 5μL of the biocide HAB-1 and B / 2 = 5 μL of the biocide HAB-2 and A / 4 = 0.25 μL of the biocide HAB-1 and B / 4 = 0.25 μL of the biocide HAB-2.

[0020] Figure 2 shows the experimental results obtained for the disc diffusion method for the qualitative analysis of the action of biocides on anaerobic bacteria in. 4. A = HAB-1 biocide; B = biocide HAB-2; Glu = glutaraldehyde, Met = methanol, A = 10 μL of biocide HAB-1 and B = 10 μL of biocide HAB-2, A / 2 = 5 μL of biocide HAB-1 and B / 2 = 5 μL of biocide HAB- 2 and A / 4 = 0.25 μL of the biocide HAB-1 and B / 4 = 0.25 μL of the biocide HAB-2.

[0021] Figure 3 shows the experimental results of the disk diffusion method for qualitative analysis of the action of HAB biocides on anaerobic bacteria 7; A = biocide HAB-1; B = biocide HAB-2; Glu = glutaraldehyde, Met = methanol, A = 10 μL of biocide HAB-1 and B = 10 μL of biocide HAB-2, A / 2 = 5 μL of biocide HAB-1 and B / 2 = 5 μL of biocide HAB- 2 and A / 4 = 0.25 μL of the biocide HAB-1 and B / 4 = 0.25 μL of the biocide HAB-2.

[0022] Figure 4 shows the diameter of the halos of biocides and controls.

[0023] Figure 5 shows the powdery colony of Aspergillus niger; white anteverse; dark back, with many droplets and septa hyphae. 40X magnification. Stained with KOH.

[0024] Figure 6 shows the results of inhibition of fungal growth (in Aspergillus niger) by the tested compositions and indicated in Table 1.

[0025] Figure 7 shows a powdery colony of hyaline (light) fungi with unsepted hyphae of the genus Aspergillus. White preview. 40X magnification. Stained with cotton blue.

[0026] Figure 8 shows the results of inhibition of fungal growth by the tested compositions and indicated in Table 1.

[0027] Figure 9 shows the image obtained by scanning electron microscopy for a virus control group in the experiments carried out to test the antiviral activity of the compositions indicated in Table 1.

[0028] Figure 10 shows the image obtained by scanning electron microscopy for another virus control group in the experiments carried out to test the antiviral activity of the compositions indicated in Table 1.

[0029] Figure 11 shows the image obtained by scanning electron microscopy for another virus control group in the experiments carried out to test the antiviral activity of the compositions indicated in Table 1.

[0030] Figure 12 shows the image obtained by scanning electron microscopy for a group of RNA viruses of the family togaviridae, genus Alphavirus treated with the compositions 50% castor oil / 50% ricinoleic oil and 100% ricinoleic.

[0031] Figure 13 shows another image obtained by scanning electron microscopy for a group of RNA viruses of the family togaviridae, genus Alphavirus treated with the compositions 50% castor oil / 50% ricinoleic oil and 100% ricinoleic.

[0032] Figure 14 shows another image obtained by scanning electron microscopy for a group of RNA viruses of the family togaviridae, genus Alphavirus treated with the compositions 50% castor oil / 50% ricinoleic oil and 100% ricinoleic.

[0033] Figure 15 shows another image obtained by scanning electron microscopy for a group of RNA viruses in the family togaviridae, genus Alphavirus treated with the compositions 50% castor oil / 50% ricinoleic oil and 100% ricinoleic.

Detailed Description of the Invention

[0034] A first object of the present patent application is a composition comprising ricinoleic acid, castor oil and additionally an amino compound and / or a defoamer.

[0035] In one embodiment, ricinoleic acid is in an amount in the composition of at least 30% by weight or by volume.

[0036] In one embodiment, ricinoleic acid is in a composition amount of at least 40% by weight or by volume.

[0037] In one embodiment, ricinoleic acid is in a composition amount of approximately 40% by weight or by volume.

[0038] In one embodiment, ricinoleic acid is in an amount of 40% by weight or by volume.

[0039] In one embodiment, ricinoleic acid is in a composition amount of at least 50% by weight or by volume.

[0040] In one embodiment, castor oil is in a composition amount of at least 30% by weight or by volume.

[0041] In one embodiment, castor oil is in a composition amount of at least 50% by weight or by volume.

[0042] In one embodiment, the defoamer is citric acid.

[0043] In one embodiment, the amino compound is diethanolamine.

[0044] In one embodiment, the amino compound is in a composition amount of up to 40% by weight or by volume.

[0045] In one embodiment, diethanolamine is in an amount in the composition of at least 10% by weight or by volume.

[0046] In one embodiment, diethanolamine is in an amount, in the composition, between 10% and 25% by weight or by volume.

[0047] In one embodiment, the composition comprises 20% diethanolamine, 40% ricinoleic acid and 40% castor oil.

[0048] In one embodiment, the composition comprises 2% (v / v) citric acid, 49% (v / v) castor oil and 49% (v / v) ricinoleic oil.

[0049] In one embodiment, the composition comprises 5% (v / v) citric acid, 47.5% (v / v) castor oil and 47.5% (v / v) castor oil.

[0050] In one embodiment, the composition comprises 10% (v / v) citric acid, 40% (v / v) castor oil and 40% (v / v) ricinoleic oil.

[0051] In one embodiment, the composition comprises 50% (v / v) castor oil and 50% (v / v) castor oil.

[0052] In one embodiment, the composition consists of 100% (v / v) Ricinoleic oil.

[0053] A second object of the present invention is a process for preparing said composition comprising the step of mixing ricinoleic acid and castor oil, and additionally the amino compound and / or the defoamer.

[0054] In one embodiment, ricinoleic acid is in a mixture amount of at least 30% by weight or by volume.

[0055] In one embodiment, the ricinoleic acid is in a mixture amount of at least 50% by weight or by volume.

[0056] In one embodiment, castor oil is in a mixture amount of at least 30% by weight or by volume.

[0057] In one embodiment, castor oil is in a mixture amount of at least 50% by weight or by volume.

[0058] In one embodiment, the amino compound is a alcohol containing the amine function.

[0059] In one embodiment, the amino compound is diethanolamine.

[0060] In one embodiment, diethanolamine is in an amount in the mixture of at least 10% by weight or by volume.

[0061] In one embodiment, diethanolamine is in an amount in the mixture of at least 25% by weight or by volume.

[0062] In one embodiment, castor oil is in a proportion of 40% by weight or volume, ricinoleic acid is in a proportion of 40% in mass or volume and diethanolamine is in a proportion of 20% in mass or by volume.

[0063] In one embodiment, citric acid is in a proportion of 2% to 10% by volume, castor oil is in a proportion of 40% to 50% by volume and ricinoleic oil is in a proportion of 40% to 50% by volume.

[0064] A third object of the present invention is a biocidal process / biocidal method comprising the step of contacting the composition as defined in this patent application with at least one microorganism selected from fungi, bacteria and combinations of fungi and bacteria.

[0065] In one embodiment, the bacteria are sulfate-reducing bacteria (BRS bacteria as defined in the present patent application).

[0066] In one embodiment, the biocidal process / biocidal method is applied to “produced water” in oil fields / basins.

[0067] It is a fourth object of the present invention to use the composition as disclosed by the present invention for the control of microorganisms.

[0068] In one embodiment, microorganisms are fungi, viruses, bacteria and combinations thereof.

[0069] In one embodiment, the bacteria are sulfate-reducing bacteria (BRS bacteria as defined in the present patent application).

[0070] In one embodiment, the bacterium is selected from the group consisting of bacteria of the genera Clostridium and Thalassosira.

[0071] In one embodiment, the bacteria are selected from the group consisting of: Clostridium botulinum, Clostridium bifermentans, Clostridium sporogenes, and Thalassospira sp ..

[0072] In one embodiment, viruses are viruses of the Togaviridae family.

[0073] In one embodiment, the viruses are of the Alphavirus genus.

[0074] In one embodiment, the fungi are of the Aspergillus genus.

[0075] In one embodiment, the fungi are of the species Aspergillus niger.

Definition of some terms / expressions used in this patent application

[0076] Microorganism (s)

[0077] The term is understood, in the present patent application, as any type of microorganism, such as, but not limited to: bacteria, fungi, protozoa, among others.

[0078] Amino compound

[0079] The term is understood, in the present patent application, as being any compound that has in its chemical structure the amine function, thus also comprising the compounds containing primary amine (-NH2), secondary amine (-NH-) and / or tertiary amine (-N-). A non-limiting example of amine compounds are the diols with a secondary amine, such as diethanolamine (molecular formula C4H11NO2) and whose structural formula is indicated below by Formula I:

[0080] Ricinoleic acid

[0081] The term is understood, in the present patent application, as 12-hydroxy-9-cis-octadecenoic acid (omega-9 fatty acid) and represented by Formula II below and, still in the context of the present patent application, Ricinoleic acid can be obtained through different processes, such as saponification or fractional distillation of hydrolyzed castor oil.

[0082] Castor oil

[0083] The term is understood, in this patent application, as being the oil obtained from the plant Ricinus communis or other varieties of the same species. The oil can be obtained from the seeds of that plant.

[0084] Biocide HAB-1 or biocide A

[0085] The term is understood, in the present patent application, as being a composition that is biocidal, presenting activity to kill or inhibit the proliferation of fungi and / or bacteria, which composition comprises: at least 50% of ricinoleic oil, castor oil and the diethanolamine compound. This biocide showed several experimental results proving its biodegradability and low environmental toxicity (including toxicity to animals).

[0086] Biocide HAB-2 or biocide B

[0087] The term is understood, in the present patent application, as being a composition that has activity to kill or inhibit the proliferation of fungi and / or bacteria, which composition comprises: ricinoleic oil, castor oil and the compound diethanolamine. For example, the composition comprises 40% ricinoleic acid and 20% diethanolamine. This biocide showed several experimental results proving its biodegradability and low environmental toxicity (including toxicity to animals).

[0088] BRS or BRS bacteria

[0089] The term is understood, in the present patent application, as any genus or species of sulfate-reducing bacteria, that is, bacteria that can promote the (chemical) reduction of sulfates to sulfides.

[0090] “Water produced”

[0091] The term is understood, in the present patent application, as it is known in the oil industry, that is: the high salinity aqueous fluid produced together with oil. It is the largest waste produced by the oil industry, and the improper management of “produced water” is associated with environmental and health damage.

[0092] Percentages by mass or by volume

[0093] For a better understanding of the present invention, with regard to the amounts of the components of the compositions disclosed in the present patent application, it should be understood that the percentages of each component are in mass (m / m) or in volume (v / v) in relation to the total mass or the total volume of the prepared composition. For example, if a composition contains at least 40% castor oil and at least 40% castor oil, it is understood that the said composition has at least 40% by weight (in relation to the total mass of the composition) of castor oil. castor oil and at least 40% by weight (in relation to the total mass of the composition) of Ricinoleic oil. Taking the same example cited, it is understood that the percentages can also refer to the volume and, in this understanding, there is at least 40% in volume (in relation to the total volume of the composition) of castor oil and at least 40% by volume (in relation to the total volume of the composition) of Ricinoleic oil.

[0094] Defoamer

[0095] In the context of the present patent application, the term "defoamer" should be understood as any agent that attenuates or prevents the formation of foam, such as citric acid. Defoamer is important, for example, but not limited to, in applications as a drilling fluid additive in the oil industry.

[0096] Example 1 - Example of embodiment of the invention

[0097] Collection of “produced water” samples and cultivation of bacterial strains

[0098] Samples of water produced (50 ml) were collected during a technical visit by the group to mature basins in Bahia, SE and Rio Grande do Norte under aseptic conditions. One of the samples was untreated water and the second sample of the same water treated with a standard biocide. The samples were taken to the laboratory, and the water was seeded in BHI (brain heart infusion) medium and grown in anaerobiosis. The BHI medium was used because the tested bacteria grew reproducibly in this medium, however other means could be used, such as Postgate, yeast extracts, among others.

[0099] The BHI medium presented itself as an excellent medium for the growth of sulfate-reducing bacteria.

[0100] Methodology for applying biocidal compositions to sulfate-reducing embacteria

[0101] After the isolation and growth of some bacterial strains, these bacteria were stored for future characterization and control experiments.

[0102] Two biocidal fractions isolated from castor bean were used in the present study and named BIOA and BIOB. 500 μL of the bacterial suspensions (108 CFU / ml) were seeded with a Drigalski loop to obtain a uniform microbial growth mat in Petri dishes (90 mm in diameter) containing 20 ml of modified BHI Agar (0.5 yeast extract %, 0.1% hemin and 0.1% menadione).

[0103] For the assessment of biocides, a new method was used in which disks made with number 1 wattman paper (6 mm in diameter) were added aseptically to the agar surface after being previously soaked with 10 μL of biocidal substance A and B with different concentrations (A, A / 2, A / 4 and B, B / 2 and B / 4). Solutions of methanol and sterile distilled water (used in dilutions of biocides) were used as a negative control and 25% glutaraldehyde as a positive control. The plates were incubated for 24 hours at 37 ° C in anaerobes.

[0104] Antibacterial effect

[0105] Results obtained for the tested biocidal compositions and non-limiting examples of anaerobic bacteria species subjected to the testing of the biocidal compositions

[0106] Several species of anaerobic bacteria have been tested, the predominant species being those of the genus Clostridium, such as: Clostridium botulinum, Clostridium bifermentans, Clostridium sporogenes, in addition to the species Thalassospira sp ..

[0107] Samples of produced water collected after standard treatment did not show any bacterial growth and have not been tested with biocides. With the described methodology, strict anaerobic bacteria named 3, 4 and 7 were isolated from the water produced without treatment with the standard biocide.

[0108] Biocide A was more effective for all samples by visualizing the inhibition halos (as can be seen in Figures 1, 2 and 3). The relationship between the diameter of the halo and the concentration of the biocides was statistically significant (Figure 4). Biocide A was effective against all samples containing bacteria and also had the technical advantage of having an excellent solubility in water, demonstrating, in the experimental tests, with a high solubility in water.

[0109] Thus, in one of the embodiments of the present invention, promising experimental results of a composition (HAB-1) containing partially (about 50% ricinoleic oil and castor oil) are shown to be biodegradable and not toxic (to the environment or to animals), as a biocidal agent against bacteria isolated from samples of water produced from Mature Basins in Northeastern Brazil. Clearly, the application of the composition in a biocidal process / biocidal method is already observed in at least one microorganism such as bacteria, viruses and fungi and, also, the use of the composition for the control of microorganisms.

[0110] The test used to verify biocidal activity is similar to the disc diffusion technique used for antibiotic analysis. This test was carried out for the first time for biocides and proved to be a fast and very promising technique for the initial selection of new biocides. The technique can contribute significantly by providing faster test response times.

[0111] Biocide testing allows for fast and efficient screening of biocides against bacteria isolated from the oil fields themselves. These biocides have also been tested for toxicity in mammalian cells to assess toxicity to humans. The tested biocides showed biocidal activity, including for Sulfate Reducing Bacteria (BRS); it is antifungal and general antimicrobial.

[0112] The disk diffusion technique was used in a Petri dish, under conditions suitable for the growth of bacteria. Preliminary results show that this technique (never used before for biocidal tests) is sensitive and reliable, and the results can be obtained within 24 hours. The HAB-1 composition was effective in inhibiting the growth of three different types of anaerobic bacteria isolated from samples of produced water.

[0113] Antifungal effect

[0114] Tests and experimental results on fungi of the genus Aspergillus with the compositions disclosed in this patent application

[0115] For the experimental tests on fungi of the Aspergillus genus, five (05) compositions were prepared, indicated as follows in Table 1 below:

[0116] Table 1. Compositions tested in experimental tests with fungi of the genus AspergillusComposition no. Composition components (percentages in

[0117] For testing the compositions indicated in Table 1, the fungi were grown on Sabourand Agar medium. After inoculation in a Petri dish, disks embedded in the compositions were added to said Petri dishes and the same dishes were incubated for 96 hours. The experimental results of the tests for the compositions indicated in Table 1 in fungi showed that all compositions were effective, presenting the biocidal effect, as indicated in figures 5 to 8 (figures 5 and 6 corresponding to the test performed on the species Aspergillus niger and figures 7 and 8 corresponding to the test performed on another fungus of the Aspergillus genus).

[0118] Antiviral effect

[0119] Tests and experimental results on viruses (antiviral effect) with the compositions disclosed in this patent application

[0120] For antiviral tests, the following compositions were tested: 50% castor oil and 50% ricinoleic; and 100% ricinoleic.

[0121] These compositions were tested against an RNA genome virus, a virus belonging to the Togaviridae family, genus Alphavirus. Biocida showed antiviral activity in non-toxic concentrations for mammalian cell culture. Figures 9 to 15 show scanning electron microscopy images of the control (three images) and treated (four images) with the biocide. Specifically, figures 9 to 11 refer to the viruses of the control samples, while figures 12 to 15 refer to the experimental results obtained with the viruses treated with the biocidal compositions.

[0122] Example of the preparation of the composition

[0123] The preparation of the composition presents the step of adding, to a reactor:

[0124] 500 ml of castor oil, 500 ml of ricinoleic acid and 250 ml of diethanolamine; an isothermal reaction is obtained by mixing the components (castor oil, ricinoleic acid and diethanolamine) for an interval of one and a half to two hours. After such a time interval, the composition with biocidal properties is obtained, as demonstrated in the tests and experimental results.

[0125] It should also be noted that, regardless of the biocidal applications presented in this patent application (applications against viruses, fungi and / or bacteria), the composition has as main components castor oil and ricinoleic oil, the compound being amine (for example, diethanolamine) also contributes to this effect, however there are variations in the experimental tests of effectiveness obtained.

[0126] Those skilled in the art will value the knowledge presented here and will be able to reproduce the invention in the modalities presented and in other variants, covered by the scope of the attached claims.

Claims (11)

1. Composition characterized by comprising: a) 30% to 50% by weight or by volume of ricinoleic acid; and b) from 30% to 50% by weight or by volume of castor oil; and c) from 10% to 40% by weight or by volume of a diethanolamine. Composition according to claim 1, characterized in that it comprises up to 40% by volume of ricinoleic acid, 40% by volume of castor oil and 25% by volume of diethanolamine. Composition according to any one of the preceding claims, characterized in that it comprises from 2% to 10% by volume of citric acid. Process for preparing the composition as defined in any one of the preceding claims, characterized in that it comprises a step of mixing castor oil, ricinoleic acid and diethanolamine. Preparation process according to claim 4, characterized in that: a) Ricinoleic oil is in the concentration of 30% to 50% by weight or by volume; b) castor oil is in the concentration of 30% to 50% by weight or by volume; and c) diethanolamine is in the concentration of 10% to 40% by weight or by volume. Preparation process according to claim 4 or 5, characterized in that: a) Ricinoleic oil is in the concentration of 40% by weight or by volume; b) castor oil is at a concentration of 40% by weight or by volume; and c) diethanolamine is at a concentration of 20% by weight or volume. Preparation process according to claim 6, characterized in that it comprises a mixing step with a citric acid in the concentration of 2% to 10% by mass or by volume. 8. Biocidal process characterized by comprising a step of contacting the composition, as defined in any one of claims 1 to 3, with at least one microorganism selected from fungi, bacteria, viruses and combinations thereof. Process according to claim 8, characterized in that the microorganism is a sulphate-reducing bacteria. 10. Use of the composition, as defined in any of claims 1 to 3, characterized by being for the control of fungi, bacteria, viruses and combinations thereof. 11. Use of a composition according to claim 10, characterized for being for the control of sulfate-reducing bacteria.

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