BRPI0805525A2 - copper algicidal compositions - Google Patents

Abstract

ALGICIDE COPPER COMPOSITIONS. This invention describes novel algicidal compositions for killing or controlling the growth of algae and other unwanted plants in water reservoir treatments and is characterized in that it contains copper in the form of chelates or proteinates prepared with amino acids or protein hydrolysates. Copper chelates or proteinates of the novel compositions are safe and do not dissociate with subsequent formation of insoluble species, remaining in solution even under strict conditions of use.

Description

"ALGICIDE COPPER COMPOSITIONS"

This disclosure relates to a patent for the invention of novel algalidal compositions for controlling the growth of algae and other undesirable plants in water reservoirs and is characterized in that it comprises copper in the form of chelates or proteinates prepared with free amino acids or protein hydrolysates, more preferably. in the form of a chelate prepared with glutamic acid. The new compositions are efficient and safer than the algicidal compositions used today, characterized by the simple association of copper and alkanolamine salts.

Industrial water reservoirs for recreation or consumption, rivers, lakes, irrigation systems, among others, are often polluted by the overgrowth of algae and aquatic plants that promote the unwanted appearance of taste and odor in water. These algae can also interfere with water flow and are harmful to health when consumed by animals and especially humans. The treatment to kill or inhibit the growth of algae and aquatic plants can be done in different ways, but among the compounds used are those based on water-soluble forms of cobresolvers. In the past, copper sulfate has been widely used to kill and control algae growth in waters with pH values below 7.0. In other cases, when the waters contain carbonates, bicarbonates or other alkaline species that may promote water pH values greater than 7.0, copper sulfate is not efficient due to precipitation of copper in the form of hydroxide or copper carbonate. Therefore, it is essential that copper remain dissolved in solution to be efficiently used as an algaecide for the treatment of algae and other aquatic plants. When copper is converted into any form of low water solubility, its efficiency as an algaecide ceases to exist. In addition, when the copper is precipitated into its insoluble salts, water disruption and material deposits occur at the bottom of water reservoirs, which can destroy other aquatic life forms or ozooplankton, which are critical for animal feed. The most widely used form of water treatment today is the use of complexes formed by the association of inorganic copper salts with alkanolamines. These products may be used in waters of relatively stable alkaline pH, depending on their compositions.

Patent document filed under US 2,734,028 describes a complex prepared by reacting a copper salt with an alkanolamine for the treatment of algal growth control. In this invention, the authors show that complexes formed by the association of copper salts with alkanolaminase, more preferably triethanolamine, do not precipitate in alkaline pH waters and become efficient as an algicidal agent. In another patent document filed under US 3,905,797, the authors claim a more efficient composition than the alkanolamine complexes described above. In this case, the complexes are formed by the association between a dipyridinium ion, copper and an alkanolamine. As in other documents, alkanolamines are preferably selected from monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, diethylethanolamine, diisopropanolamine, triisopropanolamine, methyldiethanolamine, among others, but triethanolamine is preferably used. In another document filed under US Patent No. 3,948,632, the authors claim the use of a safer and more efficient algicidal composition as a copper complex formed by the association of an inorganic copper salt with an alkanolamine in the presence of a herbicide. In this case, the herbicide is selected from cyclic carboxylic acids or alkali metal salts. In another document, filed under the US Patent No. 4,030,907, the authors claim more stable copper compositions formed by the combination of inorganic copper salts, alkanolamines and ammonium salts. Ammonium salts are preferably selected from ammonium nitrate, ammonium phosphate, ammonium chloride, ammonium thiocyanate, ammonium sulfate, among other salts. The authors claim that copper and ammonium salt alkanolamine compositions are more stable when stored for longer periods of time as well as when exposed to light and do not promote the appearance of undesirable precipitates that reduce the efficiency of copper salts as algaecides.

In another document filed under US Patent No. 4,324,578, the authors claim the preparation of an algalicidal composition by combining copper carbonate and a mixture of monoethanolamine and triethanolamine. In this paper, the authors teach that copper carbonate can be fully solubilized when treated by the combination of alkanolamines. In this case, the authors also indicate that copper is in the form of a chelate when combined with the alkanolamines of interest.

Despite being prepared in different proportions and sources of raw materials, the algicidal compositions used today are mainly based on the combination of copper salts and alkanolamines, with the aim of keeping copper in a soluble form to preserve its efficiency as an algicidal agent. In some cases, other compounds are added to the formulation to increase the solubilization efficiency or the algaecidal activity of copper. However, all of these compounds have deficiencies, as they are formed by simply associating preferentially selected copper salts with sulfate and carbonate and alkanolamines, resulting in mistakenly named complexes as chelates that have a weak inter-metal-binder interaction through the nitrogen atom of the amino acids. metal. Thus, the development of deformations that are effectively stable in alkaline media and the presence of other interfering agents and which have a high efficiency as algicidal agents is desirable. In addition, it is also desirable to develop formulations that are safer, especially for the treatment of drinking water reservoirs or other reservoirs where water ingestion may occur, such as recreation pools, among others. Accordingly, it is an object of this invention to describe a novel algicidal composition comprising amino acid copper chelates, which can be effectively used as agents for killing or controlling the growth of algae and other undesirable aquatic plants. It is also the object of this invention to disclose that the novel cobrene compositions precipitate in alkaline aqueous media or in the presence of other interferers and are effectively safe for human consumption and other animals.

OBJECTIVES OF THE INVENTION

It is an object of this invention to describe a novel algicidal composition comprising chelates or proteinates which are prepared with amino acids or protein hydrolysates, respectively, for treating waters to kill or control the growth of algae and other undesirable aquatic plants. It is also the object of this invention to show that copper chelates or proteinates can be prepared by various processes described in literature and can be efficiently used in water.

DETAILED DESCRIPTION OF THE INVENTION

Chelates are a class of compounds that are formed by the reaction between metal cations and at least two electronegative sites present in the same binder. In this case, the Ligands are characterized by amino acids. The coordination of the ligands with the centrometallic occurs through covalent and ionic bonds and, more particularly, by the interaction between metal cations with the amino acid carboxy and amine groups. The chelates resulting from these reactions are neutral compounds of cyclic structure and have high stability constants, which give a high stability to these compounds. Thus, chelates are stable over wide pH ranges, including those of interest to this invention, and do not dissociate in the presence of other interferents, that is, other organic compounds that are present in the medium. When peptides are used in place of free amino acids, usually found in the form of protein hydrolysates, the reaction products are termed as proteinates. In this case, the hydrolysates are composed of mixtures of free amino acids, dipeptides, tripeptides or low molecular weight tetrapeptides and are obtained by enzymatic or chemical hydrolysis of protein sources. When protein hydrolysates are prepared from enzymatic hydrolysis, enzymes such as endopeptidases or exopeptidases are used and protein hydrolysates are prepared by hydrolysis. Bases or acids such as calcium oxide or hydrochloric acid are used. In either case, protein hydrolysates should have a low molecular weight and preferably less than 4KDa when used for the preparation of proteinates so that a greater number of active sites can be obtained for the proper coordination of copper atoms in the protein. final product.

However, the copper chelates of this invention are preferably prepared as free amino acids and more preferably with naturally occurring free amino acids. Thus, the amino acids used for the preparation of the chelates of this invention are selected from glycine, lysine, alanine, phenylalanine, leucine, isoleucine, proline, hydroxyproline, arginine, methionine, aspartic acid, glutamic acid, valine, threonine, isotreonine, histidine, tryptophan, serine eglutamine and more preferably the chelates of this invention are more preferably prepared with glutamic acid or glycine. Copper sources for the preparation of chelates are preferably selected from salts and copper carbonates and more preferably are selected from copper sulfate, copper chloride and copper carbonate. However, chelates can also be prepared from metallic copper or copper oxide.

Importantly, the chelates of interest must be prepared under appropriate conditions that enable the formation of heterocyclic structures, termed chelates, and must have at least one amino acid fragment linked to the cobrea through covalent and ionic bonds. Other copper valence sites may be occupied by other amino acid fragments or other organic species, and this will depend on the conditions under which the chelates are prepared. Thus, chelates or proteinates are characterized by having metal-coordinated ligands with a stoichiometric ratio ranging from 1: 1 to 3: 1 and, more preferably, a stoichiometric ratio of 2: 1. It is also important to note that chelates or proteinates are not formed by simple mixing of the starting materials, even meeting the molar relationships described above and the conditions for obtaining them must be obtained to obtain products that can be characterized as metal chelates or proteinates.

These conditions are widely described in the technical literature and various techniques can be employed by those skilled in the art to obtain the compounds, and the most suitable conditions must be selected and employed, varying for each individual subject. Thus, the compounds of interest of this invention are not characterized as simple mixtures of free amino acids or protein hydrolyzate sources with copper sources, since these mixtures do not have the benefits observed by the use of chelates or proteinates as algicides.

Thus, due to their chemical nature when properly prepared, the compounds of interest of this invention have a high stability, not dissociating even in the presence of excess hydroxide ions, usually found in hard water. In other cases, the compounds of interest of this invention also do not dissociate in the presence of other organic compounds widely distributed in waters requiring treatment due to the natural presence of a large diversity of organic species or products resulting from their decomposition. Thus, they have a much higher stability than currently marketed compositions, which are based on the simple interaction between a copper salt and an alkanolamine through ionic bonds, and may decompose as a result of interactions with other organic species commonly present in the waters to be treated.

In addition to the greater inherent stability of these structures, amino acid chelates and copper proteinates have been known for decades and are mostly used as copper and animal de-supplementation forms. Thus, they are characterized as products much safer than the alternatives currently available in the market.

Hereafter, copper chelates and proteinates will be mentioned in the text only by the term chelate for ease of reading, without detracting from the reader's understanding. However, when necessary, the species will be individually named.

The copper chelates of this invention may be administered in solid form or as aqueous solutions or suspensions. When the compounds are administered as aqueous solutions or suspensions, other components may be introduced into the formulation so that formulations with higher copper concentrations are obtained. If this is not of interest, algicidal compositions can be directly prepared by dissolving copper chelates or proteinates in water and using them exclusively as simple aqueous solutions. When introduction of an auxiliary component is desired, they are preferably selected from nitrogenous compounds and more preferably from ammonium salts and nitrogenous organic compounds. More particularly, the inventive auxiliary components are preferably selected from ammonium hydroxide or alkanolamines. However, it is important to note that these auxiliary components are not determinant for the activity and stability of copper chelates during their use as agents to kill or control the growth of unwanted algae and aquatic plants in water reservoirs.

The amounts of auxiliary components used depend on the concentration of copper to be solved according to the component. Such compositions may be prepared by simply mixing the copper chelate of interest with the auxiliary component or mixtures thereof, using solvent water in concentrations ranging from 1.5: 1 to 4: 1 w: w relative to the elemental copper quantity and, more preferably, they range from 2: 1 to 3: 1 w: w relative to the amount of elemental copper. The mixtures can be prepared efficiently at room temperature, but if desired, it is possible to heat at moderate temperatures ranging from 40-70 ° C without any harm in obtaining the final formulation. When ammonium hydroxide is used as an auxiliary component, its use is preferably in the form of a water-saturated aqueous solution which has ammonia concentrations ranging from 27-35%, in which case the addition of co-solvent water is not required if desired. . Solutions containing copper chelate may be obtained at concentrations of copper ranging from 3-10% and more preferably are obtained at concentrations ranging from 6-8.5%, depending on the auxiliary component employed.

The pH values obtained for the solutions containing copper chelate of interest in solution are also suitable for use as algicidal agents for the control of aquatic plants. Thus, when copper chelates are dissolved directly in water without incorporation of other components, solutions are obtained which have pH values ranging from 6.5-8.5 and, preferably, pH values ranging from 7.0-8, 0 In other cases, when auxiliary components are used, solutions are obtained which have pH values ranging from 8.0-11.5 and preferably from 8.1-10.5. These pH values do not correspond to the highest pH values observed for aqueous solutions of auxiliary components in the absence of copper chelates. This demonstrates that the metal valence orbitals that are not coordinated with amino acid carboxyl and amine groups are coordinating with the free electrons of the auxiliary component nitrogen groups, reducing the pH values observed for these solutions.

However, as the copper concentration required for water treatment is significantly low, and ranges from 0.1 to 20ppm of elemental copper, copper chelate can be prepared as a solution using only water as a solvent. For example, when a copper chelate is prepared using glycine as amino acid, resulting in copper bis (glycinate) chelate, solutions ranging from 0.5-1.5 wt% copper may be obtained and, preferably, solutions containing 0.7-1.2% w: w copper, depending on how chelate is prepared. When chelate is prepared with glutamic acid or monosodium glutamate, copper concentrations of about 6-7% may be obtained depending on the conditions in which the product is prepared. In this case, chelate is preferably prepared in the presence of ammonium ions so that its water solubility is higher. In other cases, copper chelate with glutamic acid may be prepared from glutamatomonosodium if it is of interest to the manufacturers.

As mentioned earlier, copper-amino acid chelates have high water solubility and are often soluble even under severe alkalinity conditions. Nominal water hardness varies with the concentration of alkali metals in solution and are considered soft for water containing 0-20mg Ca / L, moderately soft for concentrations ranging from 20-40mg Ca / L, moderately hard for concentrations ranging from 60-80mg Ca / L, hard for concentrations ranging from 80-120 mg Ca / L, and many for concentrations greater than 120 mg Ca / L. For example, copper bis (glycinate) or copper bis- (L-glutamate) chelate is soluble in its use as an algaecide, even when water is considered to be hard or very hard. Thus, when 2.5 ml or 5.0 ml of a solution containing 65 mg copper as copper bis (glycinate) are added to solutions containing 1 gCa / L or 100 mg Ca / L as calcium hydroxide, In order to obtain final solutions with copper contractions ranging from 0.15-0.35mg copper / L which is the usual concentration of copper as a water treatment algicide, precipitate formation is not observed in any case, even after several rest days and light exposure. Similar results are observed when decene bis (glycinate) is introduced into saturated magnesium solutions in the form of magnesium hydroxide.

Thus, copper chelates may be stored in their solid form, or in the form of simple aqueous solutions or prepared by the addition of other components, and previously diluted for use, to copper concentrations that depend on the water reservoirs to be treated to kill or control the water. algae growth other undesirable aquatic plants. The following are examples of how to obtain the copper chelates and compositions of interest of this invention. Similar results are seen for copper parabis- (L-glutamate) and copper bis- (aspartate).

EXAMPLE 1

24 g of glycine was dissolved in 50 ml of an aqueous solution containing 12.8 g of sodium hydroxide. Next, 40 g of copper pentahydrate sulfate were added. The mixture was stirred for 30 minutes at room temperature until no further solids formed. Water was removed under reduced pressure to obtain a light blue crystalline solid which was characterized as copper oxide (glycinate). Analysis shows an elemental copper content of 17.5% w: w. Thereafter, a water treatment solution was prepared by adding 65 g of this solid in water to obtain 1 liter of a copper bis (glycinate) solution. Solution analysis showed an elemental copper concentration of 1.14 wt% and a pH of 7.8.

EXAMPLE 2

24 g of glycine was dissolved in 63 g of a ammonium hydroxide solution containing 33% ammonia. Next 40 g of copper pentahydrate desulfate were added. The mixture was stirred for 30 minutes at room temperature. The resulting solution was crystalline dark blue in color and had no suspended or deposited solids at the bottom of the flask. The product was characterized as copper bis (glycinate) dissolved in water and the solution had an elemental copper content of 8.9% w: w and a pH value of 10.2.

EXAMPLE 3

12.8 g of sodium hydroxide was dissolved in 90 g of an ammonium hydroxide solution containing 33% ammonia. Next, 24 g glycine and 40 g copper pentahydrate were added. The mixture was kept under stirring for 5 minutes at room temperature. The resulting solution is dark blue crystalline and had no solids suspended or deposited at the bottom of the flask. The product was characterized as copper bis (glycinate) dissolved in water and the solution had an elemental copper content of 7.4% w / w and a pH value of 11.35.

EXAMPLE 4

30 g of a 40% w: w solution of a collagen protein hydrolyzate previously obtained by enzymatic hydrolysis was combined with 50 g of an ammonium hydroxide solution containing 33% ammonia. Thereafter, 20 g of pentahydrate copper sulfate was added. The mixture was kept under stirring for 30 minutes at room temperature. The resulting solution is dark blue crystalline and had no solids suspended or deposited at the bottom of the flask. The product was characterized as a copper proteinate dissolved in water and the solution had an elemental copper content of 4.4% w / w and a pH value of 10.5.EXAMPLE 5

24 g of glycine was dissolved in 63 g of an aqueous solution containing 20 g of monoethanolamine. Next 40 g of copper pentahydrate desulfate were added. The mixture was stirred for 30 minutes at room temperature. The resulting solution was crystalline dark blue in color and had no suspended or deposited solids at the bottom of the flask. The product was characterized as copper bis (glycinate) dissolved in water and the solution had an elemental copper content of 7.9% w: w and a pH value of 10.5.

EXAMPLE 6

2 kg of sodium glutamate monohydrate was added to 2 kg of 17.9% (w: w) ammonium hydroxide in aqueous solution. The mixture was kept under stirring for 10 minutes when 1.33 kg of copper sulphate pentahydrate was added. Stirring was continued for 30 minutes until solids were no longer observed. The product was characterized as tetraammonium copper bis (L-glutamate) and had an elemental copper content of 6.3% w: w and a pH value of 9.8.

EXAMPLE 7

2 kg of sodium glutamate monohydrate was added to 1520 kg of 17.9% (w: w) ammonium hydroxide in aqueous solution diluted with 700ml of water. The mixture was stirred for 10 minutes when 1.33 kg of copper sulphate pentahydrate was added. Stirring was continued for 30 minutes until the presence of solids was no longer observed. The product was characterized as cobretriamoniacal bis (L-glutamate) and had an elemental copper content of 6.0% w / w and a pH value of 9.3.

EXAMPLE 8

1.57 kg L-aspartic acid was added to 1520 kg 17.9% (w: w) deammonium hydroxide in aqueous solution diluted with 700 ml water. The mixture was kept under stirring for 10 minutes when 1.33 kg of copper sulphate pentahydrate was added. Stirring was continued for 30 minutes until no further solids were observed. The product was characterized as cobretriamoniacal bis (aspartate) and had an elemental copper content of 6.0% w: w and a pH value of 9.2.

EXAMPLE 9

Stability test: 825 mg of the solution prepared according to Example 2 was dissolved in 1 liter of water. Then 2.5 ml and 5.0 ml of this solution were dissolved in previously prepared solutions containing 1 g and 0.1 g Ca / L as calcium hydroxide. The solutions were kept under exposure to light for 5 days. There was no appearance of suspended precipitates or precipitate deposits at the bottom of the vial after this period.

Claims (14)

1.) - "COPPER ALGICIDE COMPOSITIONS", characterized in that it comprises elemental copper in the form of a copper chelate or proteinate prepared from a source of copper and protein free or hydrolyzed amino acids. 2.) - "COPPER ALGICIDE COMPOSITIONS", characterized by comprising a molecule characterized by the following molecular structure: <formula> formula see original document page 19 </formula> Where: R = side chain of a naturally occurring free amino acid and, more preferably, side chains representing the ligands as aspartic acid or L-glutamic acid.χ = range from 0 to 6. 3.) - "COPPER ALGICIDE COMPOSITIONS" according to claim 1, characterized by selected amino acids delivered glycine, lysine, alanine, phenylalanine, leucine, isoleucine, proline, hydroxyproline, arginine, methionine, aspartic acid, L-glutamic acid, valine threonine, isotreonine, histidine, tryptophan, serine and glutamine and more preferably L-glutamic acid, aspartic acid or glycine. 4.) - "COPPER ALGICIDE COMPOSITIONS" according to claim 1, characterized by protein hydrolysates selected from bovine collagen, soybean, wheat, keratin hydrolysates and, more preferably, bovine collagen hydrolysates. 5.) - "COPPER ALGICIDE COMPOSITIONS" according to claim 1, characterized by selected copper sources from metallic copper, copper oxide (ll), copper sulfate (ll), copper chloride (ll), copper phosphate ( 11), copper hydroxide (11), copper carbonate (11), and more preferably copper sulfate (11), copper carbonate (11) or hydrated or anhydrous mixtures thereof. 6.) - "COPPER ALGICIDE COMPOSITIONS" according to claim 1, characterized in that copper chelates or proteinates have a copper to ligand molar ratio ranging from 1: 1 to 1: 3 and preferably a molar ratio equal to 1: 2. 7.) - "COPPER ALGICIDE COMPOSITIONS" according to claim 1, characterized by compositions in the form of aqueous solutions comprising selected auxiliary components in nitrogen compounds between ammonium hydroxides and salts, preferably ammonium hydroxide, ammonium chloride, ammonium carbonate ammonium acetate, ammonium formate, guanidine and their salts, alkanolamines, aliphatic amines, aromatic amines and amides or mixtures thereof and more preferably ammonium hydroxide. 8. "COPPER ALGICIDE COMPOSITIONS" according to claim 7, characterized by alkanolamines selected from methoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, diethylethanolamine, diisopropanolamine, methyldiethanolamine and, preferably, monoethanolamine, triethanolamine or mixtures thereof. 9.) - "COPPER ALGICIDE COMPOSITIONS" according to claim 7, characterized by compositions comprising copper bis- (L-glutamate) and ammonium hydroxide in the form of an aqueous solution. 10.) - "COPPER ALGICIDE COMPOSITIONS" according to claim 7, characterized by compositions comprising copper bis- (aspartate) and ammonium hydroxide in the form of an aqueous solution. 11.) - "COPPER ALGICIDE COMPOSITIONS" according to claims 9 and 10, characterized by compositions having a molar relationship between copper and ammonia ranging from 1: 1 to 1:10 and preferably ranging from 1: 2 to 1 : 8 and more preferably ranging from 1: 3 to 1: 6. 12.) - "COPPER ALGICIDE COMPOSITIONS" according to claim 7, characterized by the addition of auxiliary components in relation to the amount of elemental copper ranging from 1: 1 to 4: 1p: b and more preferably from 2: 1. at 3: 1 p: p, respectively. 13.) - "COPPER ALGICIDE COMPOSITIONS" according to claim 7, characterized by aqueous compositions having elemental copper concentrations ranging from 3-12% w: w and most preferably ranging from 5-9% w: p. 14) - "COPPER ALGICIDE COMPOSITIONS" according to claims 1 to 13, characterized in that they are used as an algicide in the solid form or in the form of an aqueous solution for the treatment of natural water reservoirs or not to kill or control the growth of algae and other unwanted plants.