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    • 专利摘要:
    METHOD OF DISSOLVING AND / OR INHIBITING THE CRUST DEPOSITION ON A SURFACE OF A SYSTEM A method of dissolving and / or inhibiting the crust deposition on a system surface comprises the step of bringing the system surface into contact with a composition. The composition can comprise from about 3 to about 15 parts by weight of a chelating component. The chelating component is selected from the group of MGDA, NTA, HEDTA, GLDA, EDTA, DTPA and mixtures of these. The composition may further comprise from about 3 to about 15 parts by weight of an acidic component, which is different than the chelating component. The composition can still comprise at least about 60 parts by weight of water. Each of the ranges of parts by weight above are based on 100 parts by weight of the composition. The composition may further comprise a surfactant component and / or a corrosion inhibitor.
    公开号:BR112013026490B1
    申请号:R112013026490-0
    申请日:2012-04-13
    公开日:2020-11-17
    发明作者:Kenneth L. Zack；Joseph P. Borst；David DuRocher；David E. Przybyla；Victor Leung；Gunter Decker
    申请人:Basf Se；
    IPC主号:
    专利说明:

    CROSS REFERENCE WITH RELATED REQUESTS
    [01] This application claims the benefit of US Conditional Patent Application No. 61 / 475,531, filed on April 14, 2011 and US Series Conditional Patent Application No. 61 / 494,132, filed on June 7, 2011, both which are incorporated here in their entirety. FIELD OF THE INVENTION
    [02] The present invention, in general, concerns a method of dissolving and / or inhibiting the crust deposition on a system surface by applying a composition to the system surface, with the composition comprising a chelator component , an acidic and water component and optionally, a surfactant component and / or a corrosion inhibitor. DESCRIPTION OF RELATED TECHNIQUE
    [03] During many industrial processes, such as those using heat exchangers, this is often a crust formation. The progressive formation of crust inhibits the transfer of heat, flow and water, etc. In the process and requires expensive, labor-intensive and time-consuming removal practices. Such practices can result in increased health and safety objectives. In addition, such practices result in considerable downtime required to successfully remove the crust, which leads to losses in productivity and profit.
    [04] Some scab removal methods include on-site cleaning methods, such as those that rely on pH fluctuations / inversions provided by using acidic solutions followed by basic solutions. However, such solutions are very caustic when they include high amounts of acids and bases in order to attack and remove the crust. In addition, some methods also use components that are harmful to the environment.
    [05] As such, there remains an opportunity to provide improved methods for crusting systems. An opportunity also remains to provide improved scale removal compositions from systems. SUMMARY OF THE INVENTION AND ADVANTAGES
    [06] The objective invention provides a method of dissolving and / or inhibiting the deposition of crust on a surface of a system. The method comprises the step of bringing the system's surface into contact with a composition. In certain embodiments, the composition comprises from about 3 to about 15 parts by weight of a chelator component. The chelating component is selected from the group of methylglycine-NN-diacetic acid (MGDA) and / or an alkaline salt thereof, nitriloacetic acid (NTA) and / or an alkaline salt thereof, hydroxyethylethylenediamine triacetic acid (HEDTA) and / or an alkaline salt thereof , N, N-bis (carboxymethyl) -L-glutamate (GLDA) and / or an alkaline salt thereof, ethylene diaminetetraacetic acid (EDTA) and / or an alkaline salt thereof, diethylene triaminepentaacetic acid (DTPA) and / or an alkaline salt thereof and mixtures of these. The composition further comprises from about 3 to about 15 parts by weight of an acidic component, which is different than the chelating component. The composition further comprises at least about 60 parts by weight of water. The composition can still comprise a surfactant component. The composition may further comprise a corrosion inhibitor. Each of the ranges of the parts by weight are based on 100 parts by weight of the composition. Other embodiments of the composition are also provided.
    [07] The present invention, in general, provides an excellent method and removes crust from the system. The composition had excellent crusting properties and is environmentally friendly. The composition is also easier to handle and use than other conventional compositions. DETAILED DESCRIPTION OF THE INVENTION
    [08] The present invention provides a method of dissolving and / or inhibiting the deposition of crust on a surface of a system. Typically, the method is at least useful for dissolving crust on the surface of the system and can also be useful for inhibiting the redeposition of the crust on the surface of the system, if such a problem arises. The crust can also be referred to in the art as soiling.
    [09] The system's surface is typically formed of a metal or an alloy, such as iron, steel, aluminum, chrome, copper or a combination of these. A specific example of a surface is one formed from a galvanized metal, such as galvanized metal, such as galvanized steel. The present invention is especially useful for use with such surfaces. It should be estimated that the surface can also be formed from other materials, such as a composite, rubber, plastic, ceramic, etc. The surface can be an internal or external surface of the system. Examples of internal surfaces include those seen in pipelines, boilers, chemical plants or the like. Specific examples of internal surfaces include rubber-lined containers, for example, rubber-lined storage tanks. Examples of external surfaces include those seen on evaporators, conveyors, manufacturing plants, homes or the like.
    [10] Typically, the system is one in which the formation of the crust is problematic. As such, the system can be of various types, such as a heat transfer system, a filtration system, an evaporation system, etc. Additional examples of surfaces / systems include, but are not limited to, turbines, ship hulls, solar panels, reverse osmosis membranes, heating elements, reactors, oil reservoirs, water wells, geothermal wells, gas wells and oil wells. The system can be in an industrial, commercial or residential setting.
    [11] The crust can be formed of up to several components, depending on the type of system. For example, a heat transfer system may include scabs typically encountered with the use of hard water, whereas an evaporation system may include reducing the scab of the product being dried, for example, a fertilizer. Examples of crust include crystals of solid salts, oxides and hydroxides from aqueous solutions (e.g., calcium carbonate and calcium sulfate), corrosion / rust, beerstone, milkstone, vegetable stone, phosphates, lime, silicates, etc. A specific example of a crust is calcium oxalate, which can be found in several examples, such as in paper mills or brewing. Other types of crust may be those that are found during mining, such as crust that may appear during phosphate mining.
    [12] In one embodiment, the crust includes a combination of components, including ferrous phosphate, potassium fluorosilicate, potassium fluoride and silica potassium hexafluorosilicate. The elements in the crust may include C, O, P, Si, S, K and Fe. The crust may include smaller amounts of F, Mg, Al, Na, Ca and Ti. It should be estimated, as described above, that the crust can be made of several components. In addition, although the system may be the same day to day, the crust on the system's surface may change over time. For example, fluctuations in the materials used in the system can affect the quantity and distribution of components that form the crust.
    [13] The method of the present invention comprises the step of bringing the system's surface into contact with a composition. The composition must be brought into contact with the surface by various methods, such as by applying the composition to the surface, for example, by immersing the surface in the composition, spraying the composition on the surface, rolling the composition on the surface, etc. Various application mechanisms understood in the art can be used, such as a spraying mechanism, an immersion tank, etc. It is efficient to apply the composition to the surface, such that it is directed primarily in the direction of the crust rather than on the surface that lacks crust. The composition can also be drained and / or passed on the surface, such as in a tube.
    [14] Typically, the surface does not need to be pre-treated, such as being mechanically cleaned by fragmentation, rubbing, etc., before putting the composition in contact with the surface. However, such pre-treatment steps can be used to expedite the removal of the crust from the system's surface. If the surface is an internal surface, such as those found in tubes, the crust can be removed by filling the system with the composition and, optionally, circulating the composition in the system, for example, by pumping. The surface can also be pre-washed, such as with water, in order to remove other residues before putting the composition in contact with the crust / surface.
    [15] The method may further comprise the stage of applying heat to the composition and / or the system. The step is useful for expediting the dissolution of the crust from the surface of the system. However, it must be estimated that the composition can also be placed in contact with the crust at room temperature. In general, increasing the temperature of the composition, directly or indirectly, will accelerate the rate at which the crust is dissolved by the composition once contacted. Heating can be carried out by various means known in the art. For example, the composition can be heated in the system by means of heating already present in the system. Optionally, a separate heat exchanger can be used to heat the composition.
    [16] In general, at least a portion, if not all, of the crust is removed from the surface of the system. Typically, the longer the composition is in contact with the surface, the greater the amount of crust removed from the surface. Removal can be increased by stirring the composition when in contact with the surface, such that the composition also physically removes the crust (for example, by cutting) in addition to chemically removing the crust. Stirring can be carried out by means of circulation as described above or by other means understood in the art.
    [17] The composition of the present invention comprises a chelator component. The chelating component can comprise one or more chelating agents skilled in the art. The chelating agent can also be referred to in the art as a complexing agent. In certain embodiments, the chelator component comprises methylglycine-N-N-diacetic acid (MGDA) and / or an alkaline salt thereof, more typically its alkaline salt, for example, methylglycine diacetate, trisodium salt (Nag-MGDA). MGDA is also commonly referred to in the art as methylglycine diacetate. It should be estimated that as described herein, the alkaline salt can include any alkali or alkaline earth metal and is not particularly limited.
    [18] In other embodiments, the chelator component comprises at least one of nitriloacetic acid (NTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), N, N-bis (carboxymethyl) -L-glutamate (GLDA), ethylene diaminetetraacetic acid (EDTA) , diethylenetriaminepentaacetic acid (DTPA) and / or an alkaline salt thereof from any of the proceeding chelating agents. It should be estimated that the chelating component may comprise a combination or mixture of two or more of the chelating agents described herein, for example, MGDA and GLDA. It should also be estimated that the acronyms used here, for example MGDA, can refer to the acid or salt form, for example, Nag-MGDA, of the chelating agent.
    [19] Typically, the chelating component is aqueous, such that the chelating component also includes water in addition to the chelating agent. In various embodiments, the chelating component is aqueous and such that the chelating agent, for example, MGDA, is present in the chelating component in amounts of about 35 to about 95, about 35 to about 85 or about from 35 to about 45 or about 40 parts by weight, each based on 100 parts by weight of the chelator component. It should be estimated that the chelating component can also be in the form of a powder or a gel, such that the chelating agent is the chelating component.
    [20] Non-limiting examples of suitable chelating components are commercially available from BASF Corporation of Florham Park, NJ, under the brand name TRILON®, such as TRILON® M, TRILON® A, TRILON® B, TRILON® C and TRILON® D Other non-limiting examples of suitable chelating components are commercially available from AkzoNobel of Chicago, IL under the brand name DISSOLVINE® GL, such as DIS SOL VINE® GL 47 S. Other non-limiting examples of suitable chelating components are described in US Patent No. ° 5,786,313 granted to Schneider et al. and in U.S. Patent Application Publication No. 2009/0105114 granted to Stolte et al., whose disclosures are incorporated herein by reference in their entirety to the extent that the disclosures do not conflict with the general scope of the present invention described here.
    [21] The chelator component is present in the composition in an amount of about 0.001 to about 15 parts by weight, about 0.01 to about 15, about 0.1 to about 15, about 1 to about about 15, about 3 to about 15, about 5 to about 12.5, about 7.5 to about 12.5, about 8.7 to about 14.5, about 5 or about 10 parts by weight, each based on 100 parts by weight of the composition. Typically, the amounts described here are substantiated on the assumption that the chelator component includes 100% assets, that is, 100% chelating agents. As such, if the chelator component is aqueous, the amount above can be adjusted accordingly to compensate for the% of assets in the dilution.
    [22] The chelator component is useful for inactivating hard minerals and / or removing metal ions from the crust. Typically, the chelating agent will combine with the hardness minerals and keep them in the solution, such that the hardness minerals cannot redeposit.
    [23] The composition still comprises an acidic component. Typically, the acidic component is selected from the group of an organic acid, an inorganic acid and a combination of these. Examples of suitable organic acids include straight or branched chain carboxylic acids that include, but are not limited to, lactic acid, acetic acid, formic acid, ascorbic acid, oxalic acid, hydroximaleic acid, methanesulfonic acid, mandelic acid, glycolic acid, salicylic acid, pyranosidyl acid, such as glucuronic or galacturonic acid, citric acid, tartaric acid, pamoic acid, alginic acid, gentisic acid, lactobionic acid, succinic acid, maleic and acrylic acid polymers, acid and copolymers thereof. Examples of suitable inorganic acids include hydrochloric acid, hypochlorous and chlorous acid, sulfuric acid, sulfurous acid, nitric acid, phosphoric acid, amidosulfonic / sulfamic acid and phosphorous acid.
    [24] In certain embodiments, the acid component comprises an organic sulfonic acid, such as an alkyl sulfonic acid, for example, methanesulfonic acid (MSA). Methanesulfonic acid is a strong organic acid that is completely non-oxidizing and thermally stable and forms highly soluble salts. In other embodiments, the acid component comprises citric acid. In other embodiments, the acid component comprises phosphoric acid. It should be estimated that the acid component can include two or more different acids, such as methanesulfonic acid and phosphoric acid. If two or more acids are included, they can be for several reasons with respect to each other.
    [25] Non-limiting examples of suitable acid components are commercially available from BASF Corporation, under the brand name LUTROPUR®, such as LUTROPUR® MSA. In certain embodiments, the MSA is one that is formed by an oxidation process in air, rather than from a chlorooxidation process. As such, MSA has less metal content, such as less than 1 mg / kg and little to no chlorine compounds, which are, in general, corrosive. Other non-limiting examples of suitable acid components are described in U.S. Patent No. 6,531,629 issued to Eiermann et al. And in U. S. Patent Application Publication No. 2008/0161591 granted to Richards, whose disclosures are incorporated herein by reference in their entirety to the extent that the disclosures do not conflict with the general scope of the present invention described here.
    [26] In various embodiments, the acid component is aqueous and such that the acid, for example, MSA, is present in the acid component in amounts of about 35 to about 95, about 50 to about 85 or from about 65 to about 85 or about 70 parts by weight, each based on 100 parts by weight of the acid component.
    [27] The acidic component is present in a composition in an amount of about 0.01 to about 15, about 0.1 to about 15, about 1 to about 15, about 3 to about 15 , about 5 to about 12.5, about 7.5 to about 12.5, about 8.7 to about 14.5, about 5, or about 10, parts by weight, each based on 100 parts by weight of the composition. Typically, the amounts described herein are based on the assumption that the acid component includes 100% active, that is, 100% acid. Like, if the acid component is aqueous, the above amounts can be adjusted accordingly to compensate for the% of the dilution of the assets.
    [28] In a particular embodiment, the chelator component comprises MGDA and the acid component comprises MSA. Without being bound or limited by any particular theory, it is believed that a synergy exists between MGDA and MSA. Specifically, it has been recovered that the combination of MGDA (e.g. Nas-MGDA) and MSA has a surprising improvement in crust dissolution than the component alone. This unique property is believed to be a result of the ability of MSA to dissolve insoluble metal complexes, releasing metal ions where they are captured by the soluble salts of MGDA formation. MGDA has a greater affinity for soluble metal ions than MSA thereby freezing the MSA to dissolve the additional insoluble complexes until both molecules become saturated.
    [29] In certain embodiments, the acid component (“A”) and the chelator component (“C”) are used in a composition in a molar ratio (C: A) of about 6: 1 to about 1 : 6, about 5: 1 to about 1: 5, about 4: 1 to about 1: 4, about 3: 1 to about 1: 3, about 2: 1 to about 1: 2 , about 6: 1 to about 1: 1, about 5: 1 to about 1: 1, about 4: 1 to about 1: 1, about 3: 1 to about 1: 1, about from 2: 1 to about 1: 1, or about 1: 1.
    [30] Generally, the molar ratio will depend on the number of reactive groups in the chelator component. For example, MGDA has three carboxyl groups that can react with the acid component (whereas GLDA has four). Like, one, two or all three of these groups can be reacted with the acid component, for example MSA. MSA also protons the amino group of MGDA and it is believed that this amino group is preferred in the carboxyl groups, i.e., it is preferably protonated before any of the carboxyl groups. An excess of component will generally provide only an unreacted amount of that component in the cleaning composition, such as free MSA. Such excess can be used to change the pH of the composition and / or to grant additional properties to the composition. It is believed that in certain embodiments, using a molar excess of the acid component can cause undesirable precipitation of the chelator component (in a totally neutral form, for example crystals can form and adjust over time). As such, the molar ratio of these two components can be adjusted to account for the possible degree of reaction between the two.
    [31] The composition still comprises water. The water can be of various types. In certain embodiments, the water is demineralized. Water is present in a composition in various amounts, depending on the embodiment. Water can be added to the composition as a separate component. However, it will be appreciated that some of the water can also be provided by one of the other components, such as the chelating component and / or the acid component when aqueous.
    [32] Typically, water is present in a composition in an amount of at least about 60, at least about 65, at least about 70, at least about 75, at least about 80, at least about 85, at least about 90, or at least about 95, parts by weight, each based on 100 parts by weight of the composition. In certain embodiments, water is present in the remaining amount of parts by weight of the composition including the chelator component, the acid component and optionally, the surfactant and / or corrosion inhibiting components. In the additional embodiments, the compositions are substantially free to completely free of other conventional components, such as defoamers. The compositions of the present invention generally have excellent dissolution and / or inhibiting properties without requiring additional components.
    [33] Optionally, the composition can still comprise a surfactant component. It is believed that in certain embodiments, including the surfactant component, it is useful for dissolving certain types of crusts, such as rust. If used, the surfactant component is typically selected from the group of nonionic surfactants, anionic surfactants and ionic surfactants. It will be appreciated that other types of surfactants can also be used. Examples of suitable surfactants, for the purposes of the present invention, are described in U.S. 2007/0034606 issued to Dietsche et al., The disclosure of which is incorporated herein by reference in its entirety to the point that does not conflict with the general scope of the present invention.
    [34] In certain embodiments using the surfactant component, the surfactant component comprises a non-ionic surfactant. Non-limiting examples of suitable surfactant components are commercially available from BASF Corporation, under the trade name LUTENSOL®, such as LUTENSOL® XP 80, LUTENSOL® TO 8, LUTENSOL® GD 70; under the trade name TETRONIC®, such as TETRONIC® 304; under the trade name PLURAFAC®, such as PLURAFAC® LF 711; as well as under the trade name LUTENSIT®, such as LUTENSIT® AS 2230. It will be appreciated that the surfactant component may include a combination of two or more different surfactants, for example, an ionic and a nonionic surfactant.
    [35] If used, the surfactant component is present in a composition in an amount of about 0.01 to about 15, about 0.1 to about 15, about 1 to about 15 parts by weight, about from 3 to about 15, about 5 to about 12.5, about 7.5 to about 12.5, about 8.7 to about 14.5, about 5 parts by weight, or about 10 parts by weight, each based on 100 parts by weight of the composition. Typically, the amounts described in this are based on the assumption that the surfactant component includes 100% active, that is, 100% surfactant. As such, if the surfactant component is aqueous, the amounts above can be adjusted accordingly to compensate for the% of the dilution of the assets.
    [36] Optionally, the composition can still comprise a corrosion inhibitor. It is believed that in certain embodiments, including the corrosion inhibitor, it is useful to prevent the redeposition of certain types of crusts, such as rust. Various types of corrosion inhibitors can be used. In certain embodiments, the corrosion inhibitor is a propargyl alcohol alkoxylate.
    [37] Non-limiting examples of suitable corrosion inhibitors are commercially available from BASF Corporation, under the trade name KORANTIN®, such as KORANTIN® PP and KORANTIN® PM. It will be appreciated that the composition can include a combination of two or more different corrosion inhibitors.
    [38] If used, the corrosion inhibitor is present in a composition in an amount of about 0.01 to about 5, about 0.1 to about 5, about 0.5 to about 1.5 , or about 1, parts by weight, each based on 100 parts by weight of the composition. Typically, the amounts described herein are based on the assumption that the corrosion inhibitor includes 100% of assets, that is, 100% of the inhibitor. As such, if the corrosion inhibitor is aqueous, the amounts above can be adjusted accordingly to compensate for the% of the dilution of the assets.
    [39] The composition typically has a pH of about 0 to about 9, about 3 to about 9, about 5 to about 7, or about 6. The pH of the composition is given by the type and quantity of the components used to form the composition. Suitable buffer systems, for example, a phosphate buffer or a citrate buffer, can also be for pH stabilization.
    [40] The few specific embodiments of the composition of the present invention are as follows, with parts by weight generally based on the assumption of 100% of the assets for each of the components and with each of the components as exemplified and described above: 1 ) about 3 parts MGDA, about 3 parts MSA, remaining water; 2) about 3 parts MGDA, about 3 parts citric acid, remaining water; 3) about 8.7 parts MGDA, about 3 parts MSA, remaining water; 4) about 8.7 parts MGDA, about 5 parts MSA, remaining water; 5) about 8.7 parts MGDA, about 3 parts citric acid, remaining water; 6) about 8.7 parts MGDA, about 5 parts citric acid, remaining water; 7) about 3 parts MGDA, about 8.7 parts MSA, remaining water; 8) about 5 parts MGDA, about 8.7 parts MSA, remaining water; 9) about 5 parts MGDA, about 5 parts MSA, remaining water, optionally, with about 5 parts of surfactant and / or optionally, with about 0.5 parts of the corrosion inhibitor; 10) about 10 parts MGDA, about 10 parts MSA, remaining water, optionally, with about 10 parts of surfactant and / or about 1 part of the corrosion inhibitor; 11) about 10 parts MGDA, about 10 parts of a combination of MSA and phosphoric acid, about 10 parts of surfactant, about 1 part of the corrosion inhibitor, remaining water; 12) from about 0.1 to about 5 mmol of MGDA, from about 100 to about 200 mmol of MSA, remaining water; and 13) from about 0.1 to about 5 mmol of MGDA, from about 100 to about 2000 mmol of MSA, remaining water.
    [41] In the specific embodiments above, it is believed that 9) through 11) are especially useful for dissolving corrosion / rust. It is believed that 1) to 8) are especially useful for dissolving the scabs found in fertilizer evaporation systems. Still in the embodiments of 11), the combination of MSA and phosphoric acid can vary such that there is a greater amount of MSA relative to phosphoric acid, such that there is about equal parts of each, or such that there is a smaller amount of MSA relative to phosphoric acid. In certain applications, use of MSA in that phosphoric acid may be preferred as certain surfaces may discolor or tarnish with the use of phosphoric acid. Typically, using the corrosion inhibitor which is useful for providing a clearer and cleaner search surface, if desired. It is believed that 12) is especially useful for dissolving and / or inhibiting the formation of carbonate crust, such as calcium carbonate. It will be appreciated that the present invention is not limited to the specific embodiments numbered above.
    [42] The following examples, illustrating the method and compositions of the present invention, are intended to illustrate and not to limit the invention. EXAMPLES
    [43] The compositions are prepared and tested in triplicate. The compositions are prepared by mixing the components of the composition in a bottle. A sample of the crust is weighed to determine an initial weight. The crust is representative of the crust found during the collection and manufacture of the fertilizer and generally comprises calcium carbonate (CaCCh) and can also include one or more additional compounds as well. The crust samples are relatively of equal size and shape for each test. The sample is then placed in the bottle such that the crust is in contact with the composition. The flask is then heated in an oven for four hours at a temperature of 80 ° C. The sample is then removed, rinsed with water, dried at 90 ° C and weighed again to determine a final weight. The difference in weight indicates the amount of dissolved crust. Several compositions are illustrated in the tables below. All samples are based on parts by weight, in grams, unless otherwise stated. A symbol means the data and not tested or available. TABLE 1

    [44] Chelation 1 is MGDA, commercially available from BASF Corporation.
    [45] Acid 1 is MSA, commercially available from BASF Corporation.
    [46] The amounts above and in tables 2 to 5 below are based on the percentages of active weight of the components, such as, the amount of water includes water added to the composition as well as water provided by other components of the composition. For example, Chelation 1 includes about 40 percent of assets (MGDA) and 60 percent of water, just as a portion of the water shown above is provided by Chelation 1. Acid 1 includes 70 percent of assets (MSA) and 30 percent water.
    [47] As shown in Table 1 above, the combination of MGDA and MSA removes larger crust than just the component.
    [48] Additional testing of other acidic components is performed. The results are illustrated below. As illustrated below, other acids also present synergies with MGDA. TABLE 2


    [49] Acid 2 is H2SO4.
    [50] Acid 3 is HCl.
    [51] Acid 4 is citric acid.
    [52] Additional testing of MSA and MGDA is performed. The amount of MGDA is increased from 8.7 to 14.5 to vary the pH of the composition. In another way, a pH is selected and MGDA is added until the pH is reached. Water forms the remainder of each of the compositions. All illustrated below, crust removal peaks at a pH of 6. TABLE 3

    [53] Additional testing of other chelation components is performed. The results are illustrated below. As illustrated below, other chelating agents also present synergies with MSA. The chelating agents in Table 4 below are compared on an equivalent molar basis. The pH is adjusted with NaOH (aq). TABLE 4

    [54] Chelation 2 is EDTA, commercially available from BASF Corporation.
    [55] Chelation 3 is DTPA, commercially available from BASF Corporation.
    [56] Chelation 4 is HEDTA, commercially available from BASF Corporation.
    [57] Chelation 5 is GLDA, commercially available from AkzoNobel. Chelation 5 includes 47 percent of assets (GLDA) and 53 percent of water.
    [58] Chelation 6 is NTA, commercially available from BASF Corporation.
    [59] Additional testing of another pH is performed. The amount of MGDA and MSA is maintained and the pH is varied by adding NaOH. The other way said, the pH is increased with the addition of NaOH. As illustrated below, the crust removal peaks at the mean pH values. In addition, it is believed that crust removal is minimally dependent on pH within the ranges illustrated below. TABLE 5

    [60] The additional test is performed similar to the one illustrated above. Also in the compositions, surfactants and corrosion inhibitors are used. Corrosion / rust removal is tested. The compositions are illustrated in tables 6 to 9 below. TABLE 6

    [61] Acid 5 is 85% by weight of phosphoric acid in water.
    [62] Surfactant 1 is a branched non-ionic surfactant, specifically an alkyl polyethylene glycol ether having an ethoxylation degree of 8, commercially available from BASF Corporation.
    [63] Corrosion inhibitor 1 is 65-69% by weight of propargyl alcohol alkoxylate in water, commercially available from BASF Corporation.
    [64] Corrosion inhibitor 2 is propargyl alcohol alkoxylate, commercially available from BASF Corporation.
    [65] Examples 39 and 40 have excellent rust removal relative to Example 38 which requires a chelation component, with Example 40 providing a lighter underlying metal relative to Example 39. Example 41 removes rust as well, but tends to discolor the underlying metal. Other examples also provide a level of rust removal. The additional acid and surfactant components are tested, as illustrated in Table 7 below. TABLE 7

    [66] Acid 6 is formic acid.
    [67] Acid 7 is oxalic acid.
    [68] Acid 8 is sulfamic acid.
    [69] Surfactant 2 is a nonionic surfactant made from a saturated iso-Ci3 alcohol and having an ethoxylation degree of 8, commercially available from BASF Corporation.
    [70] Surfactant 3 is a nonionic surfactant, specifically an alkyl polyglycoside, commercially available from BASF Corporation.
    [71] Surfactant 4 is an ionic surfactant, specifically a sulfated ethoxylated fatty alcohol, commercially available from BASF Corporation.
    [72] Each of the compositions provides a level of rust removal. The ratios of the acidic components, as well as another surfactant, are tested, as illustrated in tables 8 and 9 below, with the compositions in Table 9 being the dilutions of those in Table 8. The removal of rust is observed over time. In Table 8, each of the compositions has 10% active chelating agent, 10% active acids and 10% active surfactants, if used. Table 9 includes half of an amount of the assets. Each of the compositions provides a level of rust removal. TABLE 8

    [73] Surfactant 5 is a low defoaming nonionic surfactant, commercially available from BASF Corporation. TABLE 9

    [74] Additional compositions are prepared by the crust removal test formed from calcium carbonate (CaCCb). The small Carrara marble tiles (ca. 3 cm x 1.5 cm x 0.8 cm, 1 xwxd), formed from limestone, are exanguinated with water and dried in an oven at 105 ° C for at least an hour. The individual stews are weighed and placed in numbered 2.5 oz. (73.93 ml) jars. A 2.0 Molar (19.2%) MSA stock solution is prepared with DI water. The stock solution is used to prepare the tested MSA solutions to which MGDA is added in concentrations of 0.1, 0.25, 0.5, 0.75, 1.0, 2.5 and 5.0 mol. That is to say: to 100 g of the 2.0 Molar MSA solution, X grams of MGDA are added to reach the desired level of millimoles MGDA and the water is added equal to 200 g. The 200 g solution is divided into 50 g aliquots for the test, in which a pre-weighed tile is added to each numbered jar, as was 50 g of the solution. The jars with loose lids are placed in an oven at 80 ° C for one hour. After one hour, the solutions are decanted and placed and the samples are everywhere rinsed with tap water. The samples are dried for one hour at 105 ° C, allowed to cool completely and weighed again to determine the weight loss of each tile. Table 10 below illustrates the average amount of crust dissolved from each of the compositions. TABLE 10

    [75] As shown in Table 10 above, the compositions have excellent dissolving properties, even at low concentrations, especially against calcium carbonate. Additional compositions are prepared by comparing MGDA and GLDA in removing the calcium carbonate scab. The compositions are prepared in the same manner as described above by the compositions in Table 10. TABLE 11

    [76] As shown in Table 11 above, the compositions have excellent dissolving properties, even at low concentrations, especially against calcium carbonate.
    [77] In tables 12 and 13 below, the stability test is illustrated by the additional examples. The molar ratio of the acid component (“A”) to the chelation component (“C”) is also illustrated. The example compositions are stored at -10 ° C for 16 hours. The compositions are removed and allowed to warm to 25 ° C for 8 hours and examined by crystal development. The compositions are then resumed by storage at -10 ° C and the cycle is repeated. The number of cycles completed before the development of the crystal occurs is recorded and indicated in the tables. TABLE 12
    TABLE 13

    [78] It will be understood that the appended claims are not limited to express and particular compounds, compositions or methods described in the detailed description, which may vary between forms of particular embodiments that differ within the scope of the appended claims. With respect to any of the Markush groups described here the particular characteristics or aspects of various embodiments, it will be appreciated that different, special and / or unexpected results can be obtained from each member of the respective Markush group independently of all other Markush members. Each member of a Markush group can be invoked individually or in combination and provides adequate support for specific embodiments within the scope of the appended claims.
    [79] It will also be understood that any ranges and sub-ranges invoked in describing various embodiments of the present invention independently and collectively diverge within the scope of the appended claims and are intended to describe and consider all ranges including total and / or fractional values in this , still being such values are not expressly written in this. A person skilled in the art will readily recognize that the enumerated bands and sub-bands sufficiently describe and enable various embodiments of the present invention and such bands and sub-bands can still be delineated into relevant halves, thirds, quarters, fifths and so on. Just as an example, a range "from 0.1 to 0.9" can be further delineated by a smaller third, that is, from 0.1 to 0.3, an average third, that is, from 0.4 to 0.6 and an upper third, that is, 0.7 to 0.9, which individually and collectively fall within the scope of the attached claims and can be invoked individually and / or collectively and provide adequate support for specific embodiments within the scope of the appended claims. In addition, with respect to the language that defines or modified a track, such as “at least,” “greater than,” “less than,” “no more than,” and others, it will be understood that such language includes the sub-bands and / or an upper or lower limit. As another example, a “at least 10” range inherently includes a sub-range of at least 10 to 35, the sub-range of at least 10 to 25, the sub-range from 25 to 35, and so on, and each sub-range can be invoked individually and / or collectively and provides adequate support for specific achievement forms within the scope of the attached claims. Finally, an individual number within a disclosed range can be invoked and provides adequate support for specific embodiments within the scope of the appended claims. For example, a “1 through 9” range includes several individual integers, such as 3, as well as individual numbers including a decimal point (or fraction), such as 4.1, that can be invoked and provide adequate support for specific embodiments within the scope of the appended claims. [80] The present invention has been described in this in an illustrative manner and it will be understood that the terminology that was used is intended to be in the nature of the words of the description rather than the limitation. Many modifications and variations of the present invention are possible in light of the above teachings. The present invention can be practiced in another way than as specifically described within the scope of the appended claims. The main purpose of all combinations of independent and dependent claims, both simple and multiply dependent, is expressly considered here.
    权利要求:
    Claims (4)
    [0001]
    1. Method of dissolving and / or inhibiting the deposition of crust on a surface of a system, where the crust comprises calcium carbonate, the surface of the system comprising a composite, a rubber, a plastic, and / or a ceramic, characterized by the fact that said method comprises the step of bringing the system's surface into contact with a composition having a pH of 5 to 7 and comprising: A) 3 to 15 parts by weight, based on 100 parts by weight of the composition , of a chelating component comprising methylglycine-NN-diacetic acid (MGDA) and / or an alkaline salt thereof, where MGDA is present in the chelating component in an amount of 35 to 95 parts by weight, based on 100 parts by weight of the component chelator; B) from 3 to 15 parts by weight, based on 100 parts by weight of the composition, of an acid component comprising methanesulfonic acid, in an amount of 35 to 95 parts by weight, based on 100 parts by weight of the acid component; and C) at least 60 parts by weight of water, based on 100 parts by weight of the composition; D) optionally, a surfactant component; E) optionally, a corrosion inhibitor, wherein the method further comprises a step of applying heat to the composition and / or the system.
    [0002]
    Method according to claim 1, characterized in that the surfactant component D) is present in an amount of 3 to 15 parts by weight based on 100 parts by weight of the composition and the surfactant component D) comprises a surfactant non-ionic.
    [0003]
    Method according to claim 1 or 2, characterized in that the composition additionally comprises a corrosion inhibitor E) present in an amount of 0.01 to 5 parts by weight, or 0.5 to 1.5 parts by weight, based on 100 parts by weight of the composition and the corrosion inhibitor E) comprises a propargyl alcohol alkoxylate.
    [0004]
    Method according to any one of the preceding claims, characterized in that the chelating component A) is present in an amount of 5 to 12.5 parts by weight, the acid component B) is present in an amount of 5 to 12.5 parts by weight, and the surfactant component D) is present in an amount of 5 to 12.5 parts by weight, each based on 100 parts by weight of the composition.
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    同族专利:
    公开号 | 公开日
    KR101947205B1|2019-02-12|
    AU2012242671A1|2013-11-14|
    RU2013150522A|2015-05-20|
    JP5992506B2|2016-09-14|
    EP2697171B1|2020-12-23|
    ZA201308447B|2015-07-29|
    CA2833150C|2020-10-06|
    BR112013026490A2|2016-12-27|
    JP2014518752A|2014-08-07|
    EP2697171A1|2014-02-19|
    AU2012242671B8|2017-01-19|
    TW201323604A|2013-06-16|
    WO2012142396A1|2012-10-18|
    CN103562144A|2014-02-05|
    ES2855180T3|2021-09-23|
    US20120260938A1|2012-10-18|
    CA2833150A1|2012-10-18|
    MY165223A|2018-03-13|
    KR20140022068A|2014-02-21|
    AU2012242671B2|2017-01-05|
    MX2013011856A|2014-01-31|
    US9382139B2|2016-07-05|
    TWI604045B|2017-11-01|
    AU2012242671A8|2017-01-19|
    MX349860B|2017-08-16|
    RU2604366C2|2016-12-10|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-07-23| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-03-10| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2020-07-07| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-11-03| B09X| Republication of the decision to grant [chapter 9.1.3 patent gazette]|
    2020-11-17| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/04/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    2022-02-08| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 10A ANUIDADE. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161475531P| true| 2011-04-14|2011-04-14|
    US61/475531|2011-04-14|
    US201161494132P| true| 2011-06-07|2011-06-07|
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    PCT/US2012/033496|WO2012142396A1|2011-04-14|2012-04-13|Method of dissolving and/or inhibiting the deposition of scale on a surface of a system|
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