TW201439009A - Multiple uses of amine salts for industrial water treatment - Google Patents

Abstract

A method for treating in an industrial water treatment system for at least two of metal corrosion inhibition, scale inhibition, suspended matter dispersion, biocide efficacy, or biofilm removal/biofilm dispersion is taught by the use of at least one compound which is a salt derived from a thioamine or an oxyamine and an acid.

Description

Multiple uses of amine salts for industrial water treatment Field of invention

The present invention relates generally to industrial water treatment (IWT) systems, which typically produce a number of different conditions that require disposal, such as inhibition, scale inhibition, suspension dispersion, microbial control, biofilm removal, and Biofilm dispersion.

Background of the invention

Water is used in the industry to transfer heat for circulating cooling water systems and to generate steam in the boiler. In commercial air conditioners, and even in home air conditioning systems, cooling water is widely used to perform efficient and safe operation in most major manufacturing processes. Moreover, refineries, steel mills, petrochemical plants, power plants, and paper mills all rely heavily on equipment or methods that require effective temperature control and typically use cooling water to reduce this temperature. These cooling water systems are therefore important for operations that maintain these heat transfer requirements within a variety of process systems.

The heat transfer process fluid can be used to transfer heat into the cooling water to circulate the cooling water system to control the temperature. When it occurs, the cooling water itself gets hot and must be cooled by evaporation or a secondary chiller system (the water flows through a Cooling zone or with exposure to refrigeration). The water lost in this process must be replaced by freshly supplied cold water (ie, makeup water). The replacement water contains dissolved minerals, suspended solids, residues, bacteria, and other impurities. As the water continues to circulate throughout the cooling water system, other contamination begins to accumulate. These inorganic contaminants, such as rust and corrosion products, can form deposits on the heat transfer surface and within the tubing. In addition, due to the growth of microorganisms, biofilms formed on the surface cause biological clogging. These deposits result in a reduction in heat and mass transfer. As a result, the temperature of the system will rise, the cooling equipment will be compromised and the plant will be shut down. It will be a very costly consequence.

Obviously, efficient cooling water management is indispensable for the operation of these plants. Cooling water is water that is primarily used in the industry to transfer heat within such systems. If not properly controlled, the cooling system can be reduced in various ways (such as loss of production, increased cost of cleaning, increased cost and use of protective chemicals, increased use of energy, increased maintenance costs, and reduced service life of the system and its components). Short) brought major difficulties to the plant.

Industrial Water Treatment (IWT) is used to control a variety of problems such as: scale inhibition of CaCO ₃ and CaSO ₄ ; corrosion inhibition of mild steel, copper, brass and other metals; inhibition of biological plugging; Inhibition/dispersion; cleaning/removal of biofilm and rust deposits; and the following safety issues: exposure to the person performing the work, and safety issues with the disposal of these agents in the environment. There is therefore a need for a simpler cost effective method that can handle these various issues.

Industrial water treatment must control corrosion, rust, and biological plugging Plug, suspended matter deposition, and microbial activity. These issues are interrelated and one issue cannot be completely isolated from other issues. For example, rust can occur more quickly in a corrosion system; microbial induced corrosion is a potentially serious problem in almost all cooling systems; and corrosion under deposits can cause rapid failure of other uncorrupted metals. .

Corrosion, rust, biological clogging, suspended solids deposition, and similar control of microbial activity occur in another area where the oil production industry occurs, where the water system is used for down-hole oil and gas extraction. in.

The science and practice of water treatment is an ongoing and developmental effort. Today, far more than in the past, as the population increases, the need for water reuse becomes important. In particular, the use of purified wastewater suitable for reuse in IWT systems is important for water conservation and is a significant consideration for the entire population and environment. Any method that reduces the use of water is therefore advantageous. A more efficient IWT system without these problems can be a way to reduce water use.

Many attempts have been made to address these various IWT needs. There are many suggestions in the literature; however, in a commercial large-scale environment, they have not been successful. The treatments applied to all aspects of these issues have been sold and used. Some of the techniques are as follows.

Lamb (U.S. Patent No. 3,291,683) teaches the use of alkoxy or alkylthio substituted alkylamines and their acid addition salts as biocides.

Walter (U.S. Patent 4,816,061) teaches the use of alkylthioalkylamines and their acid addition salts as biocides to control biological clogging in cooling towers.

Nalepa (U.S. Patent Application No. 20090178587) teaches 2-(mercaptothio)ethylamine as a biocide and biofilm dispersant (biodispersant).

Moir (WO 2005/014491) teaches ether amines as biocides for controlling sulfate reducing bacteria to prevent H ₂ S formation and to produce problems including iron sulfide deposits and corrosion present in industrial water systems Acid addition salt.

Wolf (U.S. Patent No. 3,524,719) teaches the use of oxygen as a steel corrosion inhibitor in a sulfur-containing salt solution when another amine compound (such as N,N"-hexachloro-terphenyl) bis(ethylenediamine) is used in combination. The use of amines and thiamines.

Gartner (U.S. Patent 6,260,561) teaches the use of aliphatic amines, including oxygenated amines, for cleaning pool deposits.

Relenyi (U.S. Patents 4,982,004 and 5,025,038) teaches the preparation of antimicrobial formulations of thiamine salts, but does not provide a discussion of such as rust or corrosion inhibitors. The multiplier utility is not described.

Fontana (U.S. Patent No. 6,183,649) teaches the use of the thiamine salt of a biofilm remover as part of a multi-component composition for treating a water circulatory system to control white rust (zinc corrosion). The multiplier utility is not reported.

2-Hydroxypropane-1,2,3-tricarboxylic acid and other hydroxycarboxylic acids are known in the water treatment industry as chelate compounds which dissolve or inhibit inorganic deposits such as calcium and iron salts, relative to Inorganic salts, the present chelator requires a stoichiometric amount of a chelating agent [Frayne, C., Cooling Water Treatment: Principles and Practice, pub. Chemical Publishing Company, New York, NY, pp 145-146 (1999)]. Moreover, Amjad (U.S. Patent No. 4,952,327) teaches that 2-hydroxypropane-1,2,3-tricarboxylic acid can be used to stabilize the iron salt in the solution and prevent precipitation thereof. However, it is not a scale inhibitor and is not effective against calcium carbonates, sulfates, and phosphates. However, 2-hydroxypropane-1,2,3-tricarboxylic acid has been reported as a "threshold" inhibitor specifically for the deposition of calcium sulphate rust, which is effective at sub-stoichiometric concentrations. (Prisciandaro, M. et al., Ind. Eng. Chem. Res. (2003) 42 , 6647-6652). Many carboxylic acids are also known as corrosion inhibitors for ferrous metals (but not copper and copper-based alloys such as brass). Mayer teaches the use of certain carboxylic acids as inhibitors of mild steel corrosion at designated sites. (http://www.bkgwater.com/clients/bkgwater/upload/fichiers/sound_corrosion_inhibitors_cooling.pdf).

There are some reports of the multiplication of certain amines with carboxylic acids for the inhibition of carbon steel and copper corrosion, but the multiplication by scale inhibition or suspension dispersion is unknown.

Hollander (U.S. Patent No. 5,128,065) teaches the use of chelating compounds having triazole-type inhibitors, such as 2-hydroxypropane-1,2,3-tricarboxylic acid, in highly corrosive brackish water to inhibit the benefits of copper corrosion. Triazoles are heterocyclic amines, but do not have the typical properties of most amines, for example, their alkalinity is much lower than that of alkylamines.

Ochoa ( J. Appl. Electrochem. (2004) 34 , 487-493) teaches that a mixture of a fatty diamine and a phosphonium carboxylic acid can have a multiplicative effect on the corrosion inhibition of carbon steel. Salts are not mentioned or made, and these compounds are only used for carbon steel corrosion.

Kern (electrochimica Acta (2001) 47 , 589-598) teaches steel corrosion inhibition by the use of a basic amine having a known carboxylic acid inhibitor (each component contributes to total inhibition). Unconfirmed or taught multiplication.

Amjad (Amjad, Z., presentation AWT-00, Association of Water Technologies, Inc. 12th Annual Convention & Exposition, 2000; also: Tenside Surf. Det. (2007) 44 , 88-93) teaches cationic ammonium species (such as Tetraammonium salts have an adverse effect on poly(prop-2-en) acid scale and deposit inhibitors.

Therefore, many attempts have been made to address these problems of IWTs that require the use of multiple different agents to ideally control all of the problems required within the water cooling system. The only known agents used to control two of these problems are: (1-hydroxyethyl-1,1-diyl) bis(phosphonic acid), which is also used for scale and corrosion inhibition, and for scale inhibition. Poly(prop-2-en) acid dispersed in suspension with the suspension.

Clearly, there is still a need for an IWT compound that can be utilised to meet all of these various needs within an industrial cooling water system, which reduces the amount of chemicals required to accomplish all of these above objectives, and can be simpler and more cost effective. Effective formulations, and in general, reduce chemical exposure to humans, animals, and the environment.

Summary of invention

The present invention relates to ammonium salt compounds of formula (I) which provide a variety of uses (i.e., at least two uses) in industrial water treatment (IWT) systems. It is highly unexpected and surprising to find that the invention is only used within these IWT systems. One of the compounds can control more than one of the problems as described above. However, if necessary, two or more compounds of the formula (I) can be used.

In particular, the present invention relates to a method of treating water in an IWT system comprising using a ammonium sulphate or an oxy-ammonium salt compound of the following formula (I) as the active agent: [RXR ¹ -NH ₃ ⁺ ] _z M ^{- z} type (I)

Wherein: R is a straight or branched C ₆ -C ₂₄ alkyl group or a straight or branched chain C ₆ -C ₂₄ alkoxy-C ₂ -C ₃ -alkyl; X is S or O; R ¹ is always a chain or branched chain C ₂ -C ₃ alkyl; z is an integer of at least 1 up to the total number of acidic protons at M; and M is an ionic moiety having a charge greater than or equal to 1, which is derived An acid having one or more acidic hydrogens and having two or more groups which can coordinate with a metal cation or an electron deficient site on a metal surface, the groups being selected from a group consisting of the following anions: 2-hydroxypropane-1,2,3-tricarboxylic acid; 2,3-dihydroxysuccinic acid; phosphorus oxyhydroxide; (1-hydroxyethyl-1,1-di Bis(bisphosphonic acid); 2,3,4,5-tetrahydroxyadipate; 2,3,4,5,6-pentahydroxyhexanoic acid; hydroxysuccinic acid; 2-phosphonium butane- 1,2,4-tricarboxylic acid; 2,2',2",2"'-(ethyl-1,2-diyldiazo)tetraacetic acid; nitrogen-based acetic acid; butane tetracarboxylic acid; Hydroxyphosphoninoacetic acid; polycarboxylic acid such as poly(prop-2-enoic acid) and poly(Z)-butenedioic acid; containing 2 or more prop-2-enoic acid, (Z)-butene Acid or sulfonated prop-2-enoic acid Nature of the polycarboxylic acid copolymer of repeating units; C ₂ -C ₁₂ dicarboxylic acids, including acetic acid, succinic acid, (Z) - fumaric, adipic, and azelaic acid; and three Boron hydroxide; carboxymethyl inulin, and alginic acid; and adding the compound of formula (I) as a liquid or a solid or as part of a formulation to the water of the IWT system in the following manner: a) In a continuous or semi-continuous manner, it takes time to provide the desired control; or b) in a slug dose, from about 1 day to about 2 months to provide the desired control; at an effective amount, to provide the following At least two of the uses: metal corrosion inhibition, scale inhibition, suspension dispersion, biocidal efficacy or biofilm removal/biofilm dispersion; and observing or testing the IWT system to confirm that this control is achieved .

The concentration of the compound of formula (I) to be controlled in the treated water of the IWT system is from about 0.01 to 2000 ppm, preferably from about 1 to about 200 ppm.

In the formula (I), preferred R molecular groups are those in which R is a straight chain or a branched C ₈ -C ₁₄ alkyl group, more preferably a straight chain or a branched C ₆ -C ₁₆ alkyl group.

In formula (I), preferred M anions are derived from 2-hydroxypropane-1,2,3-tricarboxylic acid; 2,3-dihydroxysuccinic acid; phosphorus oxyhydroxide; (1-hydroxyethyl- 1,1-diyl)bis(phosphonic acid); 2,3,4,5-tetrahydroxyadipate; 2,3,4,5,6-pentahydroxyhexanoic acid; or hydroxysuccinic acid. A better M anion derived from: 2- Hydroxypropane-1,2,3-tricarboxylic acid; 2,3-dihydroxysuccinic acid; phosphorus oxyhydroxide; or (1-hydroxyethyl-1,1-diyl) bis(phosphonic acid).

In the above process, the preferred function of the compound of the formula (I) is rust scale inhibition and suspension dispersion.

A novel subgroup of the compounds of formula (I) is shown by the following formula (IA): [RXR ¹ -NH ₃ ⁺ ] _z Q ^-z (IA)

Wherein: R is a straight or branched C ₆ -C ₂₄ alkyl group or a straight or branched chain C ₆ -C ₂₄ alkoxy-C ₂ -C ₃ -alkyl; X is S or O; R ¹ is always a chain or branched chain C ₂ -C ₃ alkyl; z is an integer of at least 1, such that the compound of formula (IA) is electrically neutral; and Q is an ionic moiety having a charge greater than or equal to 1, which is derived From an acid having one or more acidic hydrogens and having two or more groups which can coordinate with a metal cation or an electron deficient site on a metal surface, the groups are selected from the following Group consisting of: 2,3-dihydroxysuccinic acid; (1-hydroxyethyl-1,1-diyl) bis(phosphonic acid); 2,3,4,5-tetrahydroxyadipate; 3,4,5,6-pentahydroxyhexanoic acid; hydroxysuccinic acid; 2-phosphonium butane-1,2,4-tricarboxylic acid; 2,2',2",2"'-(butyl -1,2-diyldiazo)tetraacetic acid; nitrogenic acetic acid; butane tetracarboxylic acid; 2-hydroxyphosphoninoacetic acid; polycarboxylic acid such as poly(prop-2-enoic acid) and poly(Z) -butenedioic acid; polycarboxylic acid copolymer containing 2 or more prop-2-enoic acid-(Z) butenedioic acid or sulfonated prop-2-enoic acid-derived repeating unit; C ₂ - C ₁₂ dicarboxylic acids, which comprises Acid, (Z) - fumaric, adipic, and azelaic acid; carboxymethyl inulin; and alginic acid.

In formula (IA), preferred Q anions are selected from the group consisting of 2,3-dihydroxysuccinic acid; (1-hydroxyethyl-1,1-diyl)bis(phosphonic acid); 2,3,4, 5-tetrahydroxyadipate; 2,3,4,5,6-pentahydroxyhexanoic acid; hydroxysuccinic acid; 2-phosphonylbutane-1,2,4-tricarboxylic acid; 2,2' , 2", 2"'-(butyl-1,2-diyldiazo)tetraacetic acid; nitrogen-based acetic acid; butane tetracarboxylic acid; 2-hydroxyphosphoninoacetic acid; polycarboxylic acid, such as poly(propylene) 2-enoic acid) and poly(Z)-butenedioic acid; containing 2 or more prop-2-enoic acid, (Z)-butenedioic acid, or sulfonated prop-2-enoic acid-derived repeats Unit of polycarboxylic acid copolymer. More preferably, the Q anion is derived from 2,3-dihydroxysuccinic acid; and (1-hydroxyethyl-1,1-diyl) bis(phosphonic acid).

The compound of the formula (IA) is used in the same manner as the compound of the formula (I) for the treatment of water in the IWT system.

These compounds of formula (I) provide control which is suitable for the needs of an IWT system as described above. Of course, these compounds are still effective if all of the above functions required for such problems in the IWT system are small. By using only one compound with multiple uses, the chances of contact with a person using these chemicals can be alleviated due to the small number of different chemicals that need to be added. Moreover, when less chemicals are required, the impact on the environment (such as chemical waste treatment and reuse of water) can be reduced.

Figure 1 is a graphical representation of the relative scale inhibition performance of the compounds of formula (I) and known compounds, wherein the tested compounds are identified in Table 1 or are known chemicals. In this illustration, the straight axis is the supersaturation ratio (S _r ) and the horizontal axis is the compound tested.

Figure 2 is a graphical representation of the relative inhibition of mild steel by the compound of the formula (I) and known compounds, wherein the tested compounds are identified in Table 1 or are known chemicals. In this illustration, the straight axis is % inhibition and the horizontal axis is the compound tested.

Figure 3 is a graphical representation of the relative inhibition of copper by a compound of formula (I) and known compounds. Wherein the tested compounds are identified in Table 1 or are known chemicals. In this illustration, the straight axis is % inhibition and the horizontal axis is each of the tested compounds.

Figure 4 is a graphical representation of the relative inhibition of copper by another compound of formula (I) and known compounds, wherein the tested compounds are identified in Table 1 or are known chemicals. In this illustration, the straight axis is % inhibition and the horizontal axis is each of the tested compounds.

Figure 5 is a graphical representation of the biocidal efficacy of an anti-plankton organism using the compound of formula (I), which took 54 hours after the biocidal efficacy, wherein the tested compounds were confirmed in Table 1. In this diagram, the straight axis is the flora determined by CFU in 10 ml of test water, and the horizontal axis is the compound tested.

Figure 6 is a graphical representation of the biocidal efficacy of the sessile-resistant organisms using the compounds of the formula (I), which took 54 hours after the biocidal efficacy, wherein the tested compounds were confirmed in Table 1. In this illustration, the straight axis is the flora determined by CFU per scrubber, and the horizontal axis is the compound tested.

Figure 7 is a graphical representation of the biocidal efficacy after 120 hours of incubation of an anti-plankton organism using the compound of formula (I), wherein the tested compounds were confirmed in Table 1. In this diagram, the straight axis is the flora determined by CFU in 10 ml of test water, and the horizontal axis is the compound tested.

Figure 8 is a graphical representation of the biocidal efficacy of an organism resistant to sessile treatment using the compound of formula (I), which took about 120 hours of biocidal efficacy, wherein the tested compounds were confirmed in Table 1. In this illustration, the straight axis is the flora determined by CFU per scrubber, and the horizontal axis is the compound tested.

Figure 9 illustrates various problems in the treatment of the compounds of formula (I) of the present invention in the process of the invention.

Detailed description of the preferred embodiment

The terminology used herein is for the purpose of description and description As used in this specification, the singular "", "," When used in this application, the following terms in the glossary are intended to be as defined below and in the context of these terms, the singular includes the plural.

Various headings are provided to assist the reader, but are not intended to be exclusive of all aspects of the subject matter mentioned, and are not considered to limit the designation of this discussion.

Moreover, certain U.S. patents and PCT published applications are incorporated herein by reference. However, the context of these patents is incorporated herein by reference to the extent to which the extent of reference is incorporated herein by reference. It does not create conflicts between declarations. In the event of such a conflict, the context of any such conflict in the U.S. Patent or PCT Application, which is incorporated herein by reference in its entirety, is hereby incorporated by reference.

Vocabulary interpretation

When used in this application, the following nouns are defined as follows and in the case of these nouns, the singular includes the plural.

By biological matrix, means a renewable source (such as sugar microbes or yeast fermentation), or other plant-derived substances, or from any living substance (such as plants).

COC means the cycle of concentration

% means percentage unless otherwise specified

g means grams

h means hour

HD means (1-hydroxyethyl-1,1-diyl) bis(phosphonic acid)

HPT means 2-hydroxypropane-1,2,3-tricarboxylic acid

IWT means industrial water treatment and generally refers to the treatment of water or aqueous fluids used to mitigate or control the conditions presented in Figure 9, and includes, but is not limited to, cooling towers, closed loops, and open loop heat exchange , plate and frame heat exchangers, chillers, fluid cooling systems, boilers, metalworking fluids, oil and gas production wells, crude oil transfer pipes, oil storage containers, natural gas transmission pipes, natural gas storage containers, formation fragmentation operations And fluids, systems using high efficiency heat transfer tower packing, pipeline cleaning (pigging), reverse osmosis membranes, ultrafiltration membranes, sand filters, and charcoal filters.

L means liter

Min meaning points

mL means ml

Mpy means the number of mils per year

Na-TAI means 1,2,3,-tris-1H-茚

Oxyamine (II) means aminopropyl oxane

RT means room temperature or ambient temperature, about 20-25 ° C

Sec means seconds

The slug dose is the dose added during the specified period, which is usually a large dose added once (rather than gradually) and repeated if necessary

Thioamine (II) means 2-(mercaptothio)ethylamine

Discussion

As specified above, for example, as described in the following web site, the IWT's issues are complex and relevant: http://imexpo.cii.in/presentations/INDUSTRIAL%20COOLING%20WATER%20MANAGEMENT.pdf. Most IWT systems have a variety of issues that need to be controlled. These issues are discussed in the paper to understand the relevant difficulties in more detail. As specified below, the following nouns are used in the IWT industry.

Metal corrosion

Corrosion is essentially related to an electrochemical oxidation process that can cause damage to the metals used to make up most of the cooling towers, such as copper, brass, iron, aluminum, and mild steel. The integrity of the cooling tower system can have serious drawbacks if left untreated for long periods of time. For example, if the iron oxide deposit is not removed, it will increase corrosion under the deposit, limit the flow of water, and cause clogging of the system. Corrosion that impedes heat transfer, provides habitat for microbial species, and causes microbiological effects. Effective corrosion control therefore typically also includes the use of scale inhibitors, biocides and dispersants. Both copper and mild steel are important materials for the construction of the IWT system. Copper is preferred in terms of efficient heat transfer properties within the heat exchanger, and mild steel is preferred for use in the cost effective structural properties of general structural components and tubing.

Another example of an important corrosion problem within the IWT is the surface corrosion of galvanized steel, such as zinc oxide (white rust) and aluminum corrosion in high pressure boilers and wind power plants.

Rust

The deposition of scale in an IWT system is a chemical process that occurs when the concentration of dissolved salts in the cooling water exceeds its solubility limit and forms a precipitate on the surface in contact with the water. The most common rust scale formation is calcium carbonate, which is a salt exhibiting reverse solubility because the solubility of the salt becomes lower as the temperature of the water increases. This property can result in the formation of calcium carbonate rust in most sensitive areas (the heat transfer surfaces of the manufacturing equipment). Since the thermal conductivity of the rust is substantially less than that of the metal, heat removal is reduced. In extreme cases, the precipitated material is sufficient to actually block the cooling water passage, thus necessitating the removal of the affected equipment from the operation for chemical (acid) or mechanical cleaning.

The chemical scale inhibitor function is carried out as follows: (A) selective adsorption on the grown rust scale crystals to convert the crystal structure into a non-rust scale type (bottom limit inhibitor) which does not form hard scale ),or (B) converting into a non-rust scale forming material (a stoichiometric inhibitor such as a chelating agent) by chemically reacting ions with the scale.

A bottom inhibitor (Prisciandaro, M. et al., Ind. Eng. Chem. Res. (2003) 42 , 6647-6652) provides a defined method that hinders or delays the formation of scale and includes the addition of additives in solution. ). These compounds are added to any particular treatment in very small quantities (ppm), and are therefore referred to as "bottom limit inhibitors" in order to illustrate the substoichiometric mechanism of the scale inhibitors. The background effect is explained by the fact that the inhibitor adsorbs to the crystal growth site of the submicroscopic crystallites originally produced in the supersaturated solution, which interferes with crystal growth and changes its growth morphology. The method prevents crystal growth or at least delays growth for a long time. Therefore, the scale inhibition by a bottom inhibitor is based on kinetic effects rather than kinetic effects. Many investigations have been shown in water-soluble additives (such as special types of polymers/copolymers: carboxyls, organophosphorus compounds, phosphonic acid derivatives, organophosphates, 2-hydroxypropane, 1,2,3) Precipitation of certain calcium salts can be significantly reduced in the presence of tricarboxylic acids, anionic and cationic surfactants, and certain metal ions.

Although sulfur scale is also a problem in the IWT system, it is not part of the present invention. Sulfur scale is chemically different from calcium carbonate and most other types of scale, because the sulfur scale is mainly elemental (non-ionic), and the hydrogen sulfide which is present in the water is Formed by different methods of biological or abiotic oxidation, and the formed sulfur precipitates and forms a deposit. Other forms of sulfur-based deposits include iron sulfide, which is the reaction product of hydrogen sulfide and metallic iron or iron salts. Iron sulfide deposit It is controlled by controlling the formation of hydrogen sulfide.

Dispersion of suspended matter

Deposition is a generic term for all matters that can cause problems with a cooling water system, which is a NOT due to rust, corrosion, or biological activity. This deposition can be formed by washing the floating material from ambient air by the cooling tower, process contamination of the cooling water due to, for example, an oil cooler, suspending or eroding the product, and replenishing the suspended solids in the water. It is possible to control the deposition of most suspended solids by adding a dispersant chemical such as poly(prop-2-enoic acid), poly[(Z)-butenedioic acid], and the like to the cooling water. . These materials can act by the charge neutralization of the suspended particles and can then act as an emulsification binder to comminute the existing deposits and prevent the particles from cohesing to form new deposits.

Biological blockage

If not controlled, the growth of microorganisms in a cooling water system causes the bio-clogging layer (biofilm) to form on all surfaces in contact with the cooling water. This biofilm is like rust and deposit, which can affect the process operation. Biofilms typically result in a large increase in corrosion rate due to the formation of anaerobic regions under the plugging layer. It can produce galvanic coupling corrosion and form metabolic by-products such as hydrogen sulfide, which can attack the base metal. The method of controlling biological clogging is to periodically administer a biocide and dispersant to the cooling system to kill as many organisms as possible and remove organisms from the surfaces and send them to a large number that can be washed away from the system. In the water.

General discussion

Obviously, the previous taste to control all these various conditions The test method has been tried with many chemicals or machinery. It is also important to understand which of these conditions is occurring or can change over time. Figure 9 illustrates the interrelationship of these issues, so all problems must be handled within an IWT system. There is currently no commercial treatment known to use only one chemical that controls all of these conditions. Due to the diverse needs of each situation, it is difficult for a compound to provide these various uses. For IWT use, the cost of a compound has been expected to be lower than the cost of multiple chemicals.

Furthermore, the present invention can continuously use water in a cyclical manner. When used in such a cyclical form, such conventional or commonly used chemicals will degrade and minerals, salts, and other molecular groups will accumulate in their water. Therefore, the water chemical has a "requirement" for it. The present invention is highly adaptable or unaffected by this accumulation and does not degrade under end use conditions. Thus, the present invention allows for a higher degree of water reuse with a higher concentration (COC) level of such accumulated molecular groups and which can reduce the need to add more chemicals. Importantly, the present invention can use wastewater within the IWT system. The use of wastewater is limited because it is highly corrosive, toxic, and promotes the accumulation of biofilm. An advantage of the present invention is that wastewater can be used, the same water can be reused (circulating and/or closed loop systems), and biofilm accumulation can be prevented.

Cooling towers, which operate in a fluid cooling mode of operation or are designed, are particularly advantageous for the present invention. Oven temperature control in manufacturing processes, such as in the manufacture of carbon fibers for aircraft wing materials, is particularly advantageous for the present invention. In such systems, water from the cooling tower is sprayed onto the pipe with the cooling water. The tube with cooling water is located in a furnace that provides the final heat treatment of the carbon fiber. The pipe is made of copper. This copper pipe is widely used It is easy to produce the following impacts: copper corrosion, biofilm formation, and rust deposition. Thus, protection of the copper corrosion can be provided via the use of a compound of formula (I) using the process of the invention. The use of each of the chemicals that provide this protection is not sufficient to provide protection within these manufacturing systems. Oxidation is the most important step in the manufacture of carbon fibers. Since oxidation is an exothermic process, a uniform and uniform gas flow is required to evenly control the heat within the process. The consistency of the method controls the quality of the carbon fiber without causing skinning and the carbon fiber can be more uniformly densified. By using the compound of formula (I) or (IA), the carbon fiber process can be improved by making the oxidation rate as fast as 30% higher and the optimum parameters of the oven design can be optimally used.

It has been surprisingly and unexpectedly found that such compounds provide these uses. The present invention provides a formula (I) or (IA) ammonium sulphate or oxy-ammonium salt whose effect is suitable for all of these uses in an IWT system. These uses include metal corrosion inhibition, scale inhibition, suspension dispersion, biocidal efficacy, or biofilm removal/biofilm dispersion. The use of one of these versatile compounds of formula (I) or (IA) can reduce the adverse effects of various chemicals on the environment and the person who is in contact with it. Moreover, the compounds of the invention exhibit greater additive effects in terms of these versatility within the IWT system. The theory that certain salts provide these versatility remains to be studied. It is not possible to predict which salts will produce these desired additive effects. More than one compound of formula (I) can be used if necessary.

Although certain thiamines and oxygenated amines (in the form of free amines) and their acid addition salts are known to increase their solubility in the IWT system, some of them are known to be useful in industrial water treatment. Biocides, biofilm dispersants, and copper inhibitors, but they are not known as soft steel corrosion inhibitors, rust Scale inhibitor or suspension dispersant. Other compounds of non-amine are known to act as effective inhibitors, scale inhibitors, suspension dispersants or solubilizers; however, these are not biocides or biofilm dispersants. In other words, although various aspects of these compounds of the invention have been used, they have not been found to be suitable for all uses; although their compounds of the invention have more utility. The selection of compounds of formula (I) or (IA) in the form of their particular salt is not previously known to control all of these various uses required for industrial water treatment systems.

The present invention provides a method of treating water in an IWT system comprising using a solution of the following formula (I) ammonium sulphate or an oxy-ammonium salt as the active agent: [RXR ¹ -NH ₃ ⁺ ] _z M ^-z formula (I)

Wherein: R is a straight or branched C ₆ -C ₂₄ alkyl group or a straight or branched chain C ₆ -C ₂₄ alkoxy-C ₂ -C ₃ -alkyl; X is S or O; R ¹ is always a chain or branched chain C ₂ -C ₃ alkyl; z is an integer of at least 1 up to the total number of acidic protons at M; and M is an ionic moiety having a charge greater than or equal to 1, which is derived An acid having one or more acidic hydrogens and having two or more groups which can coordinate with a metal cation or an electron deficient site on a metal surface, the groups being selected from a group consisting of the following anions: 2-hydroxypropane-1,2,3-tricarboxylic acid; 2,3-dihydroxysuccinic acid; phosphorus oxyhydroxide; (1-hydroxyethyl-1,1-di Bis(bisphosphonic acid); 2,3,4,5-tetrahydroxyadipate; 2,3,4,5,6-pentahydroxyhexanoic acid; hydroxysuccinic acid; 2-phosphonium butane- 1,2,4-tricarboxylic acid; 2,2',2",2"'-(ethyl-1,2-diyldiazo)tetraacetic acid; nitrogen-based acetic acid; butane tetracarboxylic acid; Hydroxyphosphoninoacetic acid; polycarboxylic acid, such as poly(prop-2-enoic acid) and poly(Z)-butenedioic acid; comprising 2 or more prop-2-enoic acid, (Z)-butene Acid or sulfonated prop-2-ene A polycarboxylic acid derivative of a copolymer of repeating units; C ₂ -C ₁₂ dicarboxylic acids, including acetic acid, succinic acid, (Z) - fumaric, adipic, and azelaic acid; and Boron trioxide; carboxymethyl inulin, and alginic acid; and adding the compound of formula (I) as a liquid or a solid or as part of a formulation to the water of the IWT system in the following manner: a a continuous or semi-continuous manner, which takes time to provide the desired control; or b) in the form of a slug, which takes about 1 day to about 2 months to provide the desired control; at an effective dosage, to provide At least two of the following uses: metal corrosion inhibition, scale inhibition, suspension dispersion, biocidal efficacy, or biofilm removal/biofilm dispersion; and observing or testing the IWT system to confirm that it has been controlled Sex.

When used in the process of the invention, some of the ammonium salts of the formula (I) are novel compounds and are claimed to be a subgroup of formula (I) in formula (A). The acids used for these compounds are those wherein Q is as follows: 2,3,4,5-tetrahydroxyadipate, 2,3-dihydroxysuccinic acid, adipic acid, sebacic acid, butyl Diacid, (Z)-butenedioic acid, (1-hydroxyethyl-1,1-diyl)bis(phosphonic acid), 2-phosphoniumbutane-1,2,4-tricarboxylic acid, hydroxyl Phosphonic acid, 2,2',2",2"'-(ethyl-1,2-diyl Dinitro)tetraacetic acid, poly(prop-2-enoic acid), carboxymethylinulin, and alginic acid. Further, when X is S and the acid is 2-hydroxypropane-1,2,3-tricarboxylic acid, oxalic acid or boron trihydroxide, the compound of the formula (IA) is a novel compound. In formula (IA), when X is O and the acid is 2-hydroxypropane-1,2,3-tricarboxylic acid, one of the compounds of formula (IA) is 2-mercaptopropyl oxane. Hydroxypropyl-1,2,3-tricarboxylate. Moreover, when z is greater than 1, there are different ratios of the anion to the cation, for example, when z is 2, the ratio of anion to anion is 1:2, and there are different compounds having different properties.

The present invention provides a use of a thiamine or an oxyamine-containing salt of formula (I) or (IA) to provide metal corrosion inhibition, rust scale printing, suspension dispersion, biocidal efficacy, or biofilm in an industrial water treatment system. Removal/biofilm dispersion method.

Preferred amines for the preparation of the compounds of formula (I) or (IA) are those wherein R is a straight or branched C ₆ -C ₁₆ alkyl group or more preferably a C ₈ -C ₁₄ alkyl group. One of the tested compounds was 2-(mercaptothio)ethylamine hydrochloride (Compound A in these examples). Thiamine is readily prepared as described in U.S. Patent No. 4,086,273 to Berazosky. Various salts of the thiamin of the formula (I) or (IA) are also tested. Various derivatives of the oxyamines of formula (I) or (IA) are prepared and tested in a similar manner. One of the tested compounds was the vinyl acrylate of aminopropyl oxane (Compound B in these examples). Oxygenated amines are prepared by methods such as those described by Utermohlen in J. Am. Chem. Soc. (1945) 67 , 1505-1506.

The composition of the amine salt is of importance. In order to have an amine salt of the formula (I) or (IA) suitable for all uses, it is important to consider which acid equivalent to Q or M can be combined to form the salt.

Preferred acids correspond to the M anions in formula (I). These acids are typically used alone in IWT as different agents that provide certain advantages such as rust or corrosion inhibition. Salts of formula (I) or (IA) provide an effective mechanism for imparting the advantages of the acid and the advantages of the amine within a compound. The amine and acid salts can produce advantages that are greater than those expected from the two components alone.

The nature and potency of the salt in the IWT also depends on the proportion of the components present. For example, in the case of a dibasic acid such as oxalic acid, the two salts may have one amine, namely ammonium hydrogen oxalate and diammonium oxalate. Each product is a different chemical compound with unique properties. It is apparent that what properties can be produced by the reaction of oxalic acid with an amine not specifically designated stoichiometric.

The method for producing these salts of the formula (I) or (IA) is carried out by using the following three methods: in the absence of a solvent, or preferably in a solvent such as water or aqueous 2-propanol, the free acid and the acid. The reaction accelerates the mixing and heat transfer of the compounds (because the reaction is exothermic). The solution of the salt of formula (I) or (IA) formed can be used directly or evaporated to the desired concentration or completely evaporated to its solvent free form. Solvent-free forms are particularly useful if they are solid, which can be formulated in a variety of user-friendly ways with less waste treatment.

Alternatively, a salt of the amine and acetic acid is converted to a salt of formula (I) or (IA) by reacting an acid with the corresponding ammonium acetate salt in an aqueous medium. When the pKa used to make the new ammonium salt is about the same as or similar to acetic acid At low levels, a significant concentration of the novel acid salt is formed. However, since acetic acid is volatile (and the acid is not volatile), the "free" acetic acid evaporates, and by LeChatelier's Principle, the equilibrium can be transferred to form more acetic acid. After a period of time, all of the acetic acid evaporates leaving only the novel ammonium salt of formula (I) or (IA). Other acids may be used in place of the acetic acid, with the proviso that they must be volatile, such as formic acid and propionic acid.

Another method by which the compound of the formula (I) or (IA) can be prepared comprises mixing a monoamine salt and a salt of the desired acid in a suitable solvent to effect the reaction.

The amine salt of the formula (I) or (IA) is prepared as described above, and the like can be used in an IWT system to control all of the above uses. Moreover, these salts can be prepared on the spot just prior to use, or in the manner in which the salt can be formed, once in use, the components (e.g., the amine and the acid) are combined.

Although it is known that certain ammonium sulphate or oxy-ammonium compounds having a different M anion salt than the currently listed and claimed salts (e.g., Cl, acetate) are suitable for various uses, it is known that they cannot be used as claimed. Scale inhibition or multiple uses. The compounds of formula (I) of the present invention have proven to have improved utility in these prior uses and are useful in more targeted applications than such prior compounds. Furthermore, it has surprisingly been found that these compounds of the formula (I) according to the invention have an unpredictable multiplicative effect (i.e. non-additive improvement) compared to the total number of efficacies derived from only the corresponding amines and acid compounds. ). These results are surprising and unpredictable because of Amjad (Amjad, Z., presentation AWT-00, Association of Water Technologies, Inc. 12th Annual Convention & Exposition, 2000; also: Tenside Surf. Det. (2007) 44 , 88-93) It has been found that certain cationic nitrogen compounds for IWT interfere with the effectiveness of anionic water treatment chemicals such as scale inhibitors and suspension dispersants. Thus, in view of the utility of the anion, an anionic ammonium salt, such as the salt represented by formula (I), is expected to have a reduced effectiveness. It is apparent that it is not expected that some of the cations and those anions (even if their respective uses are known) can be combined to obtain improved and effective use of the formed compounds; undoubtedly, it is not suitable for a variety of uses. Accordingly, the teachings of this reference are not relevant to the use of such combinations of ammonium salts and acids of the present invention. It is apparent that this reference concludes that it is practically impossible to manufacture a combination of anions and cations or compounds which may have such additive effects that can be used even for the compounds of the present invention.

When other known agents are present in a desired condition, the compounds of formula (I) or (IA) and such additional agents (groups) may be used in combination in the process of the invention (each of which may be added separately or together in a combined formulation) Inside). The use of a combination of water treatment chemicals such as scale inhibitors, corrosion inhibitors, suspension dispersants, biocides, biofilm removers, and biofilm dispersants is a common practice. The combination of such additional active ingredients does not alter the utility of the compound of formula (I) or (IA) used in the process.

Furthermore, when other known inert ingredients are present in the desired state, the compound of formula (I) or (IA) and such inert ingredients (group) may be used in combination in the process of the invention. These inert ingredients are water, solvents, diluents, excipients, stabilizers, surfactants, and antifoaming agents.

When necessary, less than all the uses disclosed in the method of the present invention In the meantime, these compounds of formula (I) or (IA) can be used alone in the process of the invention.

In the method of the invention, IWT is used to treat aqueous fluids to mitigate or control the conditions presented in Figure 9. These IWT systems cover, but are not limited to, cooling towers, closed loop and open loop heat exchangers, plate and frame heat exchangers, freezers, fluid cooling systems, boilers, metalworking fluids, oil and gas production wells. , crude oil conveying pipe, oil storage container, natural gas transmission pipe, natural gas storage container, formation fragmentation operation and fluid, system using high efficiency heat transfer tower filling, pipeline cleaning (ingot), reverse osmosis membrane, ultrafiltration membrane, sand Filters, charcoal filters, water in toilets, mobile toilets, urinals, spa equipment, mineral baths, and swimming pools.

The compound of formula (I) or (IA) is used in liquid or solid form. Moreover it can be diluted in a solution. The solids may be, for example, powders, lozenges, lumps, granules, or granules, or formulated to be suitable for controlled release. The liquid includes a solution, an emulsion, a suspension, a solventless liquid, a gel, or a dispersion. Also, other active agents may be present when necessary. The method of the present invention may introduce the compound of the formula (I) or (IA) into the IWT system in a continuous manner, in a semi-continuous manner, or in a slug dose, and the liquid may be introduced into the IWT system by a stoichiometric pump or Simply pour from a container, such as a pail, into the water to be treated. The solids in the form of a mass may be introduced directly into the IWT system, which may gradually dissolve or may be by means of a solid feeder device wherein the solid is dissolved or suspended in water and then at a controlled rate Import. This controlled or slow release can be obtained by using a semi-permeable membrane or a suitable solid formulation.

The amount of the compound of formula (I) or (IA) used in this IWT system In an amount sufficient to achieve the desired control, the amount in the treated water has a concentration of from less than 0.01 to 2000 ppm, preferably from about 1 to about 200 ppm.

In certain applications, such as oil production, the compound of formula (I) or (IA) can be forced into the formation under pressure (extrusion process). In other applications, it can also be adsorbed onto an inert substrate and then used to treat the water. Such as in a sand filter.

The invention may be further clarified by the following examples, which are considered as merely representative of the invention.

Examples of the latter are related to the preparation of raw materials and as comparative examples. Examples of such numbers are those of formula (I) and (IA) of the present invention.

The amines used in these are prepared as described above.

These acids are purchased from various sources expressed in parentheses, and are used as they are: 2-hydroxypropane-1,2,3-tricarboxylic acid monohydrate (Mallinckrodt Baker), 2-hydroxy-1, 2,3-tricarboxylic acid (anhydrous) (Southeastern Laboratories), (Z)-butenedioic acid (Fisher), succinic acid (Fisher), oxalic acid dihydrate (JT Baker), azelaic acid (Sigma- Aldrich), 2,3-dihydroxysuccinic acid (Fisher), boron trichloride (Columbia Chemical Industries), phosphorus oxyhydroxide (85%, Fisher), (1-hydroxyethyl-1,1-diyl) bis (phosphonic acid) (Belclene ^TM 660, 60% of water was obtained from BWA), poly (prop-2-enoate) (Acusol ^TM 445ND), sodium salt, average molecular weight 4500, the Dow Chemical Company), And 2,3,4,5-tetrahydroxyadipate, monopotassium salt (Sigma-Aldrich).

Production of formula (I) and comparative compounds Example A and Comparative Example A: Preparation of ammonium thiosulfate (II)

The ammonium sulphate is isolated from a liquid 15% formulation by a crystallization reaction. A sample of this solution was placed in a round bottom beaker and its original volume was reduced by half on a rotary evaporator (approximately 10 torr water aspirator vacuum and a 50 ° C water bath). Acetonitrile (having a volume approximately equal to the volume of concentrated ammonium sulphate (II) in the flask) is added to the clear, dark orange/brown liquid. The milky white solution containing a small amount of precipitate after addition was frozen at about 40 °F, during which the solution solidified. The solid was pulverized and the mixture was vacuum filtered. After washing with additional acetonitrile, the light brown/milk-yellow crystalline ammonium sulphate (II) was air-dried. The recovery % of ammonium sulphate (II) is 50-60%).

Example 1: Preparation of a salt of thiamine (II) and 2-hydroxypropane 1,2,3-tricarboxylic acid (1:1 molar concentration stoichiometry)

A clear, slightly viscous solution of ammonium sulphate (II) (13.84 g, prepared by the procedure of Example A) in distilled water (200 mL) was prepared in a 1 liter separatory funnel. In a separate vessel, 4.8 grams of a commercially available 50% NaOH solution was diluted to a volume of 10 milliliters with distilled water. When the separatory funnel was manually rotated, the aqueous NaOH solution was added in about 30 seconds. The following two layers are formed: a yellow upper layer and a hazy milky white lower layer. The lower layer is separated and discarded. 2-Propanol (3 x 10 mL) was added to the yellow upper layer remaining in the septum funnel to cause more water to separate, which was separated and discarded. The residual solution was then added directly to a solution of 2-hydroxypropane-1,2,3-tricarboxylic acid monohydrate (12.6 g) in distilled water (30 mL) and diluted to 100.0 g. The yield was 84% based on the thiamine (II) content. An aqueous solution of the present thiamine (II) and 2-hydroxypropane-1,2,3-tricarboxylic acid salt was used directly in subsequent tests.

Example 2: General Preparation Method of Oxygenated Ammonium Salt (Method 1)

A: a method for preparing the salt of the oxygenated amine (II) and (Z)-butenedioic acid (1:1 molar concentration stoichiometry)

(Z)-butenedioic acid (11.6 g) was dissolved in distilled water (60 ml). A solution of the oxyamine (II) (in its free amine form, 21.5 g) in 2-propanol (40 mL) was quickly added in one portion to the stirred solution. The empty flask was rinsed with 2-propanol (10 mL) and the liquid was poured into the reaction vessel. This mixing step is slightly exothermic (the solution temperature rises by 10-15 ° C) and produces a clear, bright green/yellow solution. The solution was transferred to an evaporating dish and the dish was left in a fume hood to evaporate the volatiles at RT. As the volatiles evaporate, the solution becomes a darker yellow with a solution of a slight orange hue and a viscous layer floats thereon. When the material appeared to be dry, the evaporating dish was placed in a vacuum desiccator (3-8 Torr) and it took several hours to complete the drying procedure. This product was obtained as a fresh orange white waxy paste (28.0 g, 85% yield).

B: The amine is reacted with the corresponding acid in a similar manner to Example 2A to give a salt of the name: oxyamine (II) and succinate (1:1 molar concentration stoichiometry) of the salt, Yield 98%, salt of oxyamine (II) and sebacate (same molar concentration of 1:1 molar), yield 99%, oxygenated amine (II) and oxalate (1:1 Mo Ear concentration stoichiometry) salt, yield 84%, oxyamine (II) and 2,3-dihydroxysuccinate (1:1 molar concentration chemistry) Amount of salt, yield 88%, salt of oxygenated amine (II) and phosphorus oxyhydroxide (1:1 molar concentration stoichiometry), yield 98%, oxygenated amines (II) and 2,3 , 4,5-tetrahydroxyadipate (1:1 molar concentration stoichiometric) salt, yield 98%,

Example B and Comparative Example B: Preparation of Oxygenated Amine (II) and Acetic Acid Salt

In a similar manner to Example 2A, a salt of the oxyamine (II) and acetic acid was obtained in a yield of 85%.

Example 3: General Preparation Method of Oxygenated Ammonium Salt (Method 2)

A: Method for preparing salt of oxyamine (II) and (1-hydroxyethyl-1,1-diyl) bis(phosphonic acid) (1:1 molar concentration stoichiometry)

A solution of (1-hydroxyethyl-1,1-diyl)bis(phosphonic acid) (3.43 g) was diluted to a volume of 5 ml with distilled water. This solution was poured in one portion into a solution of oxyamine (II) and acetic acid (2.75 g; which was prepared by the procedure of Example B) in 2-propanol (10 ml). The reaction mixture was placed in an evaporating dish in a fume hood and allowed to evaporate at RT. As the volatiles evaporate, the solution becomes a viscous, pale yellow gel. When the material appeared to be dry, it was placed in a vacuum desiccator (3-8 Torr) and it took several hours to complete the drying procedure. The product was obtained as a white solid (3.39 g, 80%).

B: In a similar manner to Example 3A, the salt of the oxygenated amine (II) and acetic acid was reacted with the corresponding acid to give the following: oxygenated amine (II) and (1-hydroxyethyl-1,1-diyl) Bis(phosphonate) salt (2:1 molar concentration stoichiometric) salt, yield 85%

Oxygenated amines (II) and poly(prop-2-enoic acid) salts (1:1 and 0.2:1 stoichiometry) Salt, the yield is 65% and 84% respectively

Oxygenated amine (II) and 2-hydroxypropane-1,2,3-tricarboxylate (1:1 molar concentration stoichiometric) salt, yield 106% (residual solvent)

Example 4: Method for preparing salt of oxygenated amine (II) and boron trihydroxide (1:3 molar concentration stoichiometry)

The process described by Vineyard, BD et al . , Inorg. Chem. (1964) 3 (8), 1144-1147 is as follows.

Adding oxyamine (II) (12.21 g), boron trihydroxide (3.53 g), and water (3.6 ml) to a round bottom flask equipped with a Dean-Stark water trap and condenser Inside toluene (50 ml). The mixture was stirred at about 45 ° C for 30 minutes and then the mixture was heated to reflux for 1 hour. The water collected in the trap was turbid and the toluene/water interface was not clearly visible. Acetonitrile (25 mL) was added and refluxing continued for a further 15 minutes. Once cooled, the reaction flask contained a gelatinous slightly greenish white translucent precipitate. The material was collected by filtration and placed in a vacuum desiccator (3-8 Torr), which took several days. This product was obtained as a white free flowing solid (14.4 g, 77.4% yield). The product formed is considered to be part of: ⁺ H ₃ NR ¹ -XR

Example 5: Various salts of formula (I) are provided in Table 1 below.

Method of using the compound of formula (I)

The following examples illustrate the use of the salt of the formula (I) listed in Table 1. Surprisingly, once the desired anion is selected, several of these salts of formula (I) can provide a variety of uses within a compound, however, as indicated below, salts containing other anions are not effective for use in a variety of applications. use.

Scale inhibition

The following general procedure was used to determine the calcium carbonate scale inhibition of various compounds of formula (I) and is generally in accordance with the method described by Drela, I. et al., Wat. Res. (1998) 32 , 3188-3191 .

Add 60 ml of HPLC grade water and 3 ml of 0.1 M calcium chloride to a 100 ml beaker. Then add a suitable amount (0.5-4 ml) An aqueous solution of the inhibitor compound of formula (I) was tested. The solution was mechanically agitated at a constant speed for all experiments. The sample was then titrated with 0.1 M sodium carbonate. After each 0.2 ml portion of the sodium carbonate titrant was added, the solution was mixed for 1 minute, and then the conductivity of the solution was measured.

As the titrant is added, the conductivity increases in a linear form. When the supersaturation point is reached, the conductivity decreases and precipitation begins. It is considered to be the endpoint of the titration. The titration endpoint volume formed is used to calculate a relative supersaturation ratio (S _r ). It is the ratio of the supersaturation of calcium carbonate to the supersaturation of water containing no inhibitor (distilled water plus 3 ml of 0.1 M calcium chloride) in the presence of the compound of formula (I) to be tested. Therefore, the compound having S _r > 1 exhibits scale inhibition.

The scale inhibition performance of each of the compounds of the formula (I) and the comparative compounds at the same molar concentration was compared. The relative calcium carbonate scale inhibition performance (supersaturation ratio, S _r ) is shown in Table 2. These compounds were tested at 60 micromolar (μM) unless otherwise specified. The compound numbers are derived from Table 1.

A portion of this data is shown graphically in Figure 1.

At this concentration, the compound showed no scale inhibition. Compound A and 2-hydroxypropane-1,2,3-tricarboxylic acid showed similar but to a small extent scale inhibition. Compound 13 showed superior scale inhibition of Compound 1, but all of them were scale inhibitors. However, at the same 60 μM, the effectiveness of compound 13 was not as good as that of the standard scale inhibitor 2-phosphoniumbutane-1,2,4-tricarboxylic acid; however, at 180 μM, the results obtained for compound 13 were 2-phosphonium butane-1,2,4-tricarboxylic acid at 60 μM is similar. Compound 13 at 120 μM is similar to (1-hydroxyethyl-1,1-diyl)bis(phosphonic acid) at 45 μM.

The effectiveness of Compound 13 (i.e., the salt of thiamin (II) and 2-hydroxypropane-1,2,3-tricarboxylate, S _r = 1.9) exceeded expectations. The additive effect of compound A (ammonium chloride (II) chloride, 1.2) plus 2-hydroxypropane-1,2,3-tricarboxylic acid (1.2) based on a 1:1 molar concentration is expected to yield S. _r = 1.4. The potency of Compound 1 (sodium salt of oxyamine (II) and 2-hydroxypropane-1,2,3-tricarboxylic acid, S _r =1.4) is higher than that of Compound A (1.0 based on 1:1 molar concentration). ; no effect) plus the additive effect expected for 2-hydroxypropane-1,2,3-tricarboxylic acid (1.2) (which is 1.2).

2-Hydroxypropane-1,2,3-tricarboxylic acid is reported to be not a CaCO ₃ scale inhibitor. It is also known that compounds A and B are not CaCO ₃ scale inhibitors. Thus, surprisingly, the 2-hydroxypropane-1,2,3-tricarboxylate of these compounds has significant scale inhibition and, more particularly, with its amine and 2-hydroxypropane-1, In comparison with the 2,3-tricarboxylic acid component, it is possible to obtain an effect larger than the additive increase in the scale inhibition effect. Due to poor water solubility, although each of the amines has not been tested, the tested hydrochloride (Compound A) or acetate (Compound B) is expected to give the same results as the individual free amines, as it is not known At these low concentrations, the chloride and acetate anions have a significant effect on scale inhibition.

Further, in the above references Drela, when the concentration of a rust inhibitor is doubled, may be generated has been reported less than the sum of S _r a result (i.e., less than twice). When the concentration was increased from 60 to 120 to 180 μM, the results were also confirmed by the data of Compound 13. Therefore, when the two inhibitors are combined at the same concentration, a small addition result is actually obtained. It is apparent that these data of the present invention found that the use of Compounds 1 and 13 gave greater additive results; these results were unpredictable and surprising.

In addition to the unpredictable advantages of the 2-hydroxypropane-12,3-tricarboxylates of the compounds 13 and 1, the thiamine (II) and the oxyamine (II), respectively, the compound 8 The effectiveness of 2,3-dihydroxysuccinic acid and oxy-amine (II), S _r =1.3) is also superior to compound A (1.0; no effect) based on 1:1 molar concentration. The additive effect of 2,3-dihydroxysuccinic acid (1.0) (which is 1.0). Therefore, the structurally similar salts of 2,3-dihydroxysuccinic acid can also be found in the non-cocoa of the 2-hydroxypropane-1,2,3-tricarboxylates of the oxyamine (II). Expected improvement.

Therefore, the ammonium sulfates and the oxygen-containing ammonium salts of the acids of the formulae (II) and (IA) have a good calcium carbonate scale inhibiting effect and, in addition, with the thiamines and the chloride or acetate salts thereof When the oxyamines are compared, respectively, or compared to the dibasic acids, an unpredictable increase in additiveness is exhibited in the scale inhibition effect.

Erosion inhibition

Erosion studies of various compounds of formula (I) were carried out according to ASTM method G31-72 (2004). The following are general test methods.

A mild steel corrosion study was conducted using an aqueous solution (900 ml) of the test compound made of municipal water, or a copper corrosion study using a dilute sea salt solution (1000 ppm in deionized water). The solutions were magnetically agitated at a constant rate in a 1 liter beaker and 3 pieces of mild steel or copper test samples were suspended in each beaker. After 5 days (steel) or 7 days (copper), the test samples were removed and cleaned according to ASTM method G1-03. The weight loss of the three test samples of each group was measured and then converted to a corrosion rate expressed in mils per year.

A. mild steel

These tests compare the inhibition of the compound of formula (I) from Table 1, in the first set of comparisons, compound A compared to compound 13, and compound B compared to compound 1, and compounds 13 and 1 and 2-hydroxyl. Comparison of propane-1,2,3-tricarboxylic acid. Thus, after 5 days, 5 samples were tested against a blank and a standard (1-hydroxyethyl-1,1-diyl) bis(phosphonic acid) at 26 μM. The results are shown in Table 3 by the corrosion rate (mpy) and relative inhibition shown by the following formula: % inhibition = [corrosion rate (inhibitor) - corrosion rate (blank)] / corrosion rate (blank) × 100% Table 3 shows the relative corrosion rate. The concentration was 26 μM.

For Table 3 with soft steel test samples, these results show that the additive inhibition of Compounds 1 and 13 is greater than Compound B and Compound A, respectively, and greater than 2-Hydroxypropane, under these test conditions and at the concentration of this inhibitor. -1,2,3-tricarboxylic acid alone. The comparative compounds B (1.6%) and A (3.3%) did not show significant inhibition. 2-Hydroxypropane-1,2,3-tricarboxylic acid is a known mild steel inhibitor and exhibits a small degree of inhibition (9.8%). Compounds 1 (60%) and 13 (94%) of formula (I) showed significantly better inhibition than 2-hydroxypropane-1,2,3-tricarboxylic acid and the like. These results are greater than the total number of comparative compounds of the 2-hydroxypropane-1,2,3-tricarboxylic acid and the like. Thus, via the use of the compound of formula (I), the inhibition has a greater unpredictable greater additive improvement. Moreover, the inhibition of compounds 1 and 13 is greater than that of (1-hydroxyethyl-1,1-diyl) bis(phosphonic acid) based on a molar concentration (which is known as mild steel for industrial water treatment). Inhibitor). Although each of the amines was not tested due to poor water solubility, the tested hydrochloride (Compound A) or acetate (Compound B) was expected to give the same results as the respective free amines, as At these low concentrations, it is not known that these chlorides and acetate anions have a significant effect on the inhibition.

An additional mild steel corrosion test was carried out at 130 μM of the compound of formula (I) and the comparative compound, which took 5 days. The next test is a comparison of compound 8 and 2,3-dihydroxysuccinic acid with compound B, and compound 4 with (1-hydroxyethyl-1,1-diyl)bis(phosphonic acid) and compound B. Comparison. Compound 1 for reference is also included. The results are shown in Table 4. The concentration in this group was 130 μM.

It is worth noting that both Compound 8 and Compound 4 found non-additive improvements relative to their components. Compound 8 (44% inhibition) was greater than the sum of 2,3-dihydroxysuccinic acid (20%) and compound 8 (-1%). Compound 4 (68% inhibition) was greater than the sum of (1-hydroxyethyl-1,1-diyl)bis(phosphonic acid) (62%) and compound (-1%). The concentration in this group was 130 μM.

It is worth noting that Compound 3 found a non-additive improvement relative to its constituents, but Compound 2 was not found. Compound 3 (55% inhibition) is greater than the sum of phosphorus oxyhydroxide (40%) and compound B (-1%). Both Compound 2 and oxalic acid are slightly corrosive with respect to the blank.

B. Copper

The first test for copper inhibition was the comparison of Compound A with Compound 13 (from Table 1), 2-hydroxypropane-1,2,3-tricarboxylic acid, and a commercially available inhibitor (Na-TAI). The results in Table 6 show the inhibitory potency of the four inhibitors relative to a blank after 7 days at equimolar concentration (17 μM).

These data are graphically represented in Figure 3 as % inhibition.

As shown in Table 6, Compound A (41%) showed significant inhibition at these test conditions using the copper test sample and the concentration of the present inhibitor. 2-Hydroxypropane-1,2,3-tricarboxylic acid (0%) did not show a significant degree of inhibition. Compound 13 (59%) showed a high degree of inhibition and its inhibition was significantly higher than that of Compound A or 2-hydroxypropane-1,2,3-tricarboxylic acid. Moreover, the additive effect of the compound is greater than that of the compound A and the 2-hydroxypropane-1,2,3-tricarboxylic acid. The inhibition of compound 13 and Na-TAI based on the concentration of one mole (the system is Copper inhibitors used in industrial water treatment are similar. For compound 13 of formula (I), this result is an unexpected and surprising improvement. The concentration in this group was 42 μM.

These data are graphically represented in Figure 4 as % inhibition.

For compound B (32%), the results in Table 7 show significant inhibition. 2-Hydroxypropane-1,2,3-tricarboxylic acid (9%) did not show a significant degree of inhibition. Compound 1 (54%) showed a high degree of inhibition and its inhibition was significantly higher than that of Compound B or 2-hydroxypropane-1,2,3-tricarboxylic acid. Moreover, the additive effect of Compound 1 is higher than the sum of Compound 2 and 2-hydroxypropane-1,2,3-tricarboxylic acid. As with compound 13, the present result of compound 1 of formula (I) is an unexpected and surprising improvement. The concentration in this group was 42 μM.

Biocidal efficacy

An experiment was conducted to evaluate the biocidal effectiveness of Compounds A and B and their respective individual compounds 13 and 1 anion analogs. Time-kill trials were performed using a hybrid plankton-sessile procedure that evaluates the bioavailability of plankton and sessile flora. A natural mixed aerobic flora collected in a sample from an operating cooling tower was used as an inoculum for the test. The biocide test concentration of Compound B was 10 ppm. In these moles All other products were tested at the concentration. The biocide exposure time is 110 minutes.

The following procedure was used, which generally followed the biocidal test method: Walter, R. W. and Cooke, L. M., "2-(Decylthio) ethanamine Hydrochloride: A New Multifunctional Biocide Which Enhances Corrosion Inhibition," NACE Paper 410, 1997.

A sample of water was collected from a cooling tower containing a population of naturally mixed microorganisms that grow at different rates when cultured on Petrifilm. The flora of these cells grown on Petrifilm at 20-24 hours, 48-54 hours, and 120 hours was treated as a separate flora.

A stainless steel scrubber (13 mm outer diameter and 5.5 mm inner diameter) was independently fastened to a nylon fishing line, suspended in 900 ml of natural cooling tower water (CTW) and magnetically stirred at room temperature at a mild rate. A biofilm was formed on the surface of the scrubbers by 7 angels. Prior to the chemical treatment, 10 ml of the entire CTW was removed from the beaker and placed in a separate exposure test tube along with a single scrubber.

Test compounds were then added to each tube at an equimolar concentration. All exposure tests including untreated controls were performed in triplicate (i.e., with 3 scrubbers in each of the tubes). After the test compound was added, the tube was briefly mixed by gentle vortexing and occasionally vortexing from start to finish during the exposure time.

The scrubber ultrasonic treatment was performed by the following chemical treatment to release the unreleased organism: after 120 minutes of exposure, the scrubber was removed from the tube, dipped in Letheen broth for 10 times, and then placed in a 9 ml without The bacteria in the Betterfield buffer tube was ultrasonicated and took 8 minutes.

The viable cell population was assayed in this total water: 1 ml of water from the exposure tube was plated on Petrifilm. An additional 1 ml was added to a 9 ml tube containing Letheen broth and mixed by shaking 10 times. One ml of the whole was plated on Petrifilm, and 1 ml of the whole portion was added to a 9 ml tube containing Butterfields broth and shaken again 10 times. Serial dilutions of the dilution and subsequent 1/10 dilutions were repeated through a 10 ^-4 to 10 ^-5 dilution.

A 1 ml portion of the Letheen broth tube (where the scrubber was soaked 10 times) was plated on Petrifilm. Serial dilutions of the Letheen wash tube were not performed in these studies, but the amount of CFU rinsed from the scrubber has been determined in this mechanical wash step. It has been hypothesized that the tube may be primarily representative of plankton organisms that continue to exist by loosely adhering to the CTW of the scrubber.

The population of cells removed from the scrubber was determined by ultrasonic treatment: after the tube with the scrubber was ultrasonically treated, 1 ml of the whole portion was plated on Petrifilm and subjected to continuous in Butterfields buffer. Diluted and each dilution was plated on Petrifilm.

Colony forming units (CFU) were determined at different incubation times: After plating each of the solutions on Petrifilm, the films were incubated at 36 ° C for 24 hours. At the 20th hour, the Petrifilms were read and the CFU was recorded. This group is defined as a fast growing group.

The Petrifilms were then incubated at 36 ° C or room temperature for additional time and read at 54 hours. This second group is different from the fast A long population is defined as an organism of moderate growth rate.

Continue to grow and read the Petrifilm after 120 hours. The third population is also treated in a manner different from the population of such rapid and moderate growth rates and is referred to as a slow growth rate population.

As described above, each compound was evaluated in triplicate using three separate scrubbers and the results obtained were averaged. The average CFU/ml value was used to calculate the total plankton test population (CFU/10 ml) and the total sessile test population (CFU/scrubber) in each test system.

Based on the results of 3 experiments, we have the following conclusions:

1. In these tests, the plankton and scleroderella were exposed to 10 ppm of Compound B, which took 110 minutes to cause a modest reduction in both populations (the total plankton population was reduced by 63% and the total sclerotia was reduced by 80%). %).

2. Under the same experimental conditions and molar concentration, the results obtained by treatment with Compound 1 are very similar (within experimental error) to the results obtained using Compound B, which proves that the anion of Compound B is changed to 2- Hydroxypropane-1,2,3-tricarboxylic acid dihydrogen has no significant effect on the biocidal effectiveness of the parent compound B molecule.

3. Treatment with Compound A under the same experimental conditions and molar concentration resulted in a significant reduction in plankton and scleroderella (reduced by 97% and 96%, respectively).

4. Under the same experimental conditions and molar concentration, the results obtained by treatment with compound 13 are very similar (within experimental error) to the results obtained using compound A, which proves that the compound is similar to the case of using compound B. The anion of A is changed to 2-hydroxypropane-1,2,3-tricarboxylic acid dihydrogen for the The biocidal effectiveness of the parent compound A molecule has no significant effect.

The results are shown in Table 8 below and are graphically represented in Figures 5-8.

While the present invention has been described with reference to the preferred embodiments of the present invention, it will be understood by those skilled in the art that the present invention may be modified and modified without departing from the scope and spirit of the invention as claimed. Accordingly, the present description is to be considered as illustrative only and illustrative of the embodiments of the invention.

Claims (23)

A method for treating water in an IWT (Industrial Water Treatment) system comprising using a solution of a thioammonium or an oxy-ammonium salt of the formula (I) as an active agent: [RXR ¹ -NH ₃ ⁺ ] _z M ^-z ( I) wherein: R is a straight or branched C ₆ -C ₂₄ alkyl group or a straight or branched chain C ₆ -C ₂₄ alkoxy-C ₂ -C ₃ -alkyl; X is S or O; R ¹ Is a straight chain or branched chain C ₂ -C ₃ alkyl; z is an integer, at least 1, up to the total number of acidic protons at M; and M is an ionic moiety having a charge greater than or equal to , which is derived from an acid having one or more acidic hydrogens and having two or more groups which can coordinate with metal cations or electron-deficient sites on a metal surface, the groups being selected from a group consisting essentially of anions derived from: 2-hydroxypropane-1,2,3-tricarboxylic acid; 2,3-dihydroxysuccinic acid; phosphorus oxyhydroxide; (1-hydroxyethyl) -1,1-diyl)bis(phosphonic acid); 2,3,4,5-tetrahydroxyadipate; 2,3,4,5,6-pentahydroxyhexanoic acid; hydroxysuccinic acid; Phosphonic butane-1,2,4-tricarboxylic acid; 2,2',2",2"'-(ethyl-1,2-diyldiazo)tetraacetic acid; nitrogen Acetic acid; butane tetracarboxylic acid; 2-hydroxyphosphoninoacetic acid; polycarboxylic acid such as poly(prop-2-enoic acid) and poly(Z)-butenedioic acid; containing 2 or more prop-2- a polycarboxylic acid copolymer of an enoic acid, a (Z)-butenedioic acid, or a sulfonated prop-2-enoic acid-derived repeating unit; a C ₂ -C ₁₂ dicarboxylic acid comprising oxalic acid, butyl Acid, (Z)-butenedioic acid, adipic acid, and sebacic acid; and boron trihydroxide; carboxymethyl inulin, and alginic acid; and added as a liquid or a solid or as a a portion of the formulation of the compound of formula (I) to the water of the IWT system: a) in a continuous or semi-continuous manner, taking the time necessary to provide the desired control; or b) in the slug dosage regimen, taking about 1 day Up to about 2 months to provide the desired control; at an effective level, to provide at least two of the following uses: metal corrosion inhibition, scale inhibition, suspension dispersion, biocidal efficacy, or biofilm removal / Biofilm dispersion; and the IWT system was observed or tested to confirm that the desired control was obtained. The method of claim 1, wherein M is the anion derived from: 2-hydroxypropane-1,2,3-tricarboxylic acid; 2,3-dihydroxysuccinic acid; phosphorus oxyhydroxide (1-hydroxyethyl-1,1-diyl) bis(phosphonic acid); 2,3,4,5-tetrahydroxyadipate; 2,3,4,5,6-pentahydroxyhexanoic acid; Hydroxybutyric acid. The method of claim 1, wherein M is the anion derived from: 2-hydroxypropane-1,2,3-tricarboxylic acid; 2,3-dihydroxysuccinic acid; phosphorus oxyhydroxide; Or (1-hydroxyethyl-1,1-diyl) bis(phosphonic acid). The method of claim 1, wherein R is a straight chain or a branched C ₆ -C ₁₆ alkyl group. The method of claim 1, wherein R is a straight chain or a branched C ₈ -C ₁₄ alkyl group. The method of claim 1, wherein X is S, and the amine component of formula (I) is thiamine. The method of claim 6, wherein the thiamine is 2-(mercaptothio)ethylamine. The method of claim 1, wherein X is O, and the amine component of formula (I) is an oxygen-containing amine. The method of claim 8, wherein the oxygen-containing amine is aminopropyl oxane. The method of claim 6 or 8, wherein M is the anion derived from 2-hydroxypropane-1,2,3-tricarboxylic acid. For example, the method of claim 1 wherein z is 1. The method of claim 1, wherein the effective amount of the compound of formula (I) is from about 0.01 to 2000 ppm in the treated water of the IWT system. The method of claim 1, wherein the effective amount of the compound of formula (I) is from about 1 to about 200 ppm in the treated water of the IWT system. The method of claim 1, wherein the use provided is scale inhibition and suspension dispersion. The method of claim 1, wherein the industrial water treatment system is selected from the group consisting of: a cooling tower, a closed loop and an open loop heat exchanger, a plate and frame heat exchanger, a chiller, a fluid cooling system, a boiler, metal Processing fluid, oil and gas production well water, crude oil transfer pipe, oil storage container, natural gas transmission pipe, natural gas storage container, formation fragmentation operation and fluid, system using high efficiency heat transfer tower filling, pipeline cleaning (ingot) Reverse osmosis membrane, ultrafiltration membrane, sand filter and charcoal filter. A compound of the following formula (IA): [RXR ¹ -NH ₃ ⁺ ] _z Q ^-z (IA) wherein: R is a straight or branched C ₆ -C ₂₄ alkyl group or a straight or branched chain C ₆ - C ₂₄ alkoxy-C ₂ -C ₃ -alkyl; X is S or O; R ¹ is a straight or branched C ₂ -C ₃ alkyl group; z is an integer of at least 1, so the formula (IA) The compound is electrically neutral; and Q is an ionic moiety having a charge greater than or equal to 1, which is derived from an acid having one or more acidic hydrogens, and having two or more ones on a metal surface a group coordinated to a metal cation or an electron-deficient site, the group being selected from the group consisting essentially of 2,3-dihydroxysuccinic acid; (1-hydroxyethyl-1,1- Diyl) bis(phosphonic acid); 2,3,4,5-tetrahydroxyadipate; 2,3,4,5,6-pentahydroxyhexanoic acid; hydroxysuccinic acid; 2-phosphonium butane -1,2,4-tricarboxylic acid; 2,2',2",2"'-(butyl-1,2-diyldiazo)tetraacetic acid; nitrogen-based acetic acid; butane tetracarboxylic acid; - hydroxyphosphoninoacetic acid; polycarboxylic acids such as poly(prop-2-enoic acid) and poly(Z)-butenedioic acid; containing 2 or more prop-2-enoic acid-(Z)butene Acid or sulfonated prop-2-enoic acid derivatization The repeating unit of poly carboxylic acid copolymer; C ₂ -C ₁₂ dicarboxylic acids, which include succinic acid, (Z) - fumaric, adipic, and azelaic acid; carboxymethyl inulin; and Alginic acid. A compound according to claim 16 wherein X is S and Q is the anion derived from 2,3-dihydroxysuccinic acid; (1-hydroxyethyl-1,1-diyl) bis(phosphine) Acid); 2,3,4,5-tetrahydroxyadipate; 2,3,4,5,6-pentahydroxyhexanoic acid; hydroxysuccinic acid; 2-phosphonylbutane-1,2,4 -tricarboxylic acid; 2,2',2",2"'-(butyl-1,2-diyldiazo)tetraacetic acid; nitrogen-based acetic acid; butane tetracarboxylic acid; 2-hydroxyphosphoninoacetic acid Polycarboxylic acids such as poly(prop-2-enoic acid) and poly(Z)-butenedioic acid; containing 2 or more prop-2-enoic acid, (Z)-butenedioic acid, or sulfonated A polycarboxylic acid copolymer of a prop-2-enoic acid-derived repeating unit. The compound of claim 16, wherein the amine component is 2-(mercaptothio)ethylamine, and Q is the anion derived from: 2,3-dihydroxysuccinic acid; (1-hydroxyl B-1,1-diyl)bis(phosphonic acid); 2,3,4,5-tetrahydroxyadipate; 2,3,4,5,6-pentahydroxyhexanoic acid; hydroxysuccinic acid; -phosphorylbutane-1,2,4-tricarboxylic acid; 2,2',2",2"'-(butyl-1,2-diyldiazo)tetraacetic acid; nitrogen-based acetic acid; Alkanetetracarboxylic acid; 2-hydroxyphosphoninoacetic acid; polycarboxylic acid such as poly(prop-2-enoic acid) and poly(Z)-butenedioic acid; containing 2 or more prop-2-enoic acids, A polycarboxylic acid copolymer of (Z)-butenedioic acid or a sulfonated prop-2-enoic acid-derived repeating unit. The compound of claim 16, wherein X is O, and Q is the anion derived from: 2,3-dihydroxysuccinic acid; (1-hydroxyethyl) -1,1-diyl)bis(phosphonic acid); 2,3,4,5-tetrahydroxyadipate; 2,3,4,5,6-pentahydroxyhexanoic acid; hydroxysuccinic acid; Phosphonic butane-1,2,4-tricarboxylic acid; 2,2',2",2"'-(butyl-1,2-diyldiazo)tetraacetic acid; nitrogen-based acetic acid; butane a tetracarboxylic acid; 2-hydroxyphosphoninoacetic acid; a polycarboxylic acid such as poly(prop-2-enoic acid) and poly(Z)-butenedioic acid; containing 2 or more prop-2-enoic acid, A polycarboxylic acid copolymer of Z)-butenedioic acid or a sulfonated prop-2-enoic acid-derived repeating unit. The compound of claim 16, wherein the amine component is an aminopropyl oxane, and Q is the anion derived from: 2,3-dihydroxysuccinic acid; (1-hydroxyethyl- 1,1-diyl)bis(phosphonic acid); 2,3,4,5-tetrahydroxyadipate; 2,3,4,5,6-pentahydroxyhexanoic acid; hydroxysuccinic acid; 2-phosphorus Mercaptobutane-1,2,4-tricarboxylic acid; 2,2',2",2"'-(butyl-1,2-diyldiazo)tetraacetic acid; nitrogen-based acetic acid; butane tetra Carboxylic acid; 2-hydroxyphosphoninoacetic acid; polycarboxylic acid such as poly(prop-2-enoic acid) and poly(Z)-butenedioic acid; containing 2 or more prop-2-enoic acid, (Z a polycarboxylic acid copolymer of -butenedioic acid or a sulfonated prop-2-enoic acid-derived repeating unit. The compound of claim 16, wherein the Q anions are derived from 2,3-dihydroxysuccinic acid; and (1-hydroxyethyl-1,1-diyl) bis(phosphonic acid). A 2-hydroxypropane-1,2,3-tricarboxylate of aminopropyl oxane. A 2-hydroxypropane-1,2,3-tricarboxylate of 2-(mercaptothio)ethylamine.