TWI546262B - Improved biocontrol through the use of chlorine-stabilizer blends - Google Patents

Description

Improved biological control via the use of a chlorine stabilizer blend [Cross-reference to related applications]

Not applicable.

[Statement on Federally Funded Research or Development]

Not applicable.

At least one invention relates to compositions and methods for reducing biological activity in process streams (e.g., water-based process streams). The biological activity in the process stream can cause problems for a variety of reasons including, but not limited to, hygiene issues, handling equipment efficiency issues, and product quality issues. For example, in the papermaking process, high levels of biological activity have a detrimental effect on equipment operation. The problems associated with the manufacture of certain paper types (such as tissue/recycle products) are more pronounced because the high fungal content causes the following problems: failure to provide a biocide that renders the biocide sufficiently stable to make it less prone to (good persistence) The procedure; and the inability to provide a biocide sufficient to counteract the periodic spikes in biological activity (requiring lower stability/lower persistence). In addition, bleaching/treatment of recycled fibers poses another problem for papermakers because papermakers need to add sulfite (which quenches halogens, such as chlorine) and maintain chlorine in the system after bleaching/treatment of recycled fibers ( More specifically, there is a trade-off between maintaining a sustained level of chlorine in the papermaking system without adding more than the necessary halogen/chlorine. Therefore, there is a need to further improve biocide-stabilizer formulations and delivery protocols that can treat the system more efficiently and in an environmentally friendly manner, such as using less chlorine/halogen, which reduces halogen The by-products are formed.

At least one invention relates to methods and compositions that can effectively stabilize oxidative biocides. Oxidative biocides such as peroxide acid and halogen chemicals such as sodium hypochlorite have been widely used in the pulp and paper industry. These oxidizing biocides are highly effective in killing large numbers of microorganisms at once. Unfortunately, after it is introduced into the process water system, the oxidative biocide does not have natural stability and is susceptible to rapid oxidation and loses its effectiveness over time. In environments with extremely high numbers of microorganisms, such as in process water enriched with organic and inorganic materials available for microbial growth, a sufficient number of microorganisms can survive until the oxidative biocide has lost effectiveness. Therefore, unless sufficient residual biocide is present, the amount of microorganisms will recover soon after treatment with the oxidizing biocide. In some cases, a halogen-tolerant bacterial strain is produced due to repeated introduction of a single oxidizing biocide. This can lead to uncontrolled growth of bacteria in the system. (See , for example, Textbook: Disinfection, Sterilization, and Preservation , 5th ed., Seymour S. Block, Lippincott Williams & Wilkins, (2001) at least page 31 - page 57).

Since the repeated application of oxidative biocides is not commercially viable in many cases, the above problems are more complicated. Many oxidizing biocides adversely affect the paper brighteners, dyes, and other additives required to produce commercially acceptable paper products. Repeated introduction of oxidizing biocides may also corrode many paper machine parts.

One technique for solving this problem is to stabilize the oxidizing biocides to inhibit the viability of the microorganisms over a long period of time while attenuating the negative effects of the oxidizing biocides on the resulting paper and papermaking equipment. Previous attempts to stabilize oxidative biocides include the use of amino sulfonic acids, amine sulfonate stabilized chlorine, monochloramine, DMH stabilization as described in U.S. Patent Nos. 3,328,294, 3,749,672, 3,170,883, 5,565,109, and 7, 516,622. Halogen, AmBr-Cl ₂ and organic nitrogen stabilize chlorine. Despite the slight stability, these attempts have demonstrated that the effectiveness of biocides is lower than expected. N-hydrogen sources have also been used to stabilize oxidative biocides, but they are also unsatisfactory because the N-hydrogen source is volatile and its dosage requirements are too stringent. This stringency impedes flexible moiré adjustments, which are often necessary to accommodate the particular conditions of the particular water system being treated with the oxidative biocide. Thus, there is a clear need and application for an enhanced stabilized halogen biocide that is effective, compatible with other biocides, and flexible in dosage and concentration.

Another technique for solving this problem is described in U.S. Published Patent Application Nos. 2006/0231505A and 2003/0029812 A1, which disclose the use of biocide blends. Such blends typically include oxidized halogens, which initially kill the organism in large amounts; and another, more durable but less effective biocide, which provides longer term microbial inhibition. Unfortunately, many biocides are not themselves compatible with other biocides, and the use of multiple biocides, each with its own manufacturing and introduction problems, requires over-investment in complex application equipment. In addition, multiple biocide feeders are installed at multiple points along the papermaking line, greatly increasing the cost and complexity of adding biocides. Therefore, there is still a need for a simplified method of preparing biocides and feeds.

The technology described in this section is not intended to be an admission that any of the patents, disclosures, or other information referred to herein are "previous techniques" of the present invention. In addition, this section should not be considered to mean that a search has been made or that there is no other relevant information as defined in 37 CFR § 1.56(a).

At least one embodiment of the invention relates to a composition comprising: a source of halogen, urea, and another halogen stabilizer other than urea, optionally a base, the base being present in a concentration sufficient to provide greater than 10 to the composition pH value. The composition excludes the stabilized bromine compound as appropriate. The stabilizer may comprise an article from the list consisting of N-hydrogen compounds, ammonia, ammonium salts, ammonium amine sulfonates, ammonium sulfate, amine sulfonic acids, sodium amino sulfonates, cyanuric acid, butyl Diimine, urea, glycoluril, glycine, amino acid, and any combination thereof. The stabilizer may comprise at least two substance compositions each acting as a halogen stabilizer. The halogen source may be selected from the group consisting of a chlorine source, an alkali hypohalite, Cl ₂ gas, NaOCl, Ca(OCl) ₂ and electrically generated chlorine. The composition may contain: an alkali hypohalite, urea, and ammonium amido sulfonate. The urea and another halogen stabilizer may be in a ratio of 50:50 to each other.

At least one embodiment of the invention is directed to a method for reducing biological activity in a process stream, the method comprising providing the composition to a process stream. The composition can be added to the process stream by the following addition mode: forming a mixture of at least one base and a basic hypohalite having a concentration sufficient to maintain the pH of the final composition above 10, and twice Mixing the mixture with a second mixture comprising urea and the other stabilizer, wherein the secondary mixing Use a T-mixer as appropriate. The process stream can be a papermaking process stream. The papermaking process can be a process selected from the group consisting of tissue paper and/or paper towels, paperboard, packaging, pulping, and recycled pulping. The process stream can contain fungi. The process stream can have a sulfite concentration between 2 ppm and 50 ppm. The method can further comprise monitoring the biological activity in the process stream before and after the addition of the composition. The biological activity can be monitored by taking a sample of the process stream and painting the sample on a Petri dish or the like; or measuring the ATP content of the sample from the process stream; or taking the process Flowing the sample and monitoring the dissolved oxygen of the sample and optionally monitoring the redox potential of the sample, and optionally by increasing or decreasing the amount of one or more chemicals added to the process stream, wherein such The chemical substance includes the composition. The method can further comprise adding a second composition to the process stream comprising a halogen, urea, and excluding another N-hydrogen compound.

At least one embodiment of the invention is directed to a method of preventing the growth of microorganisms in a process water stream. The method includes the steps of introducing a composition into a process water stream. The composition comprises: a source of halogen, a halogen stabilizer comprising a mixture of sulfur-containing material and urea and/or ammonium sulfate in any ratio, and optionally a base. Sulfur-containing materials include amine sulfonic acids or their salt equivalents. The molar ratio of the amine sulfonic acid to the halogen atom in the halogen source is greater than 2:1.

The sulfur-containing material may further comprise a nitrogen stabilizer. The nitrogen stabilizer may be an article selected from the group consisting of ammonium sulfate, sodium aminosulfonate, and any combination thereof. The molar ratio of all sulfur in the halogen to the sulfur-containing material can be more than 2:1. The base can be sodium hydroxide. Halogen can be chlorine, sodium hypochlorite, 1,3,5-trichloroisocyano cyanide (TCCA), 1-bromo-3-chloro-5,5-dimethyl-2,4-imidazolidinone (BCDMH) and 1,3-dichloro-5,5-dimethyl-2,4-imidazolidindione (DCDMH). The method may further comprise the step of first adding a base to the aminosulfonic acid and subsequently adding urea and/or sodium sulfate.

The process water stream can be enriched with microbial foods such that a single halogen oxidizing biocide is ineffective for destroying the microbial population, but the composition is effective. The process water stream can be one selected from the group consisting of a cooling tower water stream and a papermaking process water stream. The ratio of the amino sulfonic acid or its salt to the nitrogen stabilizer can be optimized in any ratio between the considerations regarding biocidal efficacy and the effect on the chemical additives present in the process water stream. The ratio of the amine sulfonic acid or its salt to the nitrogen stabilizer can be optimized in any ratio between the considerations regarding biocidal efficacy and the corrosion of equipment present in the process water stream. The composition may not reduce the effectiveness of the OBA and DYE additives on the paper produced by the process when used in a papermaking process. The salt can be sodium aminosulfonate.

Other features and advantages are described herein, and such features and advantages will be apparent from the following description.

Embodiments of the invention are described below with particular reference to the drawings.

The following definitions are provided to determine how the terms used in this application and in particular the scope of the patent application should be interpreted. The organization defined is for convenience only and is not intended to limit any definition to any particular category.

"Alkali (alkali)" means a substance serving as a pH changes in the composition of chemical bases.

" Dye (DYE) " or " dye " means one or more compositions used in the paper industry to modify the optical properties of a substrate. Dyes typically contain chromophores and color-assisting groups and have good affinity for the fibers and compatibility with other additives in the paper industry.

" Nitrogen stabilizer " means a stabilizer containing at least one nitrogen atom.

" OBA " means an optical brightener based on a dye or pigment which is a component of a coating formulation typically applied to a paper substrate. The dye or pigment absorbs ultraviolet radiation and re-emits ultraviolet radiation at a higher frequency (blue) in the visible spectrum, resulting in a white, shiny appearance.

" Pigment " means a solid substance used to modify the optical properties of a substrate in a papermaking process.

" Halogen Source " means a halogen atom itself or a halogen atom associated with a cation counterpart.

" Halogen Stabilizer " means a halogen-based substance that exists to approximate the composition of a substance that acts as an oxidizing biocide, increasing the amount of time that the composition remains in a sufficient chemical state to continue to act as a biocide. Halogen stabilizers include, but are not limited to, materials that maintain the oxidizing power of the biocide composition (or slow the rate of loss of the oxidizing power).

" Stabilizer " means a composition of matter that increases the ability of an oxidizing halogen ion to maintain an oxidizing agent and is capable of slowly releasing free ions to maintain an effective biocide in a liquid environment.

" Substrate " means a sheet of paper, a sheet of paper precursor, a block of fibers or any other cellulose-based or synthetic fiber material that can be converted into a sheet by a papermaking process.

In the event that the above definitions or statements made elsewhere in this application are inconsistent with the meanings (clear or implicit) stated in the source, the dictionary, or the source incorporated by reference in this application, the present application and Terms in the scope of the patent application are to be understood in particular to be interpreted in accordance with the definition or description in the present application, and should not be construed in accordance with the common definition, the definition of the dictionary, or the definitions incorporated by reference. According to the above, in the case where the term can only be understood by dictionary interpretation, if the term is defined by Kirk-Othmer Encyclopedia of Chemical Technology , 5th edition, (2005), (published by Wiley, John & Sons, Inc.) , the definition should control how the term should be defined in the scope of the patent application.

As indicated above, the present invention provides a composition and method of using the composition for reducing the biological activity in a process stream by providing a higher effect of the biocide. Moreover, the use of biocides more efficiently, such as increasing the persistence of biocides in the system, if necessary, can provide environmental benefits because process operators can use less biocides to combat the process flow (eg, including Various types of microorganisms and bacteria in water-based systems, one example of which is a paper-based system.

The composition contains at least the following components: halogen, urea, and another halogen stabilizer other than urea. The stabilizer can be blended with chlorine or bromine to produce a milder oxidant. The benefits of halogen stabilization include increased durability of the halogen residue to improve control of microbial growth in biofilm or surface deposits and systems with long residence times and high halogen requirements.

Halogen stabilization also improves the compatibility of halogens with sensitive process additives including dyes, optical brighteners, polymers and corrosion control products. However, it has been observed in several instances that halogens are incorporated with stabilizers such as urea. It becomes too long lasting. Therefore, the procedure may not adequately control fungi and several types of bacteria (including sphingomonas and spore-forming bacteria). Some forms of stabilized halogens have higher volatility, thereby reducing the available halogen residues in the aqueous phase and causing vapor phase corrosion.

Optionally, in at least one embodiment, there are other components: a base at a concentration sufficient to provide a pH greater than 10. In at least one embodiment, the pH is greater than 12. In another embodiment, the pH ranges from 12 to about 13.5. The base may include one or more of the following chemicals: sodium hydroxide and potassium hydroxide.

Optionally, there are other components: the stabilized bromine compound is excluded from the composition.

With regard to halogen, in at least one embodiment, the halogen is selected from at least one of the group consisting of a source of chlorine, an alkali hypohalite, a Cl ₂ gas (eg, added to the H ₂ O stream prior to blending), NaOCl, Ca ( OCl) ₂ and chlorine produced by electricity.

In at least one embodiment, the composition comprises urea in combination with another stabilizer, including ammonium amine sulfonate, to stabilize the halogen for biological control.

In at least one embodiment, the stabilizer is an N-hydrogen compound.

In at least one embodiment, the N-hydrogen compound is ammonium amido sulfonate.

In at least one embodiment, the N-hydrogen compound excludes ammonium sulfate.

In at least one embodiment, the composition comprises: an alkali hypohalite, urea, and ammonium ammine sulfonate.

The ratio between urea and another stabilizer can vary depending on system conditions (eg, fungal content). For example, consider the following Kinetics: (a) a urea having a halogen; (b) another stabilizer having a halogen; and (c) a blend of a halogen having a halogen and another stabilizer having a halogen.

In at least one embodiment, the stabilizer blend between urea and another stabilizer is 50:50.

A method for reducing biological activity in a process stream, such as a process stream contained in a water system, is also disclosed. The method comprises: providing a composition to a process stream, wherein the composition comprises: a halogen, urea, and another stabilizer other than urea, optionally a base, the base having a concentration sufficient to provide greater than 10 to the composition The pH value; and optionally, the stabilized bromine compound is excluded from the composition.

In at least one embodiment, the composition is added to the process stream by the addition mode: forming a mixture of at least one base and an alkali hypohalite, the base being at a concentration sufficient to provide a pH greater than 10, and twice The mixture is mixed with a second mixture comprising urea and the other stabilizer, wherein the secondary mixing is optionally carried out using a T-type mixer.

In at least one embodiment, the method comprises: adding a second composition to the process stream comprising a halogen, urea, and excluding another N-hydrogen compound.

With regard to the order of addition of the components, in at least one embodiment, the composition is added to the process stream by the following addition mode: forming a mixture of at least one base and a basic hypohalite, the base being present in a concentration sufficient to provide greater than 10 Preferably, the pH is from 12 to 13.5, and the mixture is secondarily mixed with a second mixture comprising urea and another stabilizer. One of ordinary skill can mix the first mixture with the second mixture via a variety of techniques, such as devices.

In at least one embodiment, the first mixture and the second mixture are mixed together using a T-type mixer. The average technician should know what a T-type mixer is.

In at least one specific example, one of ordinary skill in the art can use a mixing chamber (such as that disclosed in U.S. Patent No. 7,550,060, the disclosure of which is incorporated herein by reference in its entirety) in

The process of the invention is applicable to a variety of process streams or aqueous based systems or water based systems or industry based systems or combinations thereof.

In at least one embodiment, the process stream is a papermaking process stream.

In at least one embodiment, the papermaking process is a process selected from the group consisting of tissue paper and/or paper towels, paperboard; packaging; pulping; and recycled pulping.

In at least one embodiment, the process stream contains a fungus.

In at least one embodiment, the process stream has a sulfite concentration of between 2 ppm and 50 ppm.

The efficacy of the composition for reducing biological activity can be measured by a variety of analytical techniques and control schemes.

In at least one embodiment, the process stream further comprises monitoring the biological activity in the process stream before and after the addition of the composition.

In at least one embodiment, the biological activity is monitored by taking a sample of the process stream and applying the sample to a culture dish or the like.

In at least one embodiment, the biological activity is monitored by measuring the ATP (adenosine triphosphate) content of the sample from the process stream.

In at least one specific example, the biological activity is obtained by taking the process stream And monitoring the dissolved oxygen of the sample and optionally monitoring the redox potential of the sample and optionally monitoring by increasing or decreasing the amount of one or more chemicals added to the process stream, Wherein the chemical substance comprises the composition.

The compositions themselves or compositions for treating the process stream can be prepared outside of the process stream or within the process stream (in situ) or in combinations thereof.

In at least one embodiment, a composition comprising a halogen, a halogen stabilizer, and optionally a base is provided for inhibiting the growth of microorganisms in a papermaking environment. The stabilizer is a composition containing sulfur. Sulfur-containing materials include aminosulfonic acids (or their salt equivalents, such as sodium sulfamate). The molar ratio of halogen to aminosulfonic acid exceeds 2:1. By having such large ratios of halogens and stabilizers, it has been observed that unexpected biocidal effects can occur. This system is quite surprising because no significant anti-biological efficacy was observed at a 1:1 molar ratio of halogen to aminosulfonic acid. In addition, since a stabilizer is required to stabilize the halogen, it is expected that a more stable stabilizer will stabilize the halogen relative to the halogen, but the reverse is true.

In at least one embodiment, the stabilizer is a composition comprising a mixture of a sulfur-containing material and urea. The halogen is mixed with the amino sulfonic acid in a nitrogen:chloromo ratio of more than 2:1. By such a stabilizer mixture with a stabilized halogen, it has been observed that an unexpected synergistic effect can occur, which allows the halogen to remain stable over a longer period of time without damaging the paper produced. Quality or corrosion of papermaking equipment.

In at least one embodiment, the stabilizer is a composition comprising a mixture of a sulfur-containing material and ammonium sulfate.

In at least one embodiment, the sulfur-containing material further comprises nitrogen stable Agent.

In at least one embodiment, the nitrogen stabilizer is an article selected from the group consisting of ammonium sulfate, sodium aminosulfonate, or any combination thereof.

In at least one embodiment, the molar ratio of all sulfur in the halogen to the sulfur-containing material is more than 2:1.

In at least one embodiment, the base is sodium hydroxide.

In at least one embodiment, the halogen is chlorine, sodium hypochlorite, 1,3,5-trichloroisocyano cyanide (TCCA), 1-bromo-3-chloro-5,5-dimethyl-2,4- Imidazopyridinedione (BCDMH) and 1,3-dichloro-5,5-dimethyl-2,4-imidazolidindione (DCDMH).

In at least one embodiment, the base is first used to modify the amine sulfonic acid and then the urea/ammonium sulfate is added. Sodium hypochlorite is added to the above mixture.

In at least one embodiment, the sulfur-containing nitrogen is first combined with sodium hypochlorite in a nitrogen:chloromorbi ratio of more than 2:1 and subsequently added to the urea or ammonium sulfate.

In at least one embodiment, the urea or ammonium sulfate is first combined with sodium hypochlorite and subsequently added to the sulfur-containing nitrogen at various ratios. The order is important because different stabilized halogen species are produced at different rates due to different equilibrium constants. These differences can be considered to be caused by the administration of halogens in different amounts and in different orders. Chlorine is also capable of transferring self-stabilizing chlorine to other nitrogen species, so the order of consolidation can compensate for this.

In at least one embodiment, the composition is free of buffering agents.

In at least one embodiment, the composition is free of base.

In at least one embodiment, the composition can be formulated in situ by mixing the components together prior to mixing with the halogen oxidant.

In at least one embodiment, the composition can be formulated in situ by mixing the components as illustrated in any of Figures 1, 2, and/or 3.

In at least one specific example, the microorganism killed by the biocide is a sessile organism. In at least one embodiment, the microorganism killed by the biocide is plankton.

A significant benefit of the present invention is the fact that the amine sulfonic acid and the nitrogen stabilizer are readily combined so that a high product yield is achieved when mixing the two with minimal waste. Additionally, unlike separate stabilizers containing inorganic nitrogen stabilizers, mixtures of amine sulfonic acids with nitrogen stabilizers can function in many different ratios. Thus, the relative amounts of the amine sulfonic acid or nitrogen stabilizer may be suitably increased or decreased depending on the particular environment in which they are to be used. For example, where the nitrogen stabilizer may interfere with a particular paper additive such as OBA or DYE, the relative amount of amino sulfonic acid will increase. Conversely, in the case where the aminosulfonic acid has a compatibility problem, the amount of the nitrogen stabilizer can be increased.

In at least one specific example, the details of the formulation are for the nature of the biological infection. For example, if the bacteria are beginning to infiltrate one or more parts of the processing equipment, a formulation containing a relatively equal amount of the amino sulfonic acid and the nitrogen stabilizer is used because the formulation is optimized to cause a low impact on the additive. And low corrosivity, which is more desirable when using a highly effective biocide when the infection is weaker. Conversely, when the contamination is dense or long-term colony formation, the effectiveness of the biocide is more important than the primary effect on the additive or corrosion, and therefore the use of more amino sulfonic acid (relative to the nitrogen stabilizer) a molar amount of the formulation. Thus, by using a formulation with only two variables, many conditional ratios are available, which require a single input system but can Dynamically respond to different conditions within the life cycle of an industrial facility.

In at least one embodiment, the composition is used as a biocide in a cooling tower.

In at least one embodiment, the composition is used to reduce biofilm on the surface. The biofilm is an accumulation of solid organisms on the surface of the device. These accumulations often cause specific problems because the available exposed surface area at which the biocide acts is reduced. In addition, there is usually a trade-off between the biocide efficacy and the effect of the biocide on the biofilm, but the present invention avoids the deleterious effects on the processing equipment and still effectively neutralizes the biofilm.

In at least one embodiment, the composition is used to treat microorganisms in a thin film system. Thin film systems are generally prone to biofilm colony formation because microorganisms find the surface of the film system (due to composition, shape, or both) attractive. Because of its extreme precision relative to other forms of processing equipment, the general trade-offs are more pronounced in thin films. Fortunately, the composition is effective in treating film biofilms without damaging the biofilms. In at least one embodiment, the film system is a water permeable film. In at least one embodiment, the film is part of a water treatment system.

In at least one embodiment, the composition has a particular pH prior to introduction into the system. In at least one embodiment, the pH is greater than 5 and less than 12, and most preferably between 8 and 10.

In at least one embodiment, the ratio of the contents of the composition is balanced to optimize the effectiveness and utility of the composition. In the prior art, the chloramine sulfonate was used in a ratio of 1:1 with chlorine. This causes a stronger than desired chlorine bond and thus reduces the rate at which the amine sulfonate is released from the sulfate, thereby reducing the group The effectiveness of the adult. In at least one specific example, the ratios are different, and thus the composition is more effective. In at least one embodiment, the ratio of the amine sulfonate to the stabilizer in the composition is between (less than 4): 1 and (greater than 1): 1. Experimental data have shown that, in some cases, as a biocide, the ratio of 1:1 to 4:1 does not work at all or at least does not function adequately, the ratio of 8:1 to 4:1 is slightly effective and 3 : 1 is highly effective. This experimental data shows that the synergistic effect is not only based on the synergistic effect of concentration, the synergistic effect is completely novel and unexpected.

Example

The above is a better understanding of the present invention, which is provided for illustrative purposes and is not intended to limit the scope of the invention.

A number of biocide formulations were prepared and applied to process water samples from paper mills. Its composition and effectiveness are listed in Figure 4 and Table 1. Table 1 illustrates that a composition comprising 12% aminosulfonic acid and 3% ammonium sulfate can achieve high product yields without the addition of NaOH. Table 1 also shows that the addition of NaOH to the bleach improves the feasibility of blending the stabilizer at different rates.

Optimization of blending conditions for mixed stabilizers and sodium hypochlorite

Figure 4 illustrates that 12% amino sulfonic acid and 3% ammonium sulphate show higher inhibition of biological activity compared to other stabilizer combinations.

Without being limited by the theory and scope of the scope of the patent application provided, the salt chloride can be naturally transferred back and forth from one chlorinated nitrogen species to another chloronitrogen species according to the following equilibrium equation, and the present invention uses different equilibrium constants to produce In particular, the presence of the desired reaction of the chlorine-nitrogen species is optimized, and such chlorine-nitrogen species are effective as biocides.

In at least one embodiment, the order of administration of the compositions is corrected to optimally use the relative equilibrium rate of the plurality of chemical reactions. Each chemical reaction occurs at a different rate, and thus Cl species are constantly moving back and forth between molecules and have different availability at different times. In at least one specific example, downstream The reagents required to react are first added to the composition and the reagents are reacted slightly or completely prior to the addition of the reagents required for the faster reaction. This avoids a faster reaction and a slower reaction. In at least one embodiment, the reagent required to react the chloramine sulfonate species with the amine to form chloramine and ammonia is added to the composition only after the chloramine has been partially or completely formed.

In at least one embodiment, the composition is diluted to produce a milder (and severely reactive, less destructive or less destructive) biocide effect. In at least one embodiment, the method of diluting the biocide disclosed in U.S. Patent Nos. 6,132,628 and 7,067,063 is used. In at least one embodiment, the composition is diluted such that the materials are present in the range of 100 ppm to 150,000 ppm.

Although the invention may be embodied in many different forms, the specific preferred embodiments of the invention are shown in the drawings. The invention is exemplified by the prior art and the principles of the invention, and the invention is not intended to be limited to the specific embodiments illustrated. All patents, patent applications, scientific papers, books, and any other cited materials referred to anywhere herein are hereby incorporated by reference in their entirety. Furthermore, the invention encompasses any possible combination of some or all of the various embodiments described herein and incorporated herein.

The above disclosure is intended to be illustrative and not exhaustive. This description will present many variations and alternatives to those of ordinary skill in the art. All such alternatives and variations are intended to be included within the scope of the patent application, the term "comprising" means "including (but not limited to)". Those skilled in the art will recognize other equivalent forms of the specific embodiments described herein. The equivalents are also intended to be covered by the scope of the patent application.

All ranges and parameters disclosed herein are to be understood as encompassing any and all sub- For example, the range of "1 to 10" shall be taken to include any and all subranges between the minimum 1 and the maximum 10 (and including the endpoints); that is, from the minimum 1 or more 1 starts (eg 1 to 6.1) and ends with a maximum of 10 or less than 10 (eg 2.3 to 9.4, 3 to 8, 4 to 7), and finally every number 1, 2, 3, 4 included in this range All subranges of 5, 6, 7, 8, 9, and 10.

This completes the description of the preferred and alternative embodiments of the invention. Other equivalents of the specific embodiments described herein will be recognized by those skilled in the art, and such equivalents are intended to be covered by the scope of the accompanying claims.

1 is a flow chart illustrating a method of combining components of a biocide composition.

2 is a second flow diagram illustrating a method of combining components of a biocide composition.

3 is a third flow diagram illustrating a method of combining components of a biocide composition.

Figure 4 is a graph showing information showing the effectiveness of the present invention.

Claims (17)

A composition comprising: a halogen source, urea, and another halogen stabilizer other than urea, optionally a base, the base being present in a concentration sufficient to provide a pH greater than 10 for the composition; and optionally The stabilized bromine compound is excluded. The composition of claim 1, wherein the stabilizer comprises an article from the list consisting of N-hydrogen compounds, ammonia, ammonium salts, ammonium amine sulfonates, ammonium sulfates, amine sulfonic acids, Sodium amino sulfonate, cyanuric acid, succinimide, urea, glycoluril, glycine, amino acids, and any combination thereof. The composition of claim 1, wherein the stabilizer comprises at least two substance compositions each acting as a halogen stabilizer. The composition of claim 1, wherein the halogen source is selected from the group consisting of at least one of: a chlorine source, an alkali hypohalite, a Cl ₂ gas, NaOCl, Ca(OCl) ₂ and an electrical one. Produced chlorine. The composition of claim 1, wherein the composition comprises: an alkali hypohalite, urea, and ammonium amminesulfonate. The composition of claim 1, wherein the urea and the other halogen stabilizer are in a ratio of 50:50 to each other. A method for reducing biological activity in a process stream, comprising: providing a process stream with a composition as in claim 1 of the scope of the patent application. The method of claim 7, wherein the composition is added to the process stream by the following addition mode: forming a mixture of at least one base and a basic hypohalite, the base having a concentration sufficient to be in the final composition Offer or A pH greater than 10 is maintained, and the mixture is secondarily mixed with a second mixture comprising urea and the other stabilizer, wherein the secondary mixing is optionally carried out using a T-type mixer. The method of claim 8, wherein the process stream is a papermaking process stream. The method of claim 9, wherein the papermaking process is a process selected from the group consisting of tissue paper and/or paper towels, cardboard; packaging; pulping; and recycled pulping. The method of claim 9, wherein the process stream contains a fungus. The method of claim 9, wherein the process stream has a sulfite concentration of between 2 ppm and 50 ppm. The method of claim 9, further comprising monitoring the biological activity in the process stream before and after the addition of the composition. The method of claim 13, wherein the biological activity is monitored by taking a sample of the process stream and applying the sample to a culture dish or the like. The method of claim 13, wherein the biological activity is monitored by measuring the ATP content of the sample from the process stream. The method of claim 13, wherein the biological activity is monitored by taking a sample of the process stream and monitoring the dissolved oxygen of the sample and monitoring the redox potential of the sample as appropriate, and borrowing as appropriate Responding to increasing or decreasing the amount of one or more chemicals added to the process stream, wherein the chemical includes the composition. The method of claim 9, further comprising: adding a second composition to the process stream, wherein the second composition contains a halogen, a urea and excludes another N-hydrogen compound.