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    • 专利摘要:
    method and apparatus for producing a biocide. The present invention relates to a method and an apparatus for producing a biocide from a hypochlorite oxidant and an ammonium salt. the method includes monitoring a control parameter to optimize the ratio of hypochlorite oxidant to ammonium salt. the control parameter can be oxidation-reduction potential, conductivity, induction or oxygen saturation.
    公开号:BR112015018854B1
    申请号:R112015018854-0
    申请日:2014-02-06
    公开日:2021-08-24
    发明作者:Ayala Barak
    申请人:A.Y. Laboratories Ltd；
    IPC主号:
    专利说明:

    CROSS REFERENCE TO RELATED PATENT APPLICATIONS
    [001] Reference is made to U.S. Provisional Patent Application no. Serial 61/761,922, filed February 7, 2013 and entitled METHOD FOR CONTROLLING THE PRODUCTION OF A BIOCIDE, the description of which is incorporated by reference herein and whose priority is claimed herein in accordance with 37 CFR 1.78(a) (4) and (5)(i).
    [002] Reference is made to U.S. Patent Application no. Serial 07/892,533, filed June 1, 1992 entitled PROCESS AND COMPOSITIONS FOR WATER DISINFECTION, to U.S. Patent Application no. Serial 08/809,346, filed January 27, 1998 and entitled METHOD AND APPARATUS FOR THE TREATMENT OF LIQUIDS TO INHIBIT THE GROWTH OF LIVING ORGANISMS, and to U.S. Patent Application no. Serial No. 10/586,349, filed July 14, 2006 and entitled BIOCIDES AND APPARATUS, the descriptions of which are incorporated herein by reference. FIELD OF THE INVENTION
    [003] The present invention relates to a method to control and optimize the production of a biocide. BACKGROUND OF THE INVENTION
    [004] Several techniques are known for the production and use of biocides. BRIEF DESCRIPTION OF THE INVENTION
    [005] The present invention aims at providing a method and an apparatus to control and optimize the production of a biocide.
    [006] Thereby, according to a preferred embodiment of the present invention, there is provided a method for producing a biocide, which includes: mixing a solution of a hypochlorite oxidant with a solution of a ammonium salt; and monitoring a control parameter that indicates when a maximum yield of the biocide has been reached, where yield can be achieved without degradation of the biocide; where the control parameter is not pH. Preferably, the hypochlorite oxidant is sodium hypochlorite.
    [007] According to a preferred embodiment of the present invention, the solution of a hypochlorite oxidant is prepared by diluting a commercial starting solution of about 8 to 18% with water immediately before use. Preferably, the solution of a hypochlorite oxidant has a concentration of from about 1,000 to about 20,000 ppm, more preferably from about 3,000 to about 10,000 ppm, and even more preferably from about 3,000 to about 6,000 ppm .
    [008] According to a preferred embodiment of the present invention, the ammonium salt is selected from ammonium bicarbonate, ammonium carbonate, ammonium carbamate, ammonium hydroxide, ammonium sulfamate, ammonium bromide, ammonium chloride and sulphate ammonium. Preferably, the ammonium salt is selected from ammonium carbonate, ammonium carbamate, ammonium sulfamate, ammonium bromide, ammonium chloride and ammonium sulphate. Most preferably, the ammonium salt is selected from ammonium carbonate, ammonium carbamate and ammonium sulfamate. Even more preferably, the ammonium salt is selected from ammonium carbonate and ammonium carbamate.
    [009] According to a preferred embodiment of the present invention, the solution of an ammonium salt is prepared by diluting a commercial starting solution of about 15 to 50% with water or with the solution of a diluted hypochlorite oxidant immediately before of use. Preferably, the solution of an ammonium salt has a concentration of from about 1,000 to about 50,000 ppm and more preferably from about 12,000 to about 30,000 ppm. According to a preferred embodiment of the present invention, the solution of an ammonium salt also includes a base. Preferably, the base is sodium hydroxide.
    [0010] Preferably, the control parameter is selected from oxidation potential - reduction (ORP), conductivity, induction, total dissolved solids (TDS), oxygen concentration and oxygen saturation. In one modality, the control parameter is the ORP. In an alternative modality, the control parameter is conductivity, induction or TDS. In yet another modality, the control parameter is the oxygen concentration or oxygen saturation.
    [0011] According to a preferred embodiment of the present invention, the method includes: providing a discrete amount of the solution of an ammonium salt; and adding a plurality of discrete amounts of the solution of a hypochlorite oxidant to the discrete amount of the solution of an ammonium salt under mixing conditions; and measuring the control parameter after adding each discrete amount of a hypochlorite oxidant solution. Alternatively, a plurality of discrete amounts of an ammonium salt solution are added to a discrete amount of a hypochlorite solution under mixing conditions while measuring the control parameter.
    [0012] According to another preferred embodiment of the present invention, the method includes: mixing a stream of a hypochlorite solution with a stream of an ammonium salt solution in a mixing chamber at an initial ratio; the maintenance of the flow of one of the currents constant and the gradual increase or decrease of the flow of the other of the currents; and monitoring the value of the control parameter in a stream leaving the mixing chamber. In one modality, monitoring is continuous. In an alternative modality, monitoring includes measuring the control parameter in discrete samples of the current leaving the mixing chamber.
    [0013] According to another preferred embodiment of the present invention, there is also provided a method for producing a biocide, which includes: providing a solution of a hypochlorite oxidant; the provision of a solution of an ammonium salt; diluting the ammonium salt solution with a portion of the hypochlorite oxidant solution to form an ammonium salt dilution; and mixing the remainder of the hypochlorite oxidant solution with the ammonium salt dilution. Preferably, the hypochlorite oxidant is sodium hypochlorite.
    [0014] According to a preferred embodiment of the present invention, the solution of a hypochlorite oxidant is prepared by diluting a commercial starting solution of about 8 to 18% with water immediately before use. Preferably, the solution of a hypochlorite oxidant has a concentration of from about 2,000 to about 20,000 ppm, more preferably from about 3,000 to about 10,000 ppm, and even more preferably from about 3,000 to about 6,000 ppm .
    [0015] According to a preferred embodiment of the present invention, the ammonium salt is selected from ammonium bicarbonate, ammonium carbonate, ammonium carbamate, ammonium hydroxide, ammonium sulfamate, ammonium bromide, ammonium chloride and sulphate ammonium. Preferably, the ammonium salt is selected from ammonium carbonate, ammonium carbamate, ammonium sulfamate, ammonium bromide, ammonium chloride and ammonium sulphate. Most preferably, the ammonium salt is selected from ammonium carbonate, ammonium carbamate and ammonium sulfamate. Even more preferably, the ammonium salt is selected from ammonium carbonate and ammonium carbamate.
    [0016] According to a preferred embodiment of the present invention, the solution of an ammonium salt is prepared by diluting a commercial starting solution of about 15 to 50% with water or with the solution of a hypochlorite oxidant immediately before the use. Preferably, the solution of an ammonium salt has a concentration of from about 1,000 to about 50,000 ppm, and more preferably from about 12,000 to about 30,000 ppm.
    [0017] According to a preferred embodiment of the present invention, the solution of an ammonium salt also includes a base. Preferably, the base is sodium hydroxide. In accordance with a preferred embodiment of the present invention, the portion of the solution of a hypochlorite oxidant used to dilute the solution of an ammonium salt is from about 10% to about 50% of the solution of a hypochlorite oxidant.
    [0018] Preferably, the method also includes monitoring a control parameter that indicates when a maximum biocide yield has been reached, whereby the yield can be achieved without biocide degradation. Preferably, the control parameter is selected from oxidation-reduction potential (ORP), conductivity, induction, TDS, oxygen concentration and oxygen saturation. In one modality, the control parameter is the ORP. In an alternative modality, the control parameter is conductivity, induction or TDS. In yet another modality, the control parameter is oxygen saturation or oxygen concentration.
    [0019] According to a preferred embodiment of the present invention, the method includes: adding a plurality of discrete amounts of the solution of a hypochlorite oxidant to the ammonium salt dilution under mixing conditions; and measuring the control parameter after adding each discrete amount of a hypochlorite oxidant solution.
    [0020] According to another preferred embodiment of the present invention, the method includes: mixing a stream of a hypochlorite solution with a stream of diluting ammonium salt in a mixing chamber at an initial ratio; the maintenance of the flow of one of the currents constant and the gradual increase or decrease of the flow of the other of the currents; and monitoring the value of the control parameter in a stream leaving the mixing chamber. In one modality, monitoring is continuous. In another modality, monitoring includes measuring the control parameter in discrete samples of the current leaving the mixing chamber.
    [0021] According to another preferred embodiment of the present invention, there is also provided an apparatus for producing a biocide, which includes: a reservoir containing a solution of a hypochlorite oxidant; a reservoir containing a solution of an ammonium salt; a mixing chamber for mixing the hypochlorite oxidant with the ammonium salt to form a biocide; and a control cell for monitoring a biocide control parameter that indicates when a maximum biocide yield has been reached, whereby yield can be achieved without biocide degradation; where the control parameter is not pH. Preferably, the hypochlorite oxidant is sodium hypochlorite.
    [0022] According to a preferred embodiment of the present invention, the apparatus also includes a source of water; and a conduit in which a solution of a hypochlorite oxidant is mixed with water to form a hypochlorite dilution, in which the conduit is coupled to the mixing chamber. Preferably, the apparatus also includes a conduit in which the ammonium salt solution is mixed with water or with the hypochlorite dilution to form an ammonium salt dilution, with the conduit being coupled to the mixing chamber.
    [0023] Preferably, the ammonium salt is selected from ammonium bicarbonate, ammonium carbonate, ammonium carbamate, ammonium hydroxide, ammonium sulfamate, ammonium bromide, ammonium chloride and ammonium sulfate. Most preferably, the ammonium salt is selected from ammonium carbonate, ammonium carbamate, ammonium sulfamate, ammonium bromide, ammonium chloride and ammonium sulphate. According to a preferred embodiment of the present invention, the solution of an ammonium salt also includes a base. Preferably, the base is sodium hydroxide.
    [0024] Preferably, the control parameter is selected from oxidation potential - reduction (ORP), conductivity, induction, TDS, oxygen concentration and oxygen saturation. In one modality, the control parameter is the ORP. In an alternative modality, the control parameter is conductivity, induction or TDS. In yet another modality, the control parameter is oxygen saturation or oxygen concentration.
    [0025] According to a preferred embodiment of the present invention, the apparatus also includes a control unit configured to: keep the flow of one of the hypochlorite oxidant and the ammonium salt constant and gradually increase or decrease the flow of the other among the hypochlorite oxidant and the ammonium salt; monitor the biocide control parameter value; and adjust the flow rate of the hypochlorite oxidant or ammonium salt to achieve maximum biocide yield, where yield can be achieved without biocide degradation.
    [0026] According to another preferred embodiment of the present invention, there is also provided an apparatus for producing a biocide, which includes: a reservoir containing a solution of a hypochlorite oxidant; a reservoir containing a solution of an ammonium salt; a water source; a conduit for mixing the solution of a hypochlorite oxidant solution with water to form a hypochlorite dilution; a conduit for mixing an ammonium salt solution with a portion of the hypochlorite dilution to form an ammonium salt dilution; and a mixing chamber for mixing a portion of the hypochlorite dilution with the ammonium salt dilution to form a biocide. Preferably, the hypochlorite oxidant is sodium hypochlorite.
    [0027] Preferably, the ammonium salt is selected from ammonium bicarbonate, ammonium carbonate, ammonium carbamate, ammonium hydroxide, ammonium sulfamate, ammonium bromide, ammonium chloride and ammonium sulfate. Most preferably, the ammonium salt is selected from ammonium carbonate, ammonium carbamate, ammonium sulfamate, ammonium bromide, ammonium chloride and ammonium sulphate. According to a preferred embodiment of the present invention, the solution of an ammonium salt also includes a base. Preferably, the base is sodium hydroxide. Preferably, the portion of the hypochlorite dilution mixed with the ammonium salt solution is from about 10% to about 50% of the hypochlorite oxidant solution.
    [0028] According to a preferred embodiment of the present invention, the apparatus also includes a control cell for monitoring a biocide control parameter that indicates when a maximum yield of the biocide has been reached, whereby the yield can be achieved without degradation of the biocide. Preferably, the control parameter is selected from oxidation-reduction potential (ORP), conductivity, induction, TDS, oxygen concentration and oxygen saturation. In one modality, the control parameter is the ORP. In an alternative modality, the control parameter is conductivity, induction or TDS. In yet another modality, the control parameter is oxygen saturation or oxygen concentration.
    [0029] According to a preferred embodiment of the present invention, the apparatus also includes a control unit configured to: maintain the flow rate of one of the hypochlorite dilution and the constant ammonium salt dilution and gradually increase or decrease the flow rate of the another between the hypochlorite dilution and the ammonium salt dilution; monitor the biocide control parameter value; and adjust the flow rate of hypochlorite dilution or ammonium salt dilution to achieve maximum biocide yield, where yield can be achieved without biocide degradation. BRIEF DESCRIPTION OF THE DRAWING
    [0030] The present invention will be understood and appreciated more fully from the following detailed description, taken in conjunction with the drawing, in which:
    [0031] Figure 1 is a simplified diagram of an apparatus according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION
    [0032] As described in published European Patent Publication no. 0 517 102, the contents of which are incorporated by reference herein, biological fouling of circulating water is a well-known problem caused by algae, fungi, bacteria and other simple life forms found in circulating water. This patent publication describes the control of biofouling in waters with a high demand for chlorine by mixing two components, one of which is an oxidizer and the other an ammonium salt, and by adding the mixture substantially immediately to the aqueous system to be treated. This produces the active biocidal ingredient as described therein. A large number of examples of oxidants and ammonium salts are described in this patent publication.
    [0033] A problem encountered in this method of liquid treatment to inhibit the growth of living organisms, however, is that the concentrated active biocidal ingredient is extremely chemically unstable and decomposes rapidly with formation, with the result that there is a drop rapid in pH. This is especially so for biocidal active ingredients derived from ammonium bromide where decomposition results in the undesirable formation of HOBr. Therefore, when dosing pumps and conventional mixers are used, the biocidal active ingredient formed quickly decomposes and loses its effectiveness. Furthermore, although the pH range of such a concentrated active biocide is theoretically 8.0 to 12.5, actually the pH never exceeds 8.0 because of rapid decomposition. Also, ammonium salts must be oversupplied in order to reduce the rate of decomposition.
    [0034] In US Patent 5,976,386, the contents of which are incorporated by reference herein, a method and apparatus are provided for the production of a biocide that allows a constant oxidant/amine source ratio to be maintained, that thus avoiding the need to use an excess amine source in order to stabilize the reaction product and maintain a reproducible product that contains almost no degradation products. The new method described therein includes producing an efficient in situ dilution of both the oxidant and the amine source and synchronously introducing the two dilutions into a conduit for continuous mixing therein according to a predetermined ratio to produce an ingredient active biocide.
    As already described in U.S. Patent 5,976,386, careful control of biocide formation is necessary. The biocide production process uses a multiple feed point system that requires separate control for each feed line, as different pumps respond distinctly to changing pressure, and pump feed rates are dependent on the pressure of the flow. Water. As with any in situ process, an in-line control is necessary to ensure that the correct product is obtained at a high yield, and with minimal side products. Furthermore, as shown in the aforementioned patents, equimolar amounts of ammonium and hypochlorite are required for optimal performance. Excess hypochlorite, even in local excess, leads to the production of multichlorinated chloramines and degradation of the biocidal product monochloramine (MCA) to form NOx species and inorganic acids. With insufficient hypochlorite, the ammonia does not fully react, leading to a lower concentration of the biocide, an excessive use of chemicals, a higher treatment cost, etc. The components used to produce the biocide, such as sodium hypochlorite and ammonium carbamate, described in US Patent 7,837,883, the contents of which are incorporated by reference herein, are unstable chemicals, and degrade over time. of time during use. As a result, operation of the feed unit under predetermined constant feed rates of the two reactants will result in variable products. In addition, other parameters such as water temperature, high concentration of biocide produced and water quality can enhance biocide degradation and cause the biocide to degrade before the 1:1 equimolar ratio is reached.
    [0036] Thus, there is a need to keep the system at the equimolar point or at the point of highest possible yield of the biocide without any degradation by continuously monitoring the in-line reaction and making the necessary changes in the process to maintain equimolarity or no degradation under changing conditions (eg reagent concentration, different feed points, changes in dilution water quality, changes in dilution water temperature, etc.). Defining an end point for the reaction is also crucial for producing the biocide in the field.
    [0037] In U.S. Patent 5,976,386 the use of pH as an indicator of the end point of the reaction between an ammonium salt and sodium hypochlorite is described. Adding hypochlorite to an ammonium salt solution increases the pH. However, after the equimolar point, hypochlorite begins to degrade the MCA biocide, forming inorganic acids, which lower the pH. In this way, pH can be used as an endpoint indicator.
    [0038] However, the effect of MCA degradation on pH is only visible at a pH of up to about 10.5. Above a pH of 10.5, the amount of acid needed to visibly lower the pH is so high that a significant excess of hypochlorite must be added before the pH change is observed. Therefore, the pH loses its sensitivity to MCA degradation and is not a reliable indicator of the endpoint at high pH. Some ammonium salts, such as ammonium carbamate, are stable only at high pH levels or a high alkalinity which dictates biocide production at a high pH and therefore additional endpoint indicators for MCA production a a high pH is needed.
    [0039] It is known to use pH and oxidation-reduction potential (ORP) to monitor chlorine demand during water disinfection. See, for example,
    [0040] a. Devkota et al., "Variation of Oxidation-Reduction Potential Along the Breakpoint Curves in Low-Ammonia Effluents", Water Environment Research 2000, 72(5):610-617;
    [0041] b. Karanfil et al., "Analysis of disinfection difficulties in two municipal water pollution control plants", Disinfection '98: The Latest Trends in Wastewater Disinfection: Chlorination vs. UV Disinfection, Proceedings, Baltimore, Apr. 19-22, 1998, 111-122;
    [0042] c. Kim et al., "New process control strategy for wastewater chlorination and dechlorination using ORP/pH", Water Sci Technol. 2006; 53(4-5):431-438;
    [0043] d. Kopchynski et al., "Comparisons of online ORP and residual chlorine monitoring/control systems for wastewater treatment plant final effluent chlorination", Conference Proceedings - Water Environment Federation Annual Conference & Exposition, 74th, Atlanta, GA, United States, Oct. 13-17, 2001, 4275-4295; and
    [0044] e. Yu, "Feed-forward dose control of wastewater chlorination using online pH and ORP titration", Chemosphere. 2004 Sep, 56(10):973-980.
    [0045] Other monitoring methods, such as colorimetric analysis, are also known. See, for example,
    [0046] f. Harp, "Specific Determination of Inorganic Monochloramine in Chlorinated Wastewaters", Water Environment Research 2000, 72(6): 706-713;
    [0047] g. Kobylinski et al., "On Line Control Strategies for Disinfection Systems: Success and Failure" Proceedings of the Water Environment Federation, WEFTEC 2006: Session 81 through Session 94, pp. 6371-6394; and
    [0048] h. Pollema, "Monitoring Monochloramine, Total Ammonia, and Free Ammonia in the Chlorination of Treated Wastewater", Proceedings of the Water Environment Federation, Disinfection 2000, pp. 168-181. Woodward et al., "Relationships between observed monochloramine decay rates and other physical and chemical parameters in a large scale experimental pipe system", Proceedings - Water Quality Technology Conference (1996), Volume Date 1995, (Pt. 1) , 935-949, discloses the use of oxygen concentration in addition to ORP to monitor chlorine species concentration in water distribution systems. U.S. Patent 8,012,758 discloses the use of dissolved oxygen to measure microbiological activity. There does not appear to be any report of the use of a control parameter other than pH to produce a monochloramine biocide at the maximum yield that can be obtained without degradation of the biocide.
    [0049] According to a first embodiment of the present invention, there is provided a method for the production of a biocide, which comprises mixing a solution of a hypochlorite oxidant with a solution of an ammonium salt and monitoring a control parameter which can indicate the proper ratio of hypochlorite to ammonium salt in order to produce the maximum amount of biocide without degrading the biocide.
    [0050] In one embodiment, the biocide is produced in a batch process. The batch process comprises adding a solution of a hypochlorite oxidant to a solution of an ammonium salt as they are mixed, monitoring a control parameter that can indicate that all of the ammonium salt has reacted, or that the biocide started to degrade, and the completion of the addition of the hypochlorite solution when the control parameter indicates that all the ammonium salt has reacted. The biocide produced in this way can be used immediately or stored for later use. During storage, control parameter monitoring can be continued to ensure the quality of the biocide and determine the point in time at which the biocide must be used or else it will degrade.
    [0051] In an alternative modality, the biocide is produced in a continuous process. In the continuous process, a hypochlorite solution and an ammonium salt solution are continuously mixed in a mixer, and a control parameter is monitored in-line at the mixer or in a conduit downstream of the mixer or measured on discrete samples removed from the mixer. The flow rate of one of the solutions is kept constant while the flow rate of the other solution is varied until the control parameter indicates that the ideal flow rate ratio has been reached to produce the biocide at the highest possible yield without degradation. Typically, control parameter monitoring is continued in order to identify the need to adjust flow rates as a result of a change in the concentration of one of the solutions. The biocide produced in the continuous process can be applied to a medium while it is being produced or it can be stored for later use.
    The hypochlorite oxidizer can be any hypochlorite oxidizer, such as the hypochlorite salt of an alkali metal or an alkaline earth metal. Preferably, the hypochlorite salt is sodium hypochlorite, potassium hypochlorite or calcium hypochlorite. Most preferably, the hypochlorite salt is sodium hypochlorite.
    [0053] The hypochlorite solution is preferably prepared by mixing a concentrated starting hypochlorite solution with water to form a hypochlorite dilution. The ammonium salt solution is preferably prepared by mixing a concentrated starting ammonium salt solution with water or the hypochlorite dilution to form an ammonium salt dilution. When the starting ammonium solution is diluted with water to prepare an ammonium salt dilution that is equimolar to the hypochlorite dilution, the final biocide concentration will be half the concentration of the hypochlorite dilution. On the other hand, when the starting ammonium solution is diluted with the hypochlorite dilution, the final concentration of the biocide will be equal to the concentration of the hypochlorite dilution.
    [0054] The concentration of the hypochlorite dilution is preferably from about 1,000 to about 20,000 ppm. More preferably, the concentration of the hypochlorite solution is from about 3,000 to about 10,000 ppm. Even more preferably, the concentration of the hypochlorite solution is from about 3,500 to about 7,000 ppm. The hypochlorite solution is preferably prepared by diluting a commercial starting solution of about 8 to 18% with water immediately before use. Preferably, the hypochlorite dilution is prepared immediately before use. When the biocide is formed in a continuous process, the hypochlorite dilution is preferably prepared in-line as needed.
    [0055] Any ammonium salt can be used in the method of the present invention. Preferably, the ammonium salt is selected from ammonium bicarbonate, ammonium bromide, ammonium carbamate, ammonium carbonate, ammonium chloride, ammonium hydroxide, ammonium sulfamate and ammonium sulphate. Most preferably, the ammonium salt is selected from ammonium bromide, ammonium carbamate, ammonium carbonate, ammonium chloride, ammonium sulfamate and ammonium sulphate. Even more preferably, the ammonium salt is selected from ammonium carbamate, ammonium carbonate and ammonium sulfamate. Most preferably, the ammonium salt is ammonium carbamate.
    [0056] In one embodiment, the ammonium salt dilution is prepared by diluting a starting solution of 15 to 50% of the ammonium salt in water to a concentration of about 1,000 to about 50,000 ppm and more preferably of about from 12,000 to about 30,000 ppm. Preferably, the ammonium salt dilution is prepared immediately before use. When the biocide is formed in a continuous process, the ammonium salt dilution is preferably prepared in-line as needed.
    [0057] In an alternative embodiment, the ammonium salt dilution is prepared by diluting the starting ammonium salt solution with a portion of the diluted hypochlorite solution. This method produces an ammonium salt dilution with a higher pH since the hypochlorite solution is basic. This is advantageous for some salts, such as ammonium carbamate, which are more stable at higher pH.
    [0058] In some embodiments, the initial pH of the ammonium salt dilution is preferably at least 9.0, more preferably at least 10.0, even more preferably at least 10.4, and more preferably at least 10.4. further preferably at least 10.8. In a preferred embodiment, the ammonium salt dilution comprises sodium hydroxide.
    [0059] The control parameter can be any parameter that has a) a fixed value that changes only if and when the ammonium salt has been depleted and degradation of the monochloramine product begins; or b) a variable value that has a maximum, a minimum or an inflection at the point that the ammonium salt has been depleted and degradation of the monochloramine product begins. For example, the value of the control parameter gradually increases as the ratio of hypochlorite to ammonium salt increases as the biocide is being produced, but starts to gradually decrease as degradation occurs. At the end point of biocide production, and just before the start of degradation, a maximum value is measured. Immediately as the degradation starts, the measured values are decreasing. Even if the absolute value of the control parameter depends on conditions such as concentration, water quality, temperature, etc., there will be a relative maximum value measured just before the biocide starts to degrade.
    [0060] The control parameter value must be easy to measure reliably and must be sensitive to reaction conditions. Preferably, the control parameter is selected from oxidation-reduction potential (ORP), conductivity and dissolved oxygen saturation. Both ORP and conductivity reach a minimum at the endpoint. Conductivity is essentially a measure of ion concentration. Induction and total dissolved solids (TDS) are also measures of ion concentration and can be used in place of conductivity as a control parameter. Any other measure of ion concentration can also be used.
    [0061] Oxygen saturation is close to 100% throughout the formation of the biocide. Once the end point has been reached and MCA degradation started, oxygen saturation begins to fall as the degrading biocide reacts with oxygen to form NOx species. at a certain point the saturation quickly drops to zero. An oxygen saturation of less than 90% is indicative of degradation. The point at which oxygen saturation begins to fall rapidly can be used to determine the end point. In some modalities, two or more selected control parameters of ORP, conductivity, and oxygen saturation are used. In other modalities, all of ORP, conductivity and oxygen saturation are used as control parameters. Oxygen concentration can also be used as a control parameter. Oxygen saturation is preferred as it is responsible for changes in solution temperature.
    [0062] Reference is now made to Figure 1, which is a simplified diagram of an apparatus for producing a biocide in accordance with an embodiment of the present invention.
    [0063] As shown in Figure 1, water is fed from a source 2, which may be a reservoir, by pump 4, through a water pipe 6 through parallel flow meters 8 and to a corresponding pair of branch lines 10 and 12, which are connected to a mixer 14 that feeds common outlet piping 16 leading to medium 18 at site 20. Outlet piping 16 can be equipped with a siphon switch 22, and can also be equipped with a control cell 24 to monitor a control parameter, such as pH, ORP, conductivity and oxygen saturation, of the biocide near the outlet of the outlet pipe 16. The water from source 2 can be fresh water of technical paper mill, chemically treated water, soft water, deionized water and recovered process water.
    [0064] Pumps 26 and 28, which can be, for example, pulsatile pumps, peristaltic pumps, Venturi pumps or their equivalents as known in the prior art, pump concentrated hypochlorite and concentrated ammonium salt, respectively, from the reservoirs 30 and 32, respectively, on lines 34 and 36, respectively. Between reservoirs 30 and 32 are metering tubes 38 and 40 and valves 42.
    Line 34 contains a junction 44 for directing the flow of hypochlorite to water pipe 6 via junction 46 or to branch line 10 via junction 48. Ammonium salt is fed into the branch line 12 through a splice 50. These splice parts can be, for example, simple T-connectors, or they can be in-line static mixers designed to facilitate mixing of the joined solutions with them.
    [0066] When the hypochlorite solution from line 34 is directed to water pipe 6, the diluted hypochlorite is fed into both branch lines 10 and 12 and the result is that the ammonium salt solution is diluted with the diluted hypochlorite . When the hypochlorite solution from line 34 is fed directly into branch line 10, the ammonium salt solution is diluted with water. Depending on the concentration of components in reservoirs 30 and 32, the ratio at which these components are pumped into lines 34 and 36, respectively, and the flow of water through lines 10 and 12, the hypochlorite oxidant and the compound containing nitrogen or salt of the same, can be diluted and mixed in desired proportions.
    [0067] The product of the reaction, that is, the biocide produced by the reaction of hypochlorite and the compound containing nitrogen or salt thereof, can thus be applied directly from the outlet pipe 16 in medium 18, within a short time after the biocide formation. In alternative embodiments of the invention (not shown), the mixer 14 is replaced by an inlet chamber or a junction part, in which case the dilutions mix and react as they flow through the outlet piping 16, so that at the time fluid flowing through outlet pipe 16 is introduced into medium 18, biocide is produced. In these alternative embodiments of the invention, the outlet piping 16, rather than the mixer 14, functions as a mixing chamber. The control parameter is measured in this way immediately with the mixture.
    [0068] Regardless of whether or not a mixer 14 is used, the flow through the outlet pipe 16 must be fast enough so that the biocide does not have time to decompose before introduction into the medium 18. The length of the pipe 16 can be adjusted to obtain the desired mixing time. In some embodiments of the invention, the time from which the diluted hypochlorite and the diluted ammonium salt are mixed together to form the biocide until the biocide reaches control cell 24 is 30 seconds or less, such as 12 to 24 seconds. In other modes, the time is from 30 to 90 seconds, such as 45 to 70 seconds. In other modalities, the time is from 90 seconds to three minutes. Also in other embodiments of the invention where the biocide is stable for more than a few minutes, the biocide may be stored (eg in a reservoir, not shown) prior to application to the medium 18.
    [0069] The control of the valves and pumps above can be performed by a control system (not shown). Branch lines 10 and 12 include control valves 52 and 54, respectively, to control the flow of water therethrough. The control system can control and monitor the supply of water from source 2 through an electrical valve 56. The water piping 6 can include additional control devices, such as a flow meter 58 to indicate flow rate or flow volume. . The flow of biocide to medium 18 at different locations 20 can be controlled by valves 60.
    [0070] The apparatus can also be configured with alarms or other signaling devices that can give feedback to the control system. Control cell 24 in outlet piping 16 can provide feedback to the control system to allow control of biocide production in response thereto. The illustrated system may also include a timer (not shown) that is pre-configurable to fix both time spans to which the biocide must be fed through the outlet pipe 16 to the medium 18 to be treated, as well as the intervals of time between such biocide feeds. The control system can also be operative to control the operation of the mixer 14. EXAMPLES Example 1
    [0071] An ammonium carbonate solution was formed by dissolving 100 g of ammonium carbonate and 50 g of sodium carbonate in 400 g of water. The resulting 18% w/w solution had a density of 1.094 g/ml. A concentrated sodium hypochlorite solution was diluted to a concentration of 5,000 ppm. 4.2 ml of the ammonium carbonate solution (9.00 mmol) was mixed with 30 ml of dilute hypochlorite and the resulting solution was titrated with dilute hypochlorite. The ORP, conductivity and pH of the solution were monitored throughout the titration. Thereafter, the procedure including the dilution of a concentrated ammonium salt solution into the hypochlorite solution will be indicated as the "new method".
    [0072] Since each mole of ammonium carbonate has two ammonium ions, the predicted end point of the reaction is at a hypochlorite/carbonate ratio of 2. The ORP reached a minimum ratio of 1.80 and the conductivity reached a minimum ratio of 1.72. On the other hand, the maximum pH was not reached until a ratio of 2.58, well beyond the end point. Thus, it is shown that ORP and conductivity can be used as endpoint indicators at high pH, whereas pH is not an appropriate indicator under these conditions.
    [0073] An ammonium carbonate solution was formed by dissolving 100 g of ammonium carbonate in 400 g of water. The resulting 20% w/w solution had a density of 1.137 g/ml. A concentrated sodium hypochlorite solution was diluted to a concentration of 7,900 ppm. 1.4 ml of the ammonium carbonate solution (3.32 mmol) was diluted with 50 ml of water and the resulting solution was titrated with the diluted hypochlorite. The ORP, conductivity and pH of the solution were monitored throughout the titration. Then the procedure including the dilution of a concentrated ammonium salt solution in water will be referred to as the "old method".
    [0074] A minimum of ORP was observed at a hypochlorite to carbonate ratio of 1.34. A pH maximum at pH = 11.73 was observed at a hypochlorite/carbonate ratio of 2.01. No minimum of conductivity was observed. It can be seen in this case that, when ORP can serve as an indicator even when the ammonium salt dilution is prepared by diluting a starting ammonium salt solution in water, a minimal conductivity was not detected and thus, conductivity is not an effective control parameter under these conditions. Example 2 - Ammonium Carbamate - New Method
    [0075] Ammonium carbamate and ammonium carbonate exist in a pH dependent balance, with the higher pH favoring ammonium carbamate. Since ammonium carbamate has one ammonium ion per mole whereas ammonium carbonate has two ammonium ions per mole, the amount of hypochlorite needed to fully react with an ammonium carbamate or ammonium carbonate solution depends on the mixture. formed between these two compounds.
    [0076] A 20% stock solution of ammonium carbamate was formed by dissolving 20 g of ammonium carbamate and varying amounts of sodium hydroxide in water. 5.5 ml of the starting ammonium carbamate solution was diluted with 3200 ppm or 5,000 ppm of sodium hypochlorite, and the resulting solution was titrated with the remaining hypochlorite. The ORP, conductivity and pH of the solution were monitored throughout the titration.
    [0077] Table 1 shows the reaction conditions for various tests, as well as the maximum pH observed and the minimum ORP and conductivity. Table 1


    [0078] It can be seen from the results in Table 1 that the amount of hypochlorite needed to complete the reaction decreases with increasing pH. This is to be expected since, as the pH increases, the balance shifts to carbamate and there is less ammonium available. It was found that the ideal ratio between carbamate and hydroxide is 0.75. At this ratio, both the ORP and the minimum conductivity occur at a carbamate to hypochlorite ratio of about 1. It can be seen in all tests that the maximum pH occurs well after the minimum ORP and the minimum conductivity, showing that so the pH is not an effective control parameter under these conditions. Example 3 - Ammonium carbonate - new method
    [0079] A starting 20% solution of ammonium carbonate was formed by dissolving 20 g of ammonium carbonate and varying amounts of sodium hydroxide in water. 5.5 ml of the starting ammonium carbonate solution was diluted with 5,000 ppm of sodium hypochlorite and the resulting solution was titrated with the remaining hypochlorite. The ORP, conductivity and pH of the solution were monitored throughout the titration. Table 2 shows the reaction conditions for various tests, as well as the maximum pH and minimum observed ORP and conductivity.

    [0080] It can be seen from the results in Table 2 that the amount of hypochlorite needed to complete the reaction decreases with increasing pH. This is to be expected since as the pH increases the balance shifts to the carbamate and there is less ammonium available. It was found that the ideal ratio between carbonate and hydroxide is 1.1 to 1.2. At this ratio, both the minimum ORP and conductivity occur at a carbonate to hypochlorite ratio of about 1. It can be seen in all tests that the maximum pH occurs well after the minimum ORP and minimum conductivity, showing that so the pH is not an effective control parameter under these conditions.
    [0081] It is also expected that the ideal ratio between hydroxide and carbonate is higher than carbamate. A 1:1 ratio of hypochlorite:carbonate/carbamate is observed when all species are converted to carbamate. More hydroxide is required for this when starting with carbonate than when starting with carbamate. In both cases, under very high pH conditions, the minimum ORP and conductivity were not observed. Reaction with other ammonium salts at very high pH showed the same trend, indicating that biocide production at very high pH is less efficient. Example 4 - Ammonium Sulfate - New Method
    [0082] A 28% starting solution of ammonium sulfate was formed by dissolving 28 g of ammonium sulfate in 72 ml of water. 0.45 ml of the starting ammonium sulfate solution and 0.25 ml of a 33% NaOH solution were diluted in 30 ml of a 4,000 ppm sodium hypochlorite solution, and the resulting solution was titrated with the hypochlorite remaining. The ORP, conductivity, pH and oxygen saturation of the solution were monitored throughout the titration.
    [0083] A minimum of ORP was observed at a hypochlorite/sulfate ratio of 0.78. It was at this ratio that oxygen saturation dropped below 90%. No pH maximums or minimum conductivity were observed. It can be seen that oxygen saturation can also serve as a control parameter. It can also be seen that two control parameters can be used together to further confirm the end point of the reaction.
    [0084] Other tests performed under different conditions show that various control parameters can be used when the correct reaction conditions are chosen. The initial pH of 15 of the diluted sulfate solution is adjusted by adding sodium hydroxide. The reaction conditions and results are summarized in Table 3.Table 3
    Example 5 - Ammonium Chloride - New Method
    [0085] A 23% starting solution of ammonium chloride was formed by dissolving 23 g of ammonium carbonate in 77 g of water. 0.43 ml of the starting ammonium chloride solution and 0.25 ml of a 33% NaOH solution were diluted in 30 ml of a 4,000 ppm sodium hypochlorite solution, and the resulting solution was titrated with the hypochlorite remaining. The ORP, conductivity, pH and oxygen saturation of the solution were monitored throughout the titration.
    [0086] A minimum of conductivity was observed at a hypochlorite/chloride ratio of 0.64. It was for this reason that the oxygen saturation dropped below 90%. No maximum pH or minimum ORP was observed. It can be seen that, by using a combination of several control parameters, it is ensured that the end point of the reaction can be determined by at least one control parameter.
    [0087] Further tests were performed to determine the effect of hypochlorite concentration and initial pH. The pH of the dilute ammonium chloride solution was adjusted by adding sodium hydroxide. ORP, conductivity and oxygen saturation were measured during the tests. The test conditions and results are shown in Table 4.Table 4

    [0088] These results show that, under a very high alkalinity, the biocide degrades much faster, and it is practically impossible to produce a 1:1 molar ratio without any degraded biocide. Example 6 - Ammonium Sulfamate - New Method
    [0089] A 20% stock solution of ammonium sulfamate was formed by dissolving 50 g of ammonium sulfamate in 200 g of water. 5.0 ml of the starting ammonium sulfamate solution was diluted in 30 ml of a 5800 ppm sodium hypochlorite solution, and the resulting solution was titrated with the remaining hypochlorite. ORP, conductivity and solution pH were monitored throughout the titration.
    [0090] A minimum of conductivity was observed at a hypochlorite/sulfamate ratio of 0.94. A minimum of ORP was observed at a hypochlorite/sulfamate ratio of 1.20. A pH maximum was observed at a hypochlorite/sulfamate ratio of 1.41. The discrepancy between the ORP and conductivity measurements may be due to the longer response time of the ORP electrode.
    [0091] In another test, 10 g of NaOH was added to the starting sulfamate solution. In this case, the conductivity and ORP were minimal at a hypochlorite/sulfamate ratio of 0.94, whereas the maximum pH only occurred at a hypochlorite/sulfamate ratio of 1.95. Delay in maximum pH is expected since the pH was higher due to the addition of NaOH and thus the system was less sensitive to pH change caused by MCA degradation. Example 7 - Ammonium Bromide - Old Method
    [0092] 1.6 ml of 35% starting ammonium bromide was diluted in 100 ml of water to form a 5,500 ppm ammonium bromide solution. A 12% starting sodium hypochlorite was diluted in water to form solutions at concentrations of 3,000 ppm (test 1), 4,000 ppm (test 2) and 5,000 ppm (test 3). 50 ml of the ammonium bromide solution were titrated with each of the hypochlorite dilutions. In addition, 50 ml of ammonium bromide containing 0.25 ml of a 33% NaOH solution was titrated with hypochlorite at 4000 ppm (test 4). The pH, ORP, conductivity and oxygen saturation of the solution were monitored during all titrations. The results are shown in Table 5. Table 5

    [0093] The pH increases slowly as the biocide is produced and decreases sharply when degradation is significant. In all four tests, a wide range for the maximum pH was observed, rather than a sharp point, in particular in test 4 where the initial pH was high due to the addition of NaOH. Acute decrease in pH degradation is easier to detect, although the maximum is the equimolar point. When the concentration of hypochlorite is higher, this point is easier to detect if excess NaOH is avoided. From there, it can be seen that it is not enough to have a good detection method. Conditions for producing the biocide, such as the concentration of hypochlorite, must also be controlled.
    [0094] A minimum of ORP was observed in all tests, which means that ORP is universal as a detection and control method. The minimum ORP can form a wide range, rather than a clear sharp point. The point to be controlled is the drop to a lower ORP, even though the sharp rise in ORP due to biocide degradation is easier to detect. A broad minimum indicates that the reaction conditions to produce the biocide are not ideal. The biocide is being degraded as it is being produced, and other conditions must be chosen to effectively produce the biocide.
    [0095] A minimum of conductivity was observed only when 3000 ppm of hypochlorite was used. In order to identify a minimum conductivity, a decrease in conductivity must be observed even when hypochlorite, which increases conductivity, is added. If hypochlorite is added in large steps, the additional conductivity of the hypochlorite masks the minimum conductivity, making it impossible to use the conductivity to control the reaction. Conductivity is thus less universal as a control parameter than ORP or pH, but it can be a more useful tool when applied correctly.
    [0096] Biocide degradation results in a decrease in oxygen saturation. Since degradation consumes oxygen, this method of monitoring degradation is the most sensitive and least dependent on reaction conditions. All tests showed a drop in oxygen saturation, first slowly and then a sharp drop to zero. An excess of NaOH slows down the degradation but does not stop it. Degradation starts at the same value, or even slightly earlier, but proceeds at a lower rate. FIELD EXPERIMENTS
    [0097] The general method for field experiments was as follows: A soft water source is provided. The water source can be split into two streams before any reagent is added to the supply water (old method), or concentrated sodium hypochlorite is mixed with the supply water to form diluted hypochlorite, which is split in two chains. Ammonium salt is added to one of the hypochlorite streams that contains 10 to 50% of the total volume of hypochlorite, and both streams are mixed in a mixing chamber (new method).
    [0098] Control elements can be placed in a control cell. The cell can be placed immediately after the mixing chamber, and in a short pipe it reached 12 to 24 seconds after mixing, or at a more distant point in a long pipe it reached 40 to 76 seconds after mixing. The measurement of pH, ORP, conductivity and oxygen saturation takes place in the control cell. In addition to the results of monitoring in the control cell, similar values are also manually measured at the output of the feed unit, about five minutes after biocide production.
    [0099] During the process to produce the biocide one of the feed rates of the reagent is fixed, while the feed rate of the other reagent is varied. Both hypochlorite and ammonium salt can be fixed. The variable feed rate can start from a lower feed rate, and gradually increase until excess chemical is added (then "increasing") or it can start from the higher feed rate, above. from the predicted reaction endpoint, and gradually decreases to a low feed rate, below the predicted reaction endpoint (then "lowering"). The following examples will show test results that vary the defined conditions of the reaction. Example 8 - Comparison of old and new methods
    [00100] Old method: 38.7 l/h of a 10% sodium hypochlorite solution was mixed with 400 l/h of water and fed into a reaction chamber. 45.3 l/h of an 18% ammonium carbamate solution comprising 9% NaOH was mixed with 350 l/h of water and fed into the reaction chamber. Carbamate flow was gradually decreased to 19.3 l/h. ORP, conductivity and pH were monitored in-line in the reaction chamber, and ORP and conductivity were manually confirmed by measuring the samples exiting the reaction chamber.
    [00101] The minimum conductivity was observed at a carbamate flow rate of 36.0 l/h, which corresponds to a hypochlorite/carbamate ratio of 0.58. The minimum ORP was observed at a carbamate flow rate of 31.9 l/h, which corresponds to a hypochlorite/carbamate ratio of 0.65. No pH maximum was observed.
    [00102] New method: In an alternative study, the 10% sodium hypochlorite solution was mixed with 750 l/h of water. 400 l/h of the resulting flux was fed into the mixing chamber, and the remainder was used to dilute the 18% ammonium carbamate solution. The carbamate solution thus diluted with the hypochlorite solution was also fed into the mixing chamber. The flow rate of the 18% carbamate solution was varied as in the previous study. In this case, the minimum conductivity was observed at a carbamate flow rate of 28.3 l/h, which corresponds to a hypochlorite/carbamate ratio of 0.74, and the minimum ORP was observed at a carbamate flow rate of 25.2 l/h, which corresponds to a hypochlorite/carbamate ratio of 0.82. Also in this case, no pH maximum was observed.
    [00103] From a comparison of these tests, it can be seen that, in the old method, in which the ammonium salt is diluted in water, the control parameters indicate a reaction end at a lower hypochlorite/carbamate ratio than than in the new method. This suggests that, in the old method, some biocide starts to degrade before the end point is reached. Furthermore, it was observed that the correlation between in-line and manual conductivity measurements when using the new method, as when using the old method, the conductivity measurements were unstable. The new method appears to be superior in this case.
    [00104] When ammonium carbonate was used as the ammonium salt, the results were somewhat different. No minimum conductivity was observed when using either method, and the same minimum ORP was observed when using both methods. Thus, in the case of ammonium carbonate there was no difference between the two methods. Example 9 - Variation of feed rates
    [00105] Several tests were performed according to the new general method described in Example 8, except that in some of the tests the ammonium carbamate feed rate was constant and the hypochlorite feed rate was stably increased (rising) , whereas in other tests the hypochlorite feed rate was kept constant and the ammonium carbamate feed increased (up) or decreased (down) stably. The hypochlorite concentration was 6,000 ppm. Table 6 summarizes the basic conditions and results for each test. The percentage of total flux of water used to dilute the ammonium carbamate is given as % flux for the ammonium.

    [00106] The results in Table 6 show that a minimum of ORP can be detected when using all of the following options: keep the ammonium carbamate feed rate fixed and increase the hypochlorite feed rate gradually, or keep the feed rate of fixed hypochlorite and increasing or decreasing the ammonium carbamate feed rate, although the values for the ORP minimum were different. Tests performed with a fixed ammonium carbamate feed and a variable hypochlorite feed show higher ORP minima at a hypochlorite:carbamate molar ratio higher than 1, indicating that some ammonium carbamate was converted to ammonium carbonate during the process.
    [00107] The minimum conductivity was clearly observed when the tests were performed with a fixed feed rate of hypochlorite and a variable feed rate of ammonium carbamate. There was no significant difference between increasing or decreasing carbamate feed. No minimal conductivity was detected when tests were performed with a fixed ammonium carbamate feed rate and a variable hypochlorite feed. The increase in conductivity due to the addition of hypochlorite to the ammonium carbamate apparently masks minimal end point conductivity. The endpoint can, however, be seen if the hypochlorite feed is increased too slowly. Example 10 - Flow split variation
    [00108] Several tests were performed according to the new general method described in Example 8, except that the percentage of total water flow used to dilute the ammonium carbamate was different in each test. Table 7 summarizes the basic conditions and results for each test.

    [00109] The results presented in Table 7 show that the best results are measured when using 10% of the total volume of water to dilute the ammonium salt, since the measurements for the ORP and the conductivity are the same. Example 11 - Retention time variation
    [00110] Several tests were carried out according to the general Nov method described in Example 8, except that the retention time of the mixing chamber outlet until reaching the control cell was different in each test. Different retention times were obtained when using different flow rates and when using long or short piping. Table 8 basically summarizes the conditions and results for each test.
    [00111] In-line and manual conductivity minima are similar in most tests. The differences between online and manual ORP readings are much greater than the differences in conductivity. This highlights a disadvantage of ORP that the electrode takes time to stabilize. As such, in-line readings may not be as accurate as manual readings. High ORP values at a shorter contact time can prove that the reaction is not yet complete at that point.

    [00112] Although the ORP values depend significantly on the retention time, the molar ratio shows less variability, and the ratio decreases only slightly as the retention time increases. This shows that a retention time is very useful, and a longer retention time is better than a short retention time. Example 12 - Hypochlorite concentration variation
    [00113] Varying amounts of a 7% sodium hypochlorite solution were mixed with 800 l/h of water. 400 l/h of the resulting flux was fed into the mixing chamber, and the remainder was used to dilute an 18% ammonium carbamate solution. The carbamate solution thus diluted with the hypochlorite solution was also fed into the mixing chamber. The stroke of the ammonium salt pump was varied in order to change the carbamate flow rate. pH, ORP and conductivity were measured in-line. Conductivity was measured using two different electrodes, a standard conductivity electrode and an inductive electrode.
    [00114] The procedure described above was repeated for three different concentrations of hypochlorite, 3700 ppm (test 1), 4400 ppm (test 2) and 4,800 ppm (test 3). No pH maximum was observed in any of the tests. In test 1, no minimum of ORP or conductivity was observed.
    [00115] In test 2, the minimum ORP occurred at a pump stroke of 50%, which corresponds to a carbamate flow rate of 17.3 l/h and a hypochlorite to carbamate ratio of 1.17. Both conductivity electrodes showed minima at a pump stroke of 55%, which corresponds to a carbamate flow rate of 19.6 l/h and a hypochlorite to carbamate ratio of 1.03. In test 3, the minimum ORP occurred at a pump stroke of 55%, which corresponds to a carbamate flow rate of 19.6 l/h and a hypochlorite to carbamate ratio of 1.14. Both conductivity electrodes showed minima at a 60% pump stroke, which corresponds to a carbamate flow rate of 22.0 l/h and a hypochlorite to carbamate ratio of 1.02.
    [00116] When ammonium carbamate is added to water, the ORP increases. When ammonium carbamate is added to the hypochlorite and the biocide is produced, the ORP decreases until the hypochlorite is depleted, at which point no more biocide is produced and the ORP starts to rise again. When the biocide is produced as described in this example and the hypochlorite concentration is low, the ORP tendency is to mimic the addition of ammonium carbamate to water, and no minimum ORP is detected. Increasing the concentration of hypochlorite and producing more biocide will reveal the expected minimum ORP.
    [00117] The conductivity follows a trend similar to that of ORP. When the hypochlorite concentration is low and only a small amount of biocide is produced, the decrease in conductivity due to biocide production is masked by the increase in conductivity due to the addition of ammonium carbamate. No minimum is thus observed. The minimum can be obtained by increasing the concentration of hypochlorite. In addition, the min is more easily detected by keeping the hypochlorite concentration fixed and by varying the ammonium concentration.
    [00118] In an additional set of tests, the hypochlorite concentration was the same in each test, but the fixed hypochlorite flow rate was different in each test. Ammonium carbamate flow rate was varied in each test to find the ideal ratio. The results are summarized in Table 9. It is again observed that very little hypochlorite in the system leads to equimolar point masking defined by the ORP or conductivity minima.

    [00119] These tests prove that many factors affect the efficiency of production of a monochloramine biocide. The temperature, duration of addition and mixing of chemicals, initial alkalinity, quality of the ammonium salt and accuracy of its assumed concentration, quality of hypochlorite and changes in quality that occur during dilution and production of the biocide , can all contribute to the efficient production of a biocide without degradation. Control is required to produce the biocide at its optimal yield, without degradation, under varying conditions.
    [00120] The oxidation-reduction potential, the concentration of ions as measured by conductivity or induction or by TDS, and oxygen saturation, can be used to control the production of the biocide. By looking at the results of the above tests, it can be seen that sometimes there is no ORP minimum, or no conductivity minimum, or both are missing. By varying the reaction conditions, more preponderantly the relative concentration of the reactants, the minima can be seen, or it can disappear.
    [00121] It should be appreciated by those skilled in the art that the present invention is not limited to what has been shown and particularly described above. Rather, the scope of the present invention includes combinations and subcombinations of various features described above, as well as modifications thereof which should occur to a person skilled in the art upon reading the above description and which are not in the prior art.
    权利要求:
    Claims (27)
    [0001]
    1. Method for the production of a biocide, characterized in that it comprises: mixing a solution of a hypochlorite oxidant with a solution of an ammonium salt to produce a biocide; monitor a control parameter that indicates when a maximum yield of said biocide has been reached, in which the yield can be achieved without degradation of said biocide; where the control parameter has a) a fixed value that changes only after said yield has been reached; or b) a variable value that has a maximum, a minimum or an inflection at the point at which said efficiency was reached; in which said control parameter is selected from oxidation-reduction potential (ORP), conductivity, induction and satu -ration of oxygen.
    [0002]
    2. Method according to claim 1, characterized in that said hypochlorite oxidant is sodium hypochlorite.
    [0003]
    3. Method according to claim 1, characterized in that said solution of a hypochlorite oxidant has a concentration of about 3,500 to about 7,000 ppm.
    [0004]
    4. Method according to any one of claims 1 to 3, characterized in that said ammonium salt is selected from ammonium bicarbonate, ammonium carbonate, ammonium carbamate, ammonium hydroxide, ammonium sulfamate, ammonium bromide - nio, ammonium chloride and ammonium sulfate.
    [0005]
    5. Method according to claim 4, characterized in that said ammonium salt is selected from ammonium carbonate and ammonium carbamate.
    [0006]
    6. Method according to claim 1, characterized in that said solution of an ammonium salt has a concentration of about 12,000 to about 30,000 ppm.
    [0007]
    7. Method according to any one of claims 1 to 6, characterized in that said solution of an ammonium salt also comprises a base.
    [0008]
    8. Method according to claim 7, characterized in that said base is sodium hydroxide.
    [0009]
    9. Method according to claim 1, characterized in that said control parameter is the ORP.
    [0010]
    10. Method according to claim 1, characterized in that said control parameter is conductivity or induction.
    [0011]
    11. Method according to claim 1, characterized in that said control parameter is oxygen saturation.
    [0012]
    12. Method according to any one of claims 1 to 11, characterized in that it comprises: providing a discrete amount of said solution of an ammonium salt; adding a plurality of discrete amounts of said solution of a hypochlorite oxidant to a said discrete amount of said solution of an ammonium salt under mixing conditions; measuring said control parameter after adding each discrete amount of said solution of a hypochlorite oxidant.
    [0013]
    13. Method according to any one of claims 1 to 12, characterized in that it comprises: mixing a stream of a hypochlorite solution with a stream of an ammonium salt solution in a mixing chamber at an initial ratio; maintain the flow of one of said constant currents and the gradual increase or decrease in the flow of the other of said currents; monitor the value of said control parameter in a stream exiting said mixing chamber.
    [0014]
    14. Method according to claim 13, characterized in that said monitoring is continuous.
    [0015]
    15. Method according to claim 13, characterized in that said monitoring comprises measuring the control parameter in discrete samples of said stream leaving said mixing chamber.
    [0016]
    16. Apparatus for producing a biocide, characterized in that it comprises: a reservoir containing a solution of a hypochlorite oxidant; a reservoir containing a solution of an ammonium salt; a mixing chamber for mixing said hi oxidant - pochlorite with said ammonium salt to form a biocide; and a control cell to monitor a control parameter that indicates when a maximum yield of said biocide has been reached, in which the yield can be achieved without degradation of said biocide; in which the control parameter has a) a fixed value that only changes after said yield has been reached; or b) a variable value that has a maximum, a minimum or an inflection at the point at which said efficiency was reached; in which said control parameter is selected from oxidation-reduction potential (ORP), conductivity, induction and satu -ration of oxygen.
    [0017]
    17. Apparatus according to claim 16, characterized in that said hypochlorite oxidant is sodium hypochlorite.
    [0018]
    18. Apparatus according to claim 16 or 17, characterized in that it also comprises: a source of water; and a conduit in which said solution of a hypochlorite oxidant is mixed with said water to form a hypochlorite dilution, wherein said conduit is coupled to said mixing chamber.
    [0019]
    19. Apparatus according to claim 18, characterized in that it further comprises a conduit in which said solution of an ammonium salt is mixed with said water or with said hypochlorite dilution to form an ammonium salt dilution , wherein said conduit is coupled to said mixing chamber.
    [0020]
    20. Apparatus according to any one of claims 16 to 19, characterized in that said ammonium salt is selected from ammonium bicarbonate, ammonium carbonate, ammonium carbamate, ammonium hydroxide, ammonium sulfamate, bromide of ammonium, ammonium chloride and ammonium sulfate.
    [0021]
    21. Apparatus according to claim 20, characterized in that said ammonium salt is selected from ammonium carbonate and ammonium carbamate.
    [0022]
    22. Apparatus according to any one of claims 16 to 21, characterized in that said solution of an ammonium salt further comprises a base.
    [0023]
    23. Apparatus according to claim 22, characterized in that said base is sodium hydroxide.
    [0024]
    24. Apparatus according to claim 16, characterized in that said control parameter is the ORP.
    [0025]
    25. Apparatus according to claim 16, characterized in that said control parameter is conductivity or induction.
    [0026]
    26. Apparatus according to claim 16, characterized in that said control parameter is oxygen saturation.
    [0027]
    27. Apparatus according to any one of claims 16 to 26, characterized in that it further comprises a control unit configured to: maintain the flow of one of said hypochlorite oxidant and said ammonium salt constant and increase or decrease gradually the flow rate of the other between said hypochlorite oxidant and said ammonium salt; monitor the value of said control parameter of said biocide; and adjust the flow rate of said hypochlorite oxidant or said ammonium salt to achieve a maximum yield of said biocide, whereby yield can be achieved without degradation of said biocide.
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    法律状态:
    2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-22| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-05-25| B15K| Others concerning applications: alteration of classification|Free format text: A CLASSIFICACAO ANTERIOR ERA: C02F 1/76 Ipc: A01N 59/00 (2006.01), C02F 1/76 (2006.01), A01N 25 |
    2021-06-29| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-08-24| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/02/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201361761922P| true| 2013-02-07|2013-02-07|
    US61/761,922|2013-02-07|
    PCT/IL2014/050130|WO2014122652A1|2013-02-07|2014-02-06|Method for controlling the production of a biocide|BR122017002175-3A| BR122017002175B1|2013-02-07|2014-02-06|METHOD FOR THE PRODUCTION OF A BIOCIDE|
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