WO2007008543A2 - Procede et appareil de production et d'acheminement de monochloramine dans des flux d'eau - Google Patents

Procede et appareil de production et d'acheminement de monochloramine dans des flux d'eau Download PDF

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Publication number
WO2007008543A2
WO2007008543A2 PCT/US2006/026245 US2006026245W WO2007008543A2 WO 2007008543 A2 WO2007008543 A2 WO 2007008543A2 US 2006026245 W US2006026245 W US 2006026245W WO 2007008543 A2 WO2007008543 A2 WO 2007008543A2
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WO
WIPO (PCT)
Prior art keywords
mixing chamber
water
monochloramine
source
chlorine
Prior art date
Application number
PCT/US2006/026245
Other languages
English (en)
Other versions
WO2007008543A3 (fr
Inventor
Stephen Axtell
Robert Cumming
Sam Jaffe
Jerry Johns
Robert Kim
Joe Phillips
Original Assignee
Zentox Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zentox Corporation filed Critical Zentox Corporation
Publication of WO2007008543A2 publication Critical patent/WO2007008543A2/fr
Priority to US11/703,918 priority Critical patent/US20080006586A1/en
Publication of WO2007008543A3 publication Critical patent/WO2007008543A3/fr
Priority to US12/362,787 priority patent/US20090173697A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/685—Devices for dosing the additives
    • C02F1/686—Devices for dosing liquid additives
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • C02F1/766—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens by means of halogens other than chlorine or of halogenated compounds containing halogen other than chlorine

Definitions

  • This disclosure relates to the field of treating and disinfecting water streams including potable, process, recreational and waste water.
  • the disclosure relates to a method and apparatus for the efficient and effective mixing and production of monochloramine. It also relates to delivering the monochloramine into the target water streams in order to control, reduce or eliminate microbial load. Aspects of the disclosure also provide methods improving the safety in the production and delivery of monochloramine.
  • Monochloramine is the preferred form of chlorine treatment in potable water distribution systems.
  • the term "distribution system" is used to describe the extended piping and holding tanks used to distribute potable water through a municipality.
  • Monochloramine has become the preferred form of treatment, as monochloramine is less likely than traditional forms of chlorine (i.e., liquid chlorine, gaseous chlorine, sodium hypochlorite, etc.) to interact with organics that may be found in potable water distribution systems.
  • traditional forms of chlorine i.e., liquid chlorine, gaseous chlorine, sodium hypochlorite, etc.
  • TPMs trihalomethanes
  • monochloramine is applied up to the maximum dosage of 4-mg/liter set by the EPA.
  • Prior approaches to the application of monochloramine to a potable water distribution line have been to introduce a chlorine source and an ammonia source at separate points to the full flow of water in the line. As the water travels past these two injection points, monochloramine is randomly formed from the almost instantaneous reaction of ammonia and chlorine and the slower reaction of organic to chlorine is minimized. It has been thought that this process reduces the potential for the formation of THMs. > There are different types of chloramines that are described in the literature.
  • Inorganic, or true, chloramines are produced by controlling the ratio of chlorine and ammonia during mixing.
  • the three species of inorganic chloramine that can be formed by the chlorine-ammonia reaction are monochloramine (NH 2 Cl), dichloramine (NHCl 2 ) and nitrogen trichloride (NCl 3 , also known as trichloramine).
  • Monochloramine is the preferred inorganic chloramine species for use in disinfecting drinking water distribution systems, as monochloramine is odorless and highly soluble in water.
  • Dichloramine and nitrogen trichloride are not desirable because they are less soluble in water and can be the source of taste and odor issues.
  • Nitrogen trichloride is an irritant and is highly insoluble and therefore easily stripped from water by aeration. Because of these characteristics, it is the only inorganic chloramine species that can off-gas to cause burning of the eyes and nasal passages.
  • the species of chloramine that is produced when combining ammonia and chlorine is determined largely by the ratio of chlorine to nitrogen (Cl 2 :N) used in the mixing process.
  • Cl 2 :N ratio of chlorine to nitrogen
  • prior art methods use a Cl 2 :N ratio in the range of about 3:1 to 5:1, with a typical value of about 4:1. Ratios less than about 5:1 result in the presence of monochloramine and some excess ammonia in the distribution system. Unfortunately, excessive ammonia found in many potable water distribution systems can cause undesirable bacterial re-growth.
  • Organochloramines An entirely different set of compounds, known as organochloramines, result from the chlorination of organic materials. Organochloramines are responsible for causing foul tastes and odors in some drinking water systems. Some of these organochloramine compounds are relatively insoluble and can readily off-gas and cause human irritation. Organochloramines are responsible for producing the chlorinous odors commonly encountered in swimming pools, and are often described as "chloramines" even though they are not true inorganic chloramines. Organochloramines are also generally considered to be non-biocidal.
  • the most common forms of the chlorine used in the formation of chloramines in the water treatment process are liquid chlorine packaged in special steel containers and sodium hypochlorite (bleach).
  • the most common form of the nitrogen used is anhydrous ammonia, commonly stored and transported as a liquid in pressure vessels.
  • Another form of ammonia is aqueous ammonia, NH 4 OH, most commonly a 20-30 percent solution of ammonia in de-ionized or softened water.
  • monochloramine is formed on site and is not regulated, the regulations involved in the transportation and storage of liquid chlorine and anhydrous and aqueous ammonia are substantial due to safety concerns.
  • Bleach although more expensive than liquid chlorine, is often used in order to reduce the regulations and safety concerns involved with the on site storage of liquid chlorine.
  • nitrite When nitrite is formed it can react with naturally occurring nitrosatable nitrogen precursors such as dimethylamine (DMA) to form potentially carcinogenic N-nitrosamines such as N-nitrosodimethylamine (NDMA).
  • DMA dimethylamine
  • NDMA N-nitrosodimethylamine
  • excess free ammonia can contribute to increasing the corrosiveness of the water to yellow metals (copper and copper alloys).
  • a method and apparatus for producing a high concentration of monochloramine on demand in an inventive and highly efficient mixing pipe system containing potable water is disclosed.
  • the monochloramine is produced in a make-up stream apparatus and immediately injected into an organically laden process water stream.
  • monochloramine can be efficiently manufactured by introducing controlled quantities of an ammonia source and a chlorine source in a small side-stream of water in a mixing chamber under turbulent flow conditions.
  • the ammonia source and chlorine source can be injected in either order.
  • the two injection points are separated by a sufficient distance to ensure that the first chemical is adequately diffused throughout the water prior to the injection of the second chemical.
  • a sufficient length pipe forming the mixing chamber insures that turbulent flow is maintained for a length of time sufficient to thoroughly mix the two chemicals to produce monochloramine.
  • the preformed monochloramine according to the invention can then be injected into a main water stream to produce a selected concentration of monochloramine. More efficient mixing according to the invention eliminates the need to inject excess ammonia into the treated water stream, which minimizes the likelihood of nitrification and the formation of carcinogenic N-nitrosamines.
  • the method and apparatus according to the invention minimize the production of nitrogen trichloride and dichloramine and eliminate the necessity of using excess ammonia in the manufacturing process, which is often the case in other traditional monochloramine mixing techniques.
  • the method and apparatus according to the invention is able to take any line pressure as it normally exists in the target water stream and produce superior mixing and monochloramine transfer results.
  • the benefits of the method and apparatus according to the invention significantly improve the economics of using monochloramine as a water disinfectant.
  • the use of a non-regulated ammonia source such as ammonium chloride and a less hazardous chlorine source such as sodium hypochlorite reduce the regulatory burdens and costs often encountered in traditional monochloramine production techniques.
  • exact proportions of the chlorine and ammonia containing ingredients can be metered into a potable water side-stream, thoroughly mixed in the inventive mixing chamber described herein, and then injected back into the main process water stream without creating an off-gassing issue or introducing excess ammonia that could act as a nutrient for subsequent bacterial growth.
  • the method and apparatus according to the invention for monochloramine production described herein will also be more desirable for small water treatment plant applications where the water flow rates swing widely, since the monochloramine is manufactured only as needed and can be applied in direct proportion to the flow rate and more easily controlled via proportional control logics and metering pumps at a lower cost than full pipe flow monochloramine production.
  • the same inventive process is used, but instead of a side-stream source of water, an independent source of potable water (make-up stream) is used for in-line manufacture of monochloramine, which is then injected into the organically laden process water stream.
  • the use of potable water via a make-up stream of process water ensures the highest purity of monochloramine using the least amount of raw ingredients.
  • FIG. 1 illustrates the components comprising the monochloramine mixing apparatus according to the invention. DETAILED DESCRIPTION OF THE INVENTION
  • FIG. 1 a schematic of a monochloramine mixing apparatus 100 according to the invention is shown.
  • the monochloramine mixing apparatus 100 has a mixing pump 102 that is in fluid communication with a potable water line 103.
  • the mixing pump 102 is in further fluid communication with a potable water header pipe 104.
  • the potable water header pipe 104 may supply any number of mixing apparatus 100 that feed different recirculation process water pipes 116.
  • the mixing pump 102 centrifugal or booster as appropriate for the conditions
  • the mixing chamber 106 in a first illustrative embodiment is a pipe having an interior diameter of approximately 1 A inch, which is approximately 25 feet in length. It is contemplated within the scope of the invention that the diameters and capacities of the various components can be sized according to the water treatment's capacity and requirements.
  • the mixing chamber 106 is in further fluid communication with an injection chamber 108, which in a first illustrative embodiment is a pipe having an interior diameter of approximately 3 A of an inch.
  • the water in the potable water line 103 and potable water header 104 is maintained under laminar flow conditions. According to the invention, when the water enters the reduced diameter mixing chamber 106 at approximately 6.5 gpm, bubble froth turbulence results.
  • An aqueous chlorine source 110 which in this first illustrative embodiment is sodium hypochlorite, is injected into the mixing chamber 106 at a location toward the beginning point of the mixing chamber 106. At a point approximately one third of the distance down the mixing chamber 106, after the injected chlorine has been thoroughly dispersed throughout the water stream, a liquid ammonia source 112 is injected into the mixing chamber 106 forming a combined water stream 114. It is contemplated within the scope of the invention that the ammonia source 112 can be added to the mixing chamber 106 prior to the chlorine source 110.
  • the combined water stream 114, containing chlorine and ammonia flow through the mixing chamber 106 in bubble froth turbulence forming monochloramine.
  • the mixing technique described in this invention we are able to 5 control the mixing ratio of chlorine to ammonia at an about 5:1 ratio.
  • the chlorine to nitrogen ratio of about 5:1 is a ratio maximizing production of monochloramine and minimize other undesirable compounds such as nitrogen trichloride or excess levels of ammonia.
  • ammonium chloride has a pH of about 5 to 6 in an about 1% to 10% aqueous solution.
  • the pH of ammonium chloride is particularly advantageous for the application described in this disclosure. As long as the pH is less than about 7, virtually all of the ammonia- nitrogen in the solution is in the form of the ammonium ion, which will not off gas.
  • ammonium chloride As the pH goes up, the ammonium ion is converted to ammonia, which is a gas and can come out of solution. This lack of off gassing of ammonium chloride is important related to worker safety during transportation, storage and handling. Additionally, ammonium chloride is not considered a hazardous chemical and is therefore not subject to
  • sources for the nitrogen component of monochloramine include but are not limited to ammonium sulfate, ammonium hydroxide and ammonium chloride.
  • the mixing chamber 106 has been sized to accomplish a desired velocity and residence time for the mixing of the potable water, chlorine source 110 and ammonia source 112 in bubble froth turbulence.
  • the mixing chamber 106 has been sized to accomplish a desired velocity and residence time for the mixing of the potable water, chlorine source 110 and ammonia source 112 in bubble froth turbulence.
  • chamber 106 is a pipe having numerous bends in order to fit the mixing chamber 106 within a limited space.
  • a straight pipe is preferable in order to form the mixing chamber 106 that does not negatively impact the bubble froth turbulent mixing, however, a pipe with bends is acceptable to form the mixing chamber 106.
  • the mixing chamber 106 can have an interior configuration of any geometric shape.
  • the mixing chamber 106 creates an environment in which there is bubble froth turbulence, when the laminar flow potable water enters it. According to the invention, bubble froth turbulence rather than plug flow or slug flow turbulence is preferable.
  • the bubble froth turbulence within the mixing chamber 106 at a desired velocity and for a necessary residence time allows for the efficient mixing of the chlorine source 110, ammonia source 112 and potable water.
  • the diameter and length of the pipe used in a first illustrative embodiment to form the mixing chamber 106 must fit within certain parameters. In order to determine the diameter and length of the pipe forming the mixing chamber 106 the following system requirements must be met. The flow rate through the entire system must be determined, hi the system described in the above first illustrative embodiment the flow rate is sufficient to supply 6.5 gpm through each mixing loop. The desired material to be used in the pipe forming the mixing chamber 106 is selected and a Reynolds Number for the flow of water through the pipe constructed of the desired material is determined.
  • any standard piping material that is inert to ammonia and chlorine can be used to form the mixing chamber 106 (e.g., stainless steel, PVC tubing, etc.); however, different materials have different surface characteristics, which in turn impact the flow rates required to accomplish the desired bubble froth turbulence in the mixing chamber 106.
  • the mixing chamber 106 in a first illustrative embodiment is made of Schedule 80 PVC.
  • the diameter of the pipe forming the mixing chamber 106 and mixing pump 102 size are determined by incorporating the Reynolds Number for the selected piping material, volume flows and desired velocity of the flows, hi a first illustrative embodiment, the velocity of the water/monochlorarnine stream while in bubble froth in the pipe forming the mixing chamber 106 is about ten feet per second.
  • the selected length of the pipe forming the mixing chamber 106 is a function of the pipe's diameter.
  • the size of the pipe forming the mixing chamber 106 is determined by the overall system flow and the mixing pump 102 sizing to achieve a nominal velocity of about ten feet/second through the mixing chamber 106.
  • the combined water stream 114 containing monochloramine exits the mixing chamber 106 into the injection pipe 108 and flows directly to a recirculation process water pipe 116. There is no need to pass this combined water stream 114 through any sort of diffusion device before it enters the recirculation process water pipe 116.
  • the scope of the invention includes the use of monitors 120 that are incorporated into application points that are being fed by said recirculation process water pipe 116 for the purpose of controlling the level of monochloramine present at said application point.
  • the monitors 120 in a first illustrative embodiment are monitors that measure total chlorine which includes monochloramine. Various regulatory guidelines require that total chlorine levels cannot exceed specified limits in poultry processing.
  • the monitoring and control system in this first illustrative embodiment has a feedback control to said chlorine sourcel 10 and said ammonia source 112. It is further contemplated within the scope of the invention that the monochloramine monitor 120 can have a feedback control to said mixing pump 102.
  • 116 is a direct continuous flow.
  • the use of a contact basin or system pressurization is not required, other than a normal pressure differential required to force the water through the mixing system and inject it into the process application.
  • the mixing apparatus according to the invention allows the utilization of the existing normal pressure in the target water stream without any need for re-pressurization or other modification to the normal line pressure other than a normal pressure differential required to pull the water through the mixing system. This pressure differential can be very small since the only pressure differential required is that necessary to overcome line pressures.
  • the monochloramine mixing apparatus according to the invention was incorporated into a poultry processing plant. A substantial quantity of monochloramine was produced according to the invention.
  • the target process water stream consisted of re-circulated process water from a poultry immersion chiller. In testing conducted at the poultry processing plant, concentrations of up to 3000 ppm of monochloramine were successfully added to the Recirculation Process Water Pipe 116, which through dilution in this stream is then diluted to about 50 ppm or less of total chlorine, which includes monochloramine, entering the poultry immersion chiller. With the monitoring control system, this level has been successfully controlled throughout abroad range of processing variations encountered over a sixteen-hour processing day.
  • diluting ammonium chloride to about a 24% solution allows it to be mixed in a tank of potable water and then re-circulated via a side-stream loop to which 12.5% sodium hypochlorite (i.e., bleach) was added to form monochloramine.
  • 12.5% sodium hypochlorite i.e., bleach
  • the system was tested for monochloramine and metered into the process water.
  • a day tank of up to 3,000 PPM of monochloramine could be safely produced with non-regulated components and reliably fed to a process water stream.
  • the side stream or make-up stream apparatus can be used in any water or other fluid stream needing disinfection such as the treatment of water in cooling towers in those environments where there is an opportunity for the cooling water to be exposed to high levels of organics.
  • traditional cooling tower feed water is potable water.
  • the water in cooling towers is treated to control for corrosion, scaling and bacterial growth. In those situations where there are high levels of organics in the cooling tower water, it becomes extremely hard to control bacterial growth.
  • cooling towers that are located in industrial areas where high levels of organics are in the air (e.g., petroleum refining plants, ammonia plants, pasteurizers, paper mills, organic chemical plants, etc.) will encounter the problems with bacterial growth.
  • petrochemical cooling towers are susceptible to organic contamination from process leaks and airborne scrubbing or organic vapors from processes. In a cooling water system, these contaminants can cause rapid, production limiting biological growth and must be countered by liberal use of non- oxidizing biocides.
  • the methods and devices according to the invention for the production of monochloramine can be used to beneficially treat water in air scrubbers, air washers and head boxes in paper mills and other process water and other fluid streams in heavy organic environments. It should also be further appreciated by those skilled in the art that the methods and devices according to the invention for the production of monochloramine can be used to apply monochloramine to applications that are in need of new biocides and that the ability to introduce new biocides are restricted due to EPA and other regulatory requirements for toxicity testing. EPA already approves monochloramine as it is used in drinking water supplies throughout the U.S. and the world. The toxicity of monochloramine has been studied extensively prior to its approval for use in the drinking water supply.
  • the methods and devices according to the invention for the production of monochloramine can be used for disinfecting swimming pools and spas with high organic loads in the water.
  • swimming pool waters are disinfected with chlorine.
  • the chlorine being added to the water will form organochloramines, which are ineffective biocides, will tend to off-gas and can cause irritation to eyes and nasal passages.
  • bromine is often used for water disinfection.
  • One of the problems with bromine treatment can be a skin rash.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

La monochloramine peut être fabriquée de façon efficace par introduction de quantités régulées d'une source d'ammoniaque et d'une source de chlore dans un petit flux d'eau secondaire dans un tuyau de petit diamètre en présence de conditions d'écoulement turbulent. La source d'ammoniaque et la source de chlore peuvent être injectées dans n'importe quel ordre et elles sont séparées par une distance suffisante pour garantir que la première substance chimique soit diffusée de façon adéquate à travers l'eau avant l'injection de la seconde substance chimique. Grâce à une chambre de mélange de longueur suffisante, l'écoulement turbulent est maintenu pendant une durée suffisante pour que les deux substances chimiques soient intimement mélangées de façon à produire la monochloramine. Cette technique de mélange permet de fabriquer des concentrations élevées de monochloramine à la pression atmosphérique sans dégagement gazeux.
PCT/US2006/026245 2005-01-13 2006-07-06 Procede et appareil de production et d'acheminement de monochloramine dans des flux d'eau WO2007008543A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US11/703,918 US20080006586A1 (en) 2006-07-06 2007-02-08 Method and apparatus for the production and delivery of monochloramine into water streams
US12/362,787 US20090173697A1 (en) 2005-01-13 2009-01-30 Method and apparatus for the production and delivery of monochloramine into water streams

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US69761405P 2005-07-08 2005-07-08
US60/697,614 2005-07-08

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US12/115,152 Continuation-In-Part US7767095B2 (en) 2002-07-16 2008-05-05 Pathogen reduction using chloramines

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/703,918 Continuation-In-Part US20080006586A1 (en) 2005-01-13 2007-02-08 Method and apparatus for the production and delivery of monochloramine into water streams

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WO2007008543A2 true WO2007008543A2 (fr) 2007-01-18
WO2007008543A3 WO2007008543A3 (fr) 2007-06-28

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2703360A1 (fr) * 2012-09-03 2014-03-05 Siemens Aktiengesellschaft Processus et dispositif de purification dýeau
CN110078154A (zh) * 2013-03-12 2019-08-02 3M创新有限公司 从水性溶液除去氯和/或氯胺
US11661363B2 (en) 2021-05-24 2023-05-30 Heart Water, L.L.C. Rainwater processing system and processing steps for producing potable functional water

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2747974A (en) * 1953-08-18 1956-05-29 Olin Mathieson Mixer
US2837409A (en) * 1954-03-10 1958-06-03 Univ Ohio State Res Found Chloramine process
US3038785A (en) * 1961-01-11 1962-06-12 Grace W R & Co Manufacture of chloramine
US20030232447A1 (en) * 2002-06-16 2003-12-18 Applied Spectrometry Associates, Inc. Water chloramination control system

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2747974A (en) * 1953-08-18 1956-05-29 Olin Mathieson Mixer
US2837409A (en) * 1954-03-10 1958-06-03 Univ Ohio State Res Found Chloramine process
US3038785A (en) * 1961-01-11 1962-06-12 Grace W R & Co Manufacture of chloramine
US20030232447A1 (en) * 2002-06-16 2003-12-18 Applied Spectrometry Associates, Inc. Water chloramination control system

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2703360A1 (fr) * 2012-09-03 2014-03-05 Siemens Aktiengesellschaft Processus et dispositif de purification dýeau
CN110078154A (zh) * 2013-03-12 2019-08-02 3M创新有限公司 从水性溶液除去氯和/或氯胺
CN110078154B (zh) * 2013-03-12 2022-02-22 3M创新有限公司 从水性溶液除去氯和/或氯胺
US11661363B2 (en) 2021-05-24 2023-05-30 Heart Water, L.L.C. Rainwater processing system and processing steps for producing potable functional water

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