The present invention relates to controlling the rates of chemical additives dosed in process water in the water treatment industry. In particular, the invention relates to controlling the dosing rates and to the resulting concentration of the diluted chemical additives in the process water.
Cases of dosing chemical additives within threshold limits are well known in the water treatment industry. The threshold dosing method is an on/off method of dosing. There can be one or more threshold setpoints, depending upon the number of chemical additives to be introduced into the water stream. When one threshold setpoint is reached, the dosing will begin. When another threshold setpoint is reached, the dosing will cease. The dosing rate of the chemical additives is constant between setpoints in this dosing method. The limitation of this method is the concentration variability of the chemical additives between the threshold setpoints. Threshold dosing is designed to deliver chemical additives as a batch without concern of the concentration of the chemical additive in the water treatment system. As the dosing begins at the starting setpoint, chemical additive is dosed until the ending setpoint is reached. The concentration of chemical additive is low when the chemical additive is first introduced into the water system, and the concentration of chemical additive increases until the ending setpoint triggers the cessation of dosing. The concentration of chemical additive in the water treatment system decreases after the ending setpoint triggers dosing to stop until the starting setpoint triggers dosing to begin again. Threshold dosing is, therefore, cyclical by design, which limits consistency of concentration in water treatment systems. Threshold setpoints are triggered by measuring devices such as flow switches, timers, level switches, oxidation-reduction potential (ORP) sensors and other such measuring devices.
One case of threshold dosing chemical additives is the dosing of chlorine and acid into cooling towers. In this case, a low-level ORP reading triggers chlorine, in the form of bleach (sodium hypochlorite), to begin chlorine dosing into a water line until a high-level ORP reading is achieved, at which time chlorine dosing ceases. Next, a high-level pH reading triggers acid to be dosed into the same water line until a low-level pH reading is achieved, at which time dosing ceases. Both the chlorine and acid concentrations rise while being dosed and fall when dosing ceases. The cyclical dosing of the threshold dosing method limits the ability to consistently regulate and balance chemical additive concentrations in the water treatment industry.
In another case of threshold dosing in the water treatment industry, the precursor solutions in the generation of aqueous chlorine dioxide, as well as the aqueous chlorine dioxide itself, are dosed in a threshold manner. Chlorine dioxide poses a unique challenge to the water treatment industry because aqueous chlorine dioxide solutions are typically unstable and therefore are generated onsite, unlike traditional chemical additives which are made elsewhere and merely injected onsite. The generator of chlorine dioxide requires that a chemical reaction occur. Varying pH and precursor concentrations dramatically affect the reaction efficiency of the resulting aqueous chlorine dioxide solution. In this case of threshold dosing, a low-level sodium chlorite setting on a level switch triggers an aqueous sodium chlorite solution to be dosed into a vessel until a high-level sodium chlorite setting on the level switch is reached. The high-level sodium chlorite setting then triggers the dosing of an aqueous acid solution to be dosed into the vessel until the high-level acid setting on another level switch is reached. Both the sodium chlorite and acid concentrations rise while being dosed and fall when dosing ceases. The cyclical dosing of the threshold dosing method limits the ability to consistently regulate and balance chlorine dioxide precursor concentrations. The limited ability to regulate the concentrations of the chlorine dioxide precursor solutions results in the inefficient and inconsistent production of aqueous chlorine dioxide.
In addition to threshold dosing, modulated dosing is another dosing method used in the water treatment industry. Modulated dosing is a proportional method of dosing. Modulated dosing measures the flow of process water and doses the chemical additive proportionally to the flow of the process water. Modulated dosing more accurately controls the concentration of the chemical additive in the process water than does threshold dosing. Because process water flow changes are usually smooth and gradual, the concentration of chemical additives in the water treatment system creates a smooth oscillating wave function, but high and low concentrations continue to exist.
Threshold and modulated dosing methods are often combined by using proportional modulating dosing within threshold setpoints. The threshold setpoints are the lower and upper limits of the oscillating wave function produced by the modulated dosing method. The combination of threshold and modulated dosing results in a more consistent dosing method than either method alone, but even though the peaks and valleys of modulated dosing are limited by the threshold setpoints, they still exist.
One case of modulating dosing within threshold setpoints is the dosing of chlorine and acid into a water treatment system using the flow rate of process water to proportionally dose the chemical additives and ORP and pH sensors to set the threshold setpoints of the chlorine and acid, respectively. In this case of modulated dosing, the process water flow rate is measured by a flow meter. The chlorine is then dosed proportionally based on the process water flow rate at a predetermined dilution rate as the ORP setpoints regulate the low and high limits of the threshold dosing. Next, acid is dosed proportionally based on the process water flow rate at a predetermined dilution rate as the pH setpoints regulate the high and low limits of the threshold dosing. As the chemical additives are dosed, there is an oscillating wave function produced by the modulated dosing, but the wave is held within the threshold setpoints. This circumstance limits the ability to consistently regulate and balance chemical additive concentrations in the water treatment systems.
In addition, although chemical additive dosing rates can be proportional to process water flow and limited by threshold setpoints, concentration of the chemical additives in the process water flow cannot be directly correlated to process water flow because of the variability in both process water flow and chemical additive purity levels and concentrations. For example, it is well known that chlorine in the form of bleach degrades over time. As the concentration of the chlorine degrades, the modulate dosing rate remains proportional to the process water flow rate based on the original concentration of the bleach, resulting in a lower concentration of chlorine over time in the water treatment system.
In accordance with the present invention, it has been discovered that conductivity is useful as a control function for the dosing of chemical additives such as, e.g., sanitizing agents and sanitizing agent precursors, in water treatment systems. Aqueous solution conductivity, referred to in the water treatment industry as simply conductivity, is the measure of an aqueous solution's ability to conduct electricity. All aqueous solutions have a measurable conductivity directly proportional to the specific ions in the aqueous solution. Because conductivity relates to the ions in solution, there is a direct correlation between conductivity and concentration in aqueous solutions that does not exist with other standards used for control.
Since conductivity relates directly to concentration in aqueous solutions, it is used in the present invention as the baseline for modulated dosing control and threshold dosing control. Conductivity is used to control modulated dosing, because it gives instantaneous feedback to the pumps or other dosing apparatus just like a flowmeter does. Conductivity is used to control threshold dosing by setting the upper and lower threshold setpoints. In addition, conductivity controls modulated dosing and threshold dosing at the same time by controlling the instantaneous dosing like the flowmeter in modulated dosing and by, also, controlling the threshold setpoints, so that the peaks and troughs are contained. Essentially, concentration, in the form of conductivity, is used to control dosing, eliminating the variables in traditional water treatment dosing methods.
For example, in accordance with the present invention conductivity is used to control the dosing of precursor solutions in the generation of aqueous chlorine dioxide. By using conductivity to control the dosing of precursor solutions in the generation of aqueous chlorine dioxide, the aqueous chlorine dioxide concentration produced is consistently regulated and balanced.
In a preferred embodiment of the present invention, conductivity is used to determine an aqueous solution's concentration, and the determined concentration's conductivity is used to control the dosing of chemical additives into a water treatment system.
Therefore, in accordance with the present invention chemical additives are sequentially dosed (diluted) into a stream of process water in a water treatment system. The conductivity of the diluted chemical additives is a known parameter. The conductivities of the process water, initially, and the water stream after dosing each additive are measured. Each measured conductivity is subtracted from the next-measured conductivity to determine the conductivity of the additive dosed between the two measurements. The determined conductivity of each dosed (diluted) chemical additive is compared to the known conductivity of each diluted chemical additive. The dosing rate of each additive is, then, modulated so that the determined conductivity of each diluted chemical additive in the water stream is matched to its known conductivity.
In addition, in accordance with the present invention chemical additives are separately dosed into separate process water streams, respectively, before then being combined into the final process water stream.
Further, in accordance with the present invention the chemical additives are dosed into a process water in any order.
Still further, in accordance with the present invention the chemical additives are one or more precursor solutions for the generation of aqueous chlorine dioxide in order to achieve a consistent concentration of aqueous chlorine dioxide.
In describing the present invention, specific terminology is used, and embodiments provided, for the sake of clarity. However, the invention is not necessarily limited to the specific terminology used, or to the specific embodiments disclosed.
As used herein, the following terms shall have the meanings stated. The term “solution” means a mixture formed by a process by which a solid, liquid, or gaseous substance is mixed with a liquid, whether that liquid is a droplet, aerosol, vapor, or mist. The term “chemical additive” is used to mean any solution or combination of solutions used in the water treatment industry such as, e.g., sanitizing agents and their precursors. The term “modulate” is used to mean the continuous adjustment of the dosing of chemical additive(s), such as, e.g., chlorine dioxide precursor solution(s), to keep them in proper measure or proportion. The term “known conductivity” is used to mean the conductivity that corresponds to the concentration of one or more chemical additives in the solution. The term “sequential” is used to mean the dosing of chemical additives, such as, e.g., chlorine dioxide precursor solutions, one after another in the same dilution water source or water system. The term “separate” is used to mean the dosing of chemical additives, such as, e.g., chlorine dioxide precursor solutions, independently of each other in independent dilution water sources or water systems. The term “precursor solution” is used to mean any solution or combination of solutions used to generate a product such as, e.g., chlorine dioxide. The term “water treatment system” is used to mean any system or conduit containing water that requires modification by chemical or mechanical means. The term “process water” is used to mean any inlet water, recycled water, and/or discharge water found in any residential, commercial, or industrial application. The term “flow regulator” is used to mean a device that controls/adjusts the flow rate (linear, nonlinear, mass or volumetric) of a liquid there through, such as, e.g., a valve, a pump, an eductor, and the like. The term “flow meter” is used to mean an instrument that measures/monitors the flow rate (linear, nonlinear, mass or volumetric) of a liquid there through. There are various types of, and different names for, flow meters, such as, e.g., a rotameter (variable area flow meter), a spring and piston flow meter, a turbine flow meter, a paddlewheel sensors, a positive displacement flow meter, a vortex meter, and the like.
There are many controllers that can be used within the scope of the present invention. These include but are not limited to microprocessors and programmable logic controllers (PLCs). Controlling methods must provide feedback to modulate the dosing rates of the chemical additives, and it is within the scope of those skilled in the art to select an appropriate controller for modulating the dosing of chemical additives to a water treatment system.
In one form of the present invention, conductivity is used to determine an aqueous solution's concentration, and the determined concentration's conductivity is used to control the dosing of chemical additives into a water treatment system by modulating the chemical additives into the water treatment system within threshold limits, which are also controlled by conductivity.
In another form of the present invention, chemical additives are sequentially dosed into a water treatment system. The conductivities of the process water and the water stream after adding each chemical additive is determined. Each conductivity is subtracted from the conductivity after it to determine the conductivity of the individual diluted additive. Each determined conductivity is compared to the known conductivity of each diluted chemical additive. The dosing rate of each chemical additive is modulated to achieve a determined conductivity matching the known conductivity of the diluted chemical additive.
In another form of the present invention, the chemical additives are dosed separately into independent sources of process water. The conductivities are measured of the independent water source and the water stream after each of the chemical additives has been added. Each conductivity is subtracted from the next measured conductivity to calculate the determined conductivity of each diluted chemical additive. The determined conductivities are then compared to the known conductivities of the diluted chemical additive solutions. The dosing rates of the solutions are modulated to achieve the known conductivities of each diluted chemical additive solution. These modulated diluted chemical additive solutions result in consistent concentrations of diluted chemical additive in the final water system.
In yet another form of the present invention, conductivity is used to determine the concentration of chlorine dioxide precursor solutions, and the determined chlorine dioxide precursor solution's concentration's conductivity is used to modulate the dosing of and set threshold limits for the chlorine dioxide precursor solutions for the generation of aqueous chlorine dioxide.
In a further embodiment an apparatus of the instant invention is illustrated in
Examples 1 A and 1B use concentrated sodium chlorite (25% active sodium chlorite). The known conductivity for sodium chlorite diluted to 1,250 mg/L is 1,500 μS, which known conductivity is used in Example 1B to modulate the dosing (dilution) rate of the sodium chlorite.
Examples 1A and 1B use the dosing system of
In this example, the flow rate—as measured by the flow meter—is used to modulate the dilution (dosing) rate of the concentrated sodium chlorite solution, i.e., via the dosing pump, and the first and second conductivity probes are used for monitoring purposes. The flow rate of the dilution water through the system is 0.5 L/min. The solution of the dilution water containing the sodium chlorite additive is referred to as the diluted sodium chlorite solution. The flow rate is used to modulate the dilution rate of the sodium chlorite dosing pump. The first conductivity probe records the dilution water conductivity (P1), and the second conductivity probe records the conductivity of the diluted sodium chlorite solution, i.e., after the concentrated sodium chlorite solution is injected into the dilution water (P2). The first conductivity probe reading is subtracted from the second conductivity probe reading (P2-P1) to determine the conductivity of the diluted sodium chlorite solution. The conductivity of the diluted sodium chlorite solution is recorded and graphed in
In this example, conductivities measured by the two conductivity probes are used to modulate the dilution (dosing) rate of the concentrated sodium chlorite solution, i.e., via the dosing pump, and the flow meter is used for monitoring purposes. The flow rate of the dilution water through the system is 0.5 L/min. The first conductivity probe records the dilution water conductivity (P1). The second conductivity probe records the conductivity of the diluted sodium chlorite solution, i.e., downstream of injecting the concentrated sodium chlorite solution into the dilution water. The first conductivity probe reading is subtracted from the second conductivity probe reading (P2-P1) to determine the conductivity of the diluted sodium chlorite solution. The determined conductivity of the diluted sodium chlorite solution (P2-P1) is compared to the desired, known conductivity of the diluted sodium chlorite solution. The dilution (dosing) rate of the concentrated sodium chlorite solution is then modulated so that the determined conductivity of the diluted sodium chlorite solution (P2-P1) matches the desired, known conductivity of the diluted sodium chlorite solution. The conductivity of the diluted sodium chlorite solution is recorded and graphed in
Examples 2A and 2B use 25% active sodium chlorite (concentrated sodium chlorite) and 35% (w/w) sulfuric acid (concentrated sulfuric acid) as the precursor chemicals. The known conductivity for sodium chlorite diluted to 1,250 mg/L is 1,500 μS, and the known conductivity for diluted sulfuric acid at a pH of 1.8 is 2,000 μS. These known conductivities are used in the following examples to modulate the dilution rate of the precursor chemicals to generate a concentration of aqueous chlorine dioxide.
Examples 2A and 2B use the serial dosing system of
In this example, the flow rate—as measured by the flow meter (6)—is used to modulate the dilution rate of the concentrated sodium chlorite solution and concentrated sulfuric acid solution, i.e., via first and second dosing pumps (3, 4), respectively, and the conductivity probes are used for monitoring purposes. The flow rate of the dilution water through the system is 0.5 L/min. The first conductivity probe (7) records the dilution water conductivity, the second conductivity probe (9) records the conductivity downstream of injecting the concentrated sodium chlorite solution into the dilution water, the third conductivity probe (11) records the conductivity downstream of injecting the concentrated sulfuric acid solution into the dilution water containing the sodium chlorite, and the dilution water containing the sodium chlorite and sulfuric acid downstream of the third conductivity probe (i.e., the diluted, sodium chlorite and sulfuric acid solution) is continuously fed through a catalyst to generate aqueous chlorine dioxide (13), the concentration of which is measured using the Hach 2700 Spectrophotometer, and recorded in Table 1. As shown in Table 1, the first conductivity probe reading subtracted from the second conductivity probe reading (P2-P1) determines the conductivity of the diluted sodium chlorite solution, the second conductivity probe reading subtracted from the third conductivity probe reading (P3-P2) determines the conductivity of the diluted sulfuric acid solution, and the Hach 2700 Spectrophotometer records the chlorine dioxide concentration in the aqueous chlorine dioxide downstream of the catalyst.
The values recorded in Table 1 show that using flow rate modulation and sequential precursor injection effects inconsistent conductivities in the diluted sodium chlorite solution (P2-P1) and the diluted sulfuric acid solution (P3-P2). The observed inconsistencies are due to the flow regulator's inability to provide sensitive feedback to the controller (2) that sets (modulates) the dosing rates of the pumps (3, 4).
In this example, conductivities measured by three conductivity probes (7, 9, 11) are used to modulate the dilution rate of the concentrated sodium chlorite and sulfuric acid solutions, i.e., via the first and second dosing pumps (3, 4), respectively, and the flow meter (6) is used for monitoring purposes. The flow rate of the dilution water through the system is 0.5 L/min. The first conductivity probe (7) records the dilution water conductivity, the second conductivity probe (9) records the conductivity downstream of injecting the concentrated sodium chlorite solution into the dilution water, the third conductivity probe (11) records the conductivity downstream of injecting the concentrated sulfuric acid solution into the dilution water containing the sodium chlorite. (See Table 2). As shown in Table 2, the first conductivity probe reading subtracted from the second conductivity probe reading (P2-P1) determines the conductivity of the diluted sodium chlorite solution and the second conductivity probe reading subtracted from the third conductivity probe reading (P3-P2) determines the conductivity of the diluted sulfuric acid solution (Table 2).
The determined conductivities of the diluted sodium chlorite solution (P2-P1) and the diluted sulfuric acid solution (P3-P2) are compared to the desired, known conductivities of the diluted sodium chlorite solution and the diluted sulfuric acid solution, respectively. The dilution (dosing) rates of the concentrated sodium chlorite solution and the concentrated sulfuric acid solution are then modulated so that the determined conductivities of the diluted sodium chlorite solution (P2-P1) and the diluted sulfuric acid solution (P3-P2) match the desired, known conductivities of the diluted sodium chlorite solution and the diluted sulfuric acid solution, respectively. The dilution water containing the sodium chlorite and sulfuric acid downstream of the third conductivity probe (i.e., the diluted, sodium chlorite and sulfuric acid solution) is continuously fed through a catalyst to generate aqueous chlorine dioxide, the concentration of which is measured using the Hach 2700 Spectrophotometer, and recorded (Table 2).
The values recorded in Table 2 show that conductivity modulation and sequential chlorine dioxide precursor injection effect consistent conductivities of the precursors, and consistent concentration of aqueous chlorine dioxide produced, over time.
A cooling tower recirculating water treatment system includes the serial dosing system exemplified in
Number | Name | Date | Kind |
---|---|---|---|
3619110 | Borezee | Nov 1971 | A |
3619650 | Marchfelder | Nov 1971 | A |
3684437 | Callerame | Aug 1972 | A |
3828097 | Callerame | Aug 1974 | A |
3857737 | Kemp et al. | Dec 1974 | A |
3936502 | Barber | Feb 1976 | A |
4006095 | Hoffman et al. | Feb 1977 | A |
4269619 | Bilofsky | May 1981 | A |
4504442 | Rosenblatt et al. | Mar 1985 | A |
4648043 | O'Leary | Mar 1987 | A |
4659459 | O'Leary | Apr 1987 | A |
4662747 | Isaacson | May 1987 | A |
4681739 | Rosenblatt et al. | Jul 1987 | A |
4880711 | Luczak et al. | Nov 1989 | A |
4925645 | Mason | May 1990 | A |
5008096 | Ringo | Apr 1991 | A |
5059406 | Sheth et al. | Oct 1991 | A |
5078908 | Ripley et al. | Jan 1992 | A |
5100652 | Kross et al. | Mar 1992 | A |
5116620 | Chvapil et al. | May 1992 | A |
5122285 | Mason | Jun 1992 | A |
5185161 | Davidson | Feb 1993 | A |
5324477 | Schroder | Jun 1994 | A |
5342510 | Eden | Aug 1994 | A |
5391533 | Peterson et al. | Feb 1995 | A |
5435984 | Daly et al. | Jul 1995 | A |
5639436 | Benson | Jun 1997 | A |
5651996 | Roozdar | Jul 1997 | A |
5820822 | Kross | Oct 1998 | A |
RE36064 | Davidson et al. | Jan 1999 | E |
5960808 | Ferguson | Oct 1999 | A |
6024850 | Sampson et al. | Feb 2000 | A |
6063425 | Kross et al. | May 2000 | A |
6077495 | Speronello et al. | Jun 2000 | A |
6123966 | Kross | Sep 2000 | A |
6200557 | Ratcliff | Mar 2001 | B1 |
6238643 | Thangaraj et al. | May 2001 | B1 |
6265343 | Daly et al. | Jul 2001 | B1 |
6287533 | Khan et al. | Sep 2001 | B1 |
20010001655 | Kuke | May 2001 | A1 |
20020037248 | Bechberger | Mar 2002 | A1 |
20040071627 | DiMascio | Apr 2004 | A1 |
20040211731 | Ferguson | Oct 2004 | A1 |
20050079230 | Lee | Apr 2005 | A1 |
20050084411 | Childers, II | Apr 2005 | A1 |
20050222287 | Roberts | Oct 2005 | A1 |
20060096930 | Beardwood | May 2006 | A1 |
20110129388 | Alarid | Jun 2011 | A1 |
20110132815 | Angelilli | Jun 2011 | A1 |
20110250123 | Sampson et al. | Oct 2011 | A1 |
20120183469 | Mussari | Jul 2012 | A1 |
20150125382 | Kuke | May 2015 | A1 |
20150218022 | Doak | Aug 2015 | A1 |
20160376166 | Lawryshyn | Dec 2016 | A1 |
20170008784 | Shimpo et al. | Jan 2017 | A1 |
20170349436 | Alvarado | Dec 2017 | A1 |
20180001262 | Rao et al. | Jan 2018 | A1 |
20180179058 | von Rege | Jun 2018 | A1 |
Number | Date | Country |
---|---|---|
0365501 | Apr 1990 | EP |
2502541 | Sep 2012 | EP |
791680 | Mar 1958 | GB |
Entry |
---|
Grant et al. Grant & Hackh's Chemical Dictionary, 5th Edition, 1987, p. 118. |
White, Geo Clifford, Handbook of Chlorination and Alternative Disinfectants, 4th Edition, 1999, pp. 1153-1202. |
Gordon et al. The Chemistry of Chlorine Dioxide, Progress in Inorganic Chemistry, vol. 15, 1972, pp. 201-286. |
Helfferich, Ion Exchange, 1995, pp. 519-550. |
Duolite Ion-Exchange Manual, Chemical Process Company, 1960. |
McPeak et al. Iron in Water and Processes for its Removal, 21st Annual Liberty Bell Corrosion Course, 1983. |
Manganese Greensand CR & IR, Iversand Company; 1998. |
Masschelein, Chlorine Dioxide, Chemistry and Environmental Impact of Oxychlorine Compounds, Ann Arbor Science Publishers, Inc. 1979. |
XP-002227957; JP 6271301; Suido Kiko Co. Ltd; 1994, abstract. |
Aieta et al. Determination of chlorine dioxide, chlorine chlorie and chlorate in water, American Water Works Associate, Journal, vol. 76, No. 1, 1984, pp. 64-70. |
National Exposure Research Laboratory, U.S. Environmental Protection Agency: Method 300.1, Determination of inorganic anions in drinking water by ion chromatography, 1999, pp. 300.1-1-300.1-39. |
Vogt, Helmut et al. Chlorine Oxides and Chlorine Oxygen Acids, 5. Chlorine Dioxide. Ullmann's Encyclopedia of Industrial Chemistry, vol. 8, Apr. 14, 2010, pp. 637-652. |
Lentech, Disinfectants Chlorine Dioxide, 2009, pp. 1-5 taken from https://web.archive.org/web/20090922222758/http://www/lenntech.com/processes/disinfection/chemical/disinfectants-chlorine-dioxide.htm. |
Gates, Don, PhD, The Chlorine Dioxide Handbook, Water Disinfection Series, AWWA, 1998. |
Lewatit, Bayer AG, Catalytic Removal fo Dissolved Oxygen from Water. |
Dence et al. Pulp Bleaching Principles and Practice, Tappi Press, 1996. |
Simpson et al. A Focus on Chlorine Dioxide: The “Ideal” Biocide. |
Encyclopedia.com, Mechanism of Catalysis. |
Number | Date | Country | |
---|---|---|---|
20200262717 A1 | Aug 2020 | US |
Number | Date | Country | |
---|---|---|---|
62807559 | Feb 2019 | US |