Abstract:
An automated process for controlling the rate chlorine dioxide made from sodium chlorate-chloride and sulfuric acid is generated. The process automatically adjusts the rate of chlorine dioxide production to the needs of the system treated with chlorine dioxide by controlling the feed of one or more of the reactants by means of a multiple feed-back loop system which provides adequate oxidative treatment while avoiding overfeed or underfeed conditions.

Description:
This application is a continuation-in-part application Ser. No. 07/709,010 filed on May 31, 1991, now U.S. Pat. No. 5,227,306. 
    
    
     FIELD OF THE INVENTION 
     This invention relates to an automated process for controlling the rate chlorine dioxide made from sodium chlorate-chloride and sulfuric acid is generated. The process automatically adjusts the rate of chlorine dioxide production to the needs of the system treated with chloride dioxide by controlling the feed of one or more of the reactants by means of a multiple feed-back loop system which provides adequate oxidative treatment while avoiding overfeed or underfeed conditions. 
     BACKGROUND OF THE INVENTION 
     Chlorine dioxide has long been recognized as an oxidizing treatment having great utility in a variety of applications. Chlorine dioxide is used in the paper industry as a bleaching agent for paper pulp, in the water and waste treatment industry as a biocide for bacteria, algae and various water-borne microorganisms, in the fat rendering and tallow industry as both a biocide and bleaching agent, and generally as an oxidant useful in destroying certain organic materials, such as phenols. In whatever application chlorine dioxide is used, the need for treatment is likely to fluctuate depending on variations in the amount of material being treated, the degree of pollution or contamination of the material, the degree of bleaching required, and so forth. 
     The process of treating water and other materials with chlorine dioxide consists generally of introducing and mixing a quantity of chlorine dioxide with the material. wherein the quantity of chlorine dioxide is sufficient to completely and effectively treat the material. In some applications, chlorine dioxide is sufficient to completely and effectively treat the material. In some applications, chlorine dioxide is continuously generated in quantities large enough to meet the treatment requirements of peak demand. There are problems associated with operating a chlorine dioxide generator in this manner. During periods of low demand. Operating in an overtreatment mode is uneconomical, inefficient, and may even result in excessive wear and tear on mechanical and electronic equipment and those materials exposed to the high concentrations of ClO 2  and reactants. During periods of extremely high demand, undertreatment conditions may result, leaving materials incompletely sanitized or bleached. 
     To overcome the problems inherent in the fixed rate generation of chlorine dioxide, chlorine dioxide generator operators can manually adjust the generation rate in response to variations noted from periodic measurements of the need for treatment. The measurements may be based on, for example, the amount of material requiring treatment, the amount of pollutants needing treatment, and the oxidation-reduction potential of the water. However, unless the measurements of the need for treatment and the accompanying adjustments have a high frequency, or coincide fortuitously with rapid increases and decreases in the need for treatment, over and undertreatment conditions may occur. 
     Automated systems have been developed for supplying chlorine dioxide on an as needed basis to treat water. One such system known to the inventors comprises a chlorine dioxide generator which operates on a constant rate basis, sending an aqueous stream of ClO 2  produced by the generator to a holding tank. The volume of ClO 2  solution in the tank released to the water treatment site is based on a signal received from a treatment need detecting device, such as a flow monitoring device in the water treatment sluice. In the event the holding tank becomes filled with chlorine dioxide solution, the generator is shut down until more ClO 2   is needed. 
     Because chlorine dioxide is released from water solution on standing, a ClO 2  solution held in the tank will lose strength and hence effectiveness, thus making complete treatment of materials with that solution uncertain. The chlorine dioxide which has left the solution may become trapped in the free space of the holding tank if not properly vented. Should the concentration of ClO 2  in the air above the tank reach a critical level, a spontaneous explosion of the chlorine dioxide may occur. 
     An automated ClO 2  generating system was developed by Rio Linda (Fischer &amp; Porter Co., Warminster, Pa.) and installed at a drinking water treatment facility in Shreveport, La. The Shreveport system is described in an article entitled &#34;Automated Approach for ClO 2  Disinfection&#34; found in the October, 1988 issue of Water Engineering Magazine, pp. 35-38. It appears that the generator equipment of the Rio Linda Shreveport system is of the vacuum eductor type which uses the chlorite-chlorine route to produce ClO 2 . 
     The control portion of the Rio Linda Shreveport system operates by receiving signals from a water flow monitoring device and simultaneously adjusting mechanical valves associated with the supply sources of both the sodium chlorite and chlorine gas reactants feeding the generator. It is well known that it is difficult to mechanically control gas flowing through a valve to the degree of accuracy needed to achieve the desired 2:1 ratio of reactants in order to operate the system at the most desired levels of efficiency and economy. Furthermore, the control system associated with the supply valves does not take into account the flow differences caused by the level of reactants in their respective tanks, the pressure at which the materials are delivered, or the relative concentrations of the reactants. The result is that the reactants are not used economically. 
     It will be well understood by practitioners of the art of oxidation treatment that the equipment and processes used in the treatment of water with ClO 2  may be used in the paper and pulp industry, the fat rendering industry and others. It is believed that little or no modification is necessary to adapt a method and apparatus for use in applications other than water treatment. 
     SUMMARY OF THE INVENTION 
     The invention relates to a method of treating a system with chlorine dioxide produced by means feeding two reactants into a chlorine dioxide generator wherein said reactants are (a) a solution of and alkaline earth metal chlorate-chloride, and (b) sulfuric acid, said generator having an inlet for feed of reactants and an outlet means for egress of a product stream wherein the amount of chlorine dioxide used to treat the system is automatically controlled in response to the amount of treatment required by the system, said method comprising the steps of: 
     (a) measuring the need for chlorine dioxide treatment; 
     (b) adjusting the quantity of one of said reactants fed to he chlorine dioxide generator to an amount proportional to the measured need for treatment; 
     (c) monitoring the product stream exiting the generator to determine the composition thereof; and 
     (d) adjusting the quantity of the second reactant for chlorine dioxide fed to the chlorine dioxide generator to bring the composition of the product stream to a predetermined state, thereby producing a quantity of chlorine dioxide sufficient to meet the measured need for treatment, 
     wherein said alkaline earth metal chlorate is selected from the group consisting of sodium chlorate, lithium chlorate, potassium chlorate, rubidium chlorate, cesium chlorate and francium chlorate. 
     The method of the present invention provides a system for controlling the generation of chlorine dioxide so that the amount of ClO 2  treatment delivered is responsive to the need for treatment with ClO 2 . The method of the invention is based on the premise that the rate at which chlorine dioxide is generated may be automatically controlled by a multiple-loop feedback system. The invention operates by adjusting the amount of reactants fed to the chlorine dioxide generator in response to the detected need for treatment; monitoring the product stream exiting the generator for the composition thereof and adjusting the amount of the remaining reactants fed to the generator until the composition of the product stream exiting the generator reaches a predetermined state, thus effecting adequate ClO 2  treatment responsive to the detected need for treatment. 
    
    
     BRIEF DESCRIPTION OF THE DRAWING 
     FIG. 1 illustrates the apparatus for automatically controlling the generation of chlorine dioxide. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     In FIG. 1, a sluice 1 is shown in which the material to be treated (for example, water, paper pulp, rendered fat, sewage, etc.) is carried. The overall direction of the flow of materials in the sluice is shown by the arrow. A treatment need sensing device 10 is shown in contact with the contents of the sluice. The sensing device detects the need for treatment of materials flowing in the sluice by monitoring such parameters as flow rate or volume, residual pollution (such as with a phenol or hydrogen sulfide detector), residual chlorine dioxide (if previously treated with ClO 2 ), oxidation-reduction potential, or the number of bacteria present in the material, for example. 
     A signal from the treatment need sensing device which indicates the need for treatment is sent to the controller 20 via signal transmitting means 11. The signal may be conveyed via the connection by electronic, optical, mechanical or other suitable means. Controller 20 reads the information sent by the treatment need sensing device and signals the sodium chlorate supply 30 to proportionally adjust the amount of sodium chlorate delivered via conduit 31 to the chlorine dioxide generator 50 for adequate treatment of the material flowing in the sluice. It will be understood that a signal from the treatment need detector indicating an increased need for treatment will cause the controller to increase the amount of sodium chlorate delivered to the generator in an amount proportional to the increased need for treatment. Conversely, it will be understood that a signal indicating decreased need for treatment will cause the controller to decrease the amount of sodium chlorate delivered to the generator in an amount proportional to the decreased need for treatment. 
     It will also be understood by practitioners skilled in the art that when the amount of one of the reactants for ClO 2  fed to the generator is altered, the relative composition of the product stream of the generator will also change. This change in the product stream can be detected and measured by such parameters as pH, a temperature thermal couple, oxidation-reduction potential, or on-line specific monitors. For example, when an increased amount of chlorate is delivered to the generator, the concentration of the effluent stream will rise. Conversely, if you reduce the chlorate, then the concentration of the effluent stream will decrease. 
     In the figure, a means for monitoring the relative composition of the product stream 60, for example, a glass pH electrode is shown in conduit 51. Changes in the composition of the product stream are detected by the means for monitoring and the controller 20 is signalled of these changes. The controller responds to changes in the product stream composition by signalling the sulfuric acid supply 40 to deliver more or less sulfuric acid to the generator, as required. 
     The preferred controller is a microprocessor based controller having multiple channel capability. An off the shelf controller, such as the Model 95G controller with four-channel capacity commercially available from Great Lakes Instruments, Milwaukee, Wi. is very suitable for this application. The controller should accommodate at least two input control signals, process the same, and have the ability to produce two output control signals. 
     Generation equipment suitable for use in association with this embodiment of the method and apparatus of the invention are described in U.S. Pat. Nos. 4,013,761 and 4,147,115. It is believed other generation equipment for the chlorate-chloride and sulfuric reaction route may be used with the method and apparatus of the present invention with little or no modification of the generation equipment required. 
     Not shown in the figure are the various means which may be used to control the delivery of sodium chlorate to the generator. Such means include, but are not limited to, variable rate pumps, valves and metering devices. Also not shown in the figure, it will be apparent to practitioners of the art that various means can be employed to control the delivery of sulfuric acid to the generator. Such means include, but are not limited to, variable rate pumps, valves and metering devices. 
     It will be apparent to the practitioner that the apparatus described in FIG. 1 may alternatively be set up to adjust the sulfuric acid supply fed to the reactor in response to the signal for the need for treatment and make the chlorate supply responsive to the change in pH of the effluent stream. It will be noted that due to current technical limitations in the metering of sulfuric acid, this form of the first embodiment, while operable, does not give as good results as when the control of the chlorate is responsive to the need for treatment. 
     In the typical chlorate reaction route to ClO 2  sodium chlorate and sulfuric acid react as follows: 
     
         3NaClO.sub.3 +2NaCl+2H.sub.2 SO.sub.4 →3 ClO.sub.2 +Cl.sub.2 +2Na.sub.2 SO.sub.4 +2H.sub.2 O 
    
     It will be understood that other alkaline earth metal forms of the chlorates may be used in the reaction. The preferred alkaline earth metal chlorate is sodium, but other chlorates derived from one or more alkaline earth metals selected from the group consisting of Li, K, Na, Rb, Cs and Fr may be used. The preferred alkaline earth metal chloride is sodium, but other chlorates derived from one or more alkaline earth metals selected from the group consisting of Li, K, Na, Rb, Cs and Fr may be used. 
     Preferably, detecting the need for treatment is related to the chlorate, although the feed of either the chlorate or the sulfuric acid reactant may be responsive to the detected need for treatment with the feed of the remaining reactant being responsive to the relative composition of the product stream of the generator. 
     
         ______________________________________VARIABLES          AMOUNT PER POUND OF          CHLORINE DIOXIDEBASIS FOR CONTROL          GENERATED______________________________________chlorate       1.64sulfuric acid  1.45-3.00______________________________________ 
    
     In practicing this embodiment of the invention, it is necessary to calibrate or otherwise configure the controller and/or means for adjusting the amount of reactants fed to the generator to accommodate reactants controlled in pairs which may not be of the same concentration and/or which react with the paired reactant in other than a 1:1 stoichiometric ratio. The controller and/or means for adjusting the amount of reactants fed to the generator must be configured to allow the stoichiometrically correct amounts of the reactants be fed to the generator. If the paired reactants, are in solutions of the same concentration, the stoichiometry of the reaction requires that twice the volume to be fed to the generator. In the likely situation that the paired reactants are not of the same concentration, the controller and/or means for adjusting the amount of reactants fed to the generator would have to be configured to take both the concentration of reactants and the stoichiometry of the reaction into account.