CA2130911C - Electrolytic cell for generating sterilization solutions having increased ozone content - Google Patents
Electrolytic cell for generating sterilization solutions having increased ozone contentInfo
- Publication number
- CA2130911C CA2130911C CA002130911A CA2130911A CA2130911C CA 2130911 C CA2130911 C CA 2130911C CA 002130911 A CA002130911 A CA 002130911A CA 2130911 A CA2130911 A CA 2130911A CA 2130911 C CA2130911 C CA 2130911C
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- Prior art keywords
- anode
- electrolytic solution
- flow
- ozone
- region
- Prior art date
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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
- C02F1/72—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4611—Fluid flow
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4612—Controlling or monitoring
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4612—Controlling or monitoring
- C02F2201/46125—Electrical variables
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4612—Controlling or monitoring
- C02F2201/46145—Fluid flow
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4618—Supplying or removing reactants or electrolyte
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/78—Details relating to ozone treatment devices
- C02F2201/782—Ozone generators
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/02—Fluid flow conditions
- C02F2301/022—Laminar
Abstract
An electrolytic cell (10) for generating a mixed oxidant that is rich in ozone is disclosed. The cell disassociates a brine solution to generate ozone and chlorine based oxidants. The improved cell design allows the ratio of ozone to the other oxidants to be optimized, thereby providing a more efficient sterilization solution. The ozone production is adjusted by adjusting the residence time of the brine solution in the cell and the orientation of the cell.
Description
2 1 3 0 9 1 1 PCI~/US93/01949 ELECTROLYTIC CFI,T, FOR GFl~ERATING STER~I,T7~TION
SOLUTIONS HAVING INCRF~SED OZONE CONTENT
Field of the Invention The present invention relates to water sterilization equipment, and more particularly, to an electrolytic cell for generating oxidant solutions that include ozone.
0 R~ ^Ir~ound of the Invention Mai~ ing the sterility of drinking water supplies is a major factor in reducing the health risks to the human population. While large metropolitan water systems can make use of highly toxic chlorine gas for sterilizing drinking water.
such systems are impractical in remote locations which lack highly trained personnel and the equipment to m~int~in the systems. To be effective in rural settings, a system must be capable of running for long periods of time with little or no m~inten~nce. In addition, the raw materials required by the system must be readily available.
Systems based on the electrolytic production of chlorine and ozone based germicidal agents are particularly attractive. These systems require only electricity and common salt as raw materials. One such system is described in U.S. Patent 4,761~208 to Gram, et al. which is incorporated herein bv reference.This system utilizes an electrolytical cell to generate a mixed strearn of oxidants including chlorine compounds, ozone, and H22 from common salt. This oxidant stream may be added directly to the drinking water at a high dilution ratio. thereby sterilizing the drinking water without causing the water to become unpalatable.
This system is particularly attractive because of its simplicity and long maintenance free operation time.
While this system represents a major improvement over the prior svstems.
it is less than optimal. For example, the most effective mixed oxidant stream has been found to be an oxidant stream in which the ratio of ozone and H22 to the 3s chlorine based compounds is ma~imi7~fl In addition to providing more effective , .~, .
~ .
''~ ' ' ~ s ~ ~13~qll sttqrili7~tion, the ozone and H2O2 oxidants provide a more palatable ~irinking water supply.
Broadly, it is the object of the present invention to provide an improved mix oxidant generating system.
It is a further object of the present invention to provide a mixed oxidant generating system with increased ratios of ozone to chlorine based compounds.
These and other objects of the present invention will become apparent to those skilled in the art from the following detailed description of the invention and the accompanying drawings.
Summary of the Invention The present invention comprises an apparatus for generating a mixed oxidant stream including ozone. The apparatus includes anode means comprising a first surface and cathode means comprising a second surface. An electrical potential is m~int~ined between the first and second surfaces. An electrolytic solution is caused to flow between the first and second surfaces and to be subsequently divided into cathode and anode streams. The anode stream comprises the portion of the electrolytic solution that was caused to flow between the first and second surfaces adjacent to the first sufface. An electrochemical interaction zone is bounded by the first and second surfaces.
The electrolytic solution undergoes electrochemical interactions within the zone, with the electrolytic solution flowing through the interaction zone in the same direction that bubbles generated on the first and second surfaces would travel in the absence of the flow of electrolytic solution.
s8 .~
~ ' ~13~qll -2a-The present invention also comprises an apparatus for generating a mixed oxidant stream including ozone as well as chlorine based oxidants. The apparatusincludes a flow chamber having two subst~nti~lly planar walls which form the anode and cathode of an electrical circuit. A DC electric potential is maintained between the anode 5 and cathode. An electrolytic solution is caused to flow between the anode and cathode surfaces. This stream is subsequently divided into cathode and anode streams. The anode stream provides the mixed oxidant stream in question. The flow rate through the apparatus determines the ratio of the various oxidants in the anode stream. This flow rate is adjusted with the aid of a sensor that measures a parameter which is correlated with ozone production to maintain optimum ozone production. For optimum ozone production to be obtained the zone between the anode and cathode must be defined such that an electrochemical interaction zone bounded by the anode and cathode exists that has a shape such that electrolytic solution caused to flow through said interaction zone has substantially the same residence time in said interaction zone independent of the path 15 taken through the interaction zone.
Brief Description of the Drawin~
Figure 1 is a prospective view of an electrolytic cell according to the present invention.
~.s~5 r ~' .
- -WO 93/18854~ 0 5 11 PCI/US93/01949 Figure 2 is a side view of an electrolytic cell according to the present invention.
sFigures 3 is a cross-sectional view of an electrolytic cell according to the present invention.
Figure 4 is a top view of a cell having a more optimally defined electrochemical interaction zone.
Figure 5 is a block diagrarn of a water purification system according to the present invention.
15~et~iled Description of the lnvention The manner in which an electrolytic cell 10 according to the present invention operates can be more easily understood with references to Figures 1-3.Electrolytic cell 10 includes an anode 12 and a cathode 14 which are separated by 20 an insulating gasket 16 thereby forming a flow charnber 24 through which a salt solution is passed. The salt solution is introduced through an input port 18 andexits through an anode port 20 and a cathode port 22. A DC voltage is maintainedbetween anode 12 and cathode 14 with the aid of a power source 24. Anode l 2 and cathode 14 are preferably constructed from titaniurn. In addition~ anode 12 2s preferably includes a Group VIII metal for the reasons discussed below.
Referring to ~igure 3, the flow of salt solution is divided by an extension of gasket 25 into anode and cathode output strearns which exit through anode port 20 and cathode port 22, respectively. The flow in charnber 24 is laminar in nature.
30 As the salt so~ution traverse the chamber 24, the pH of the solution chan~es. The portion of the salt solution that is adjacent to anode 12 decreases in pH, while the portion ofthe salt solution that is adjacent to cathode 14 increases in pH.
Various oxidants are generated in the salt solution as the solution 35 progresses through the electrolytic cell. The solution leaving anode port includes ozone and various chlorine con~ g oxidants. This solution will be referred to 21~0911 4 .
as the anode stream in the following discussion. The solution leaving the cathode port will be referred to as the cathode stream. The division of the input streamfrom input port 18 into the anode and cathode streams is aided by an extension of gasket 16 which forms a flow separator 2~. As will be explained in more detail 5 below, the shape and location of separator 25 is a significant factor in the concentration of ozone in the anode stream.
The anode stream is added to the water supply to be sterilized. The anode stream is plef~lled because it contains higher concentrations of desired oxidants o and because it has an acidic pH. Regulatory requirements governing drinking water dictate that the final drinking water supply be neutral or acidic. In addition the germicidal effects of the mixed oxidants are increased in acidic environments.
The specific oxidants that are generated in the anode stream as it 5 progresses through the cell depend on the pH of the solution at the corresponding point in the cell and on the material from which the anode is constructed. The concentrations of ozone produced in the electrolytic cell depend much more sensitively on these factors than do the concentrations of the chlorine based compounds. In particular, ozone is produced over a relatively narrow range of pH20 values. At pH values above the ol,Li-.lulll, little ozone is produced. At pH values below the optimum, the ozone is converted to less effective compounds and - radicals.
The ozone production is also dependent on the material from which the 25 anode is constructed. In particular, it is found experimentally that ozone production is catalyzed by Group VIII metals such as platinum, iridium~ rhodium.or ruthenium. In addition, these metals are highly resistant to corrosion and do not dissolve easily. Hence, the preferred embodiment of anode 12 in electrolytic cell 10 is constructed from titanium that has been plated with iridium. However. other 30 combinationc will be al~palel-l to those skilled in the art. In addition. electrolvtes other than NaCI may be used. A nurnber of possible combinations of salts and materials are tliccllcsed in U.S. Patent 4,761,208 discussed above.
In contrast, the production of the chlorine based oxidants is far less 35 sensitive to pH and anode construction. It is this difference in sensitivity which is utilized in the present invention to provide increased ratios of ozone to chlorine WO 93/188~ 3 0 9 1 1 PCr/US93/01949 -s based compounds. In principle, an operating parameter that effects ozone production can be altered until an ozone sensor in the anode stream indicates that optimum ozone production is being achieved. Alternatively, some other measurement that is related to the ozone production may be used in the servo loop.
s For any given salt concentration and flow rate of the salt solution through the electrolytic cell, there is a narrow pH range in which ozone production will be maximi7.~d Hence, either ozone production or pH may be used to run the servo loop. Since pH electrodes are inexpensive and reliable, a servo loop based on p~o provides an attractive alternative to a servo loop based on ozone.
If o~ pH range is generated just before the salt solution reaches the location of separator 25, i.e., in region 27 shown in Figure 3, the ozone production of electrolytic cell 10 will be optimi7.~-1 If the optimum pH range is not obtained 5 by the time the salt solution reaches region 27, too little ozone will be generated.
If, on the other hand, the optimum pH range is reached well before the salt solution reaches region 27, the pH of the salt solution along the anode in region 27 will be significantly below the o~ nuln pH. As a result, the ozone generated in the region of optimum pH will be lost in the below optimum pH conditions in 20 region 27.
It should be noted that separator 2~ is an electrical insulator. As a resulL
further electrolytic reactions of the salt solution at anode 12 and cathode 14 in the regions between the end of separator 25 and ports 20 and 22 are negligible. The 25 anode stream effectively represents a sampling of the salt solution at the end of separator 25. As noted above, the ozone production is related to the pH of the electrolyte at the location of the separator. Hence, it is important that the shape the separator be chosen such that the pH of the electrolyte at the anode surface i~
substantially constant along the edge of separator 25. If this condition is not met.
3() the anode strearn will be derived from regions of differing pH. Those regions that have pH's outside the optimum will contribute less ozone to the anode stream:
hence. Iess than optimal ozone production will be obtained.
The pH at any point in the cell depends on the flow pattern of the 3s electrolytic solution between input port 18 and the point in question. Consider ~e points located along the anode. As the electrolytic solution progresses through ~e electrolytic cell, the pH decreases as noted above. The amount of decrease will depend on the amount of time the electrolyte has spent in contact with the anode.
This, in turn, is related to the transit time of the electrolyte from the point at which it encounters sufficient electric field to undergo significant electrochemical 5 reactions to the point in question. Hence, the optimum shape for the edge of separator 25 is that which guarantees that fluid at each point along the edge of the separator has spend substantially the same time in contact with the anode in that portion of the flow chamber in which significant electrochemical interactions take place, i.e., interactions that significantly change the pH of the electrolyte.
In the pref~..cd embodiment of the present invention, flow chamber 24 is substantially rectilinear in shape with small openings for input port 18 and output ports 20 and 22. Such cell designs are particularly easy to construct at minim~1cost. In this case, the flow within the chamber itself is not rectilinear because of 15 the need for the fluid to "fan-out" from the input port and be recollected at the output ports. A rectilinear flow region, can, however, be defined within this region by introducing a rectiline~r insulator at the input end of the flow charnber.
Such an arrangement is shown in Figure 4 at 150. Figure 4 is a top view of a flow cell acco,..ling to the present invention illustrating the location and shape of two insulating members for limiting the electrochemical interaction area to those regions of the cell in which the flow is rectilinear. At the input end of the flow chamber the inc~ tor 151 may be attached to the electrode which is opposite the input port 160. Insulator 151 serves the function of preventing current flow through the electrolyte in the region of the flow chamber at which the fluid is still fanning out. Insulator 152 is a separator analogous to separator 25 shown above.Insulator 152 divides the flow into anode and cathode streams and shields the portion of the flow in which the fluid is collected into the two streams from electrochemical interactions. The rem~ining region 155 is a region of parallel flow in which the transit time along all paths is essentially the same. This region is not shielded by the inc~ r; hence, the electrochemical reactions described above occur in this region.
Alternatively, the input insulator may be omitted and non-linearities introduced into the shape of separator 25 to assure that the fluid traversing the 35 various portions of the boundary of separator 25 had spent equal time in contact with the anode surface. Alternative insulator designs which provide an -WO 93/18854 PCr/US93/01949 -electrochemical interaction region in which all portions of the electrolyte flo~A
have the same residency time will be appat~ to those skilled in the art.
The goal of the optimization process of the present invention is to assure s that the various structural and opcldling parameters of electrolytic cell 10 are chosen such that the optimum pH range for ozone production occurs at the end of separator 25. This optimization may be accomplished by a servo mech~nism that operates on any of a number of op~lalillg parameters. The preferred parameter isthe flow rate of the salt solution through the cell which may be adjusted by 0 adjusting the pressure of the salt solution at port 18. As the pressure is increased.
the flow rate increases and the drop in pH between input port 18 and region 25 is decreased. Similarly, if the ples~ule is decreased, the salt solution will spendmore time in contact with the anode which results in a decrease in the pH of theanode stream.
Alternatively, the voltage across electrolytic cell 10 may be adjusted to optimize the pH of the anode stream. At higher opel~ling voltages, the rate of reaction also increases thereby reducing the pH of the anode stream.
Unfor~unately~increasing the operating voltage across electrolytic cell 10 results 20 in other problems. In particular, the production of various gaseous products such as H2 and 2 increases with increased voltage. The H2 poses an explosion hazard.In addition, these products are less efficient from a germicidal prospective. The rate at which the coatings on the inner surface of the anode are eroded also increases rapidly with increasing voltage; hence~ the lifetime of the cell is 2~ significantly decreased if the operating voltage is increased. For these reasons.
adjustment of operating voltage to obtain optimum pH in the anode stream is not plefelled.
Similarly, the concentration of salt could be adjusted to optimize the anode 30 stream pH. However, the equipment for providing variable mixing of solution is more complex, and hence, to be avoided.
As noted above, the amount of ozone produced is also determined by the coating material used on the anode. This coating material represents a significant 3s portion ofthe cost of electrolytic cell 10; hence, it is advantageous to minimi7t~
the area that must be plated. The coated area may be minimi7~cl by limiting the WO 93/18854 2 ~ 3 ~ 9 1 ~ -8- PCI/US93/01949 Group VIII catalyst to region 27 shown in Figure 3. This arrangement allows a significantly thicker coating to be provided for the same cost. As a result, an electrolytic cell with increased lifetime is obtained.
s It has been found e~ llentAlly that the orientation of electrolytic cell 10 also effects the ozone content of the anode stream. In particular, if electrolytic cell 10 is mounted vertically with anode port 20 above input port 18, the conc~ 1dlion of-ozone in the anode stream is significantly increased.
o A block diagram of a water purification system 200 utili7ing an electrolytic cell 210 according to the present invention is shown in Figure 4.
Electrolytic cell 210 is supplied with a brine solution from a salt reservoir 212 that provides brine at a pl~;s~we above some minimurn design pressure. Reservoir 212 preferably includes a storage tank that is mounted at a fixed distance above electrolytic cell 210. However, it will be appalellt to those skilled in the art that a tank and pump arrangement will also provide the required functionality. A
control valve 214 is used to control the flow rate of the brine solution throughelectrolytic cell 210. Control valve 214 is operated by controller 210 which is comlec~ed to the output of sensor 215. Sensor 215 measures the ozone concentration in the anode stream leaving port 208 or some other parameter that is correlated with ozone concentration, e.g. pH. The anode stream is combined at a predetermined ratio with water from a drinking water source 216 to generate a purified water stream. This mixing is accomplished with the aid of mixing valve 218.
2s Accordingly, an improved apl~a~ s for generating a mixed oxidant stream suitable for disinfecting water has been disclosed. Various modifications to thepresent invention will become appa~enl to those skilled in the art from the foregoing description and accoll,pallying drawings. Accordingly, the present invention is to be limited solely by the scope of the following claims.
SOLUTIONS HAVING INCRF~SED OZONE CONTENT
Field of the Invention The present invention relates to water sterilization equipment, and more particularly, to an electrolytic cell for generating oxidant solutions that include ozone.
0 R~ ^Ir~ound of the Invention Mai~ ing the sterility of drinking water supplies is a major factor in reducing the health risks to the human population. While large metropolitan water systems can make use of highly toxic chlorine gas for sterilizing drinking water.
such systems are impractical in remote locations which lack highly trained personnel and the equipment to m~int~in the systems. To be effective in rural settings, a system must be capable of running for long periods of time with little or no m~inten~nce. In addition, the raw materials required by the system must be readily available.
Systems based on the electrolytic production of chlorine and ozone based germicidal agents are particularly attractive. These systems require only electricity and common salt as raw materials. One such system is described in U.S. Patent 4,761~208 to Gram, et al. which is incorporated herein bv reference.This system utilizes an electrolytical cell to generate a mixed strearn of oxidants including chlorine compounds, ozone, and H22 from common salt. This oxidant stream may be added directly to the drinking water at a high dilution ratio. thereby sterilizing the drinking water without causing the water to become unpalatable.
This system is particularly attractive because of its simplicity and long maintenance free operation time.
While this system represents a major improvement over the prior svstems.
it is less than optimal. For example, the most effective mixed oxidant stream has been found to be an oxidant stream in which the ratio of ozone and H22 to the 3s chlorine based compounds is ma~imi7~fl In addition to providing more effective , .~, .
~ .
''~ ' ' ~ s ~ ~13~qll sttqrili7~tion, the ozone and H2O2 oxidants provide a more palatable ~irinking water supply.
Broadly, it is the object of the present invention to provide an improved mix oxidant generating system.
It is a further object of the present invention to provide a mixed oxidant generating system with increased ratios of ozone to chlorine based compounds.
These and other objects of the present invention will become apparent to those skilled in the art from the following detailed description of the invention and the accompanying drawings.
Summary of the Invention The present invention comprises an apparatus for generating a mixed oxidant stream including ozone. The apparatus includes anode means comprising a first surface and cathode means comprising a second surface. An electrical potential is m~int~ined between the first and second surfaces. An electrolytic solution is caused to flow between the first and second surfaces and to be subsequently divided into cathode and anode streams. The anode stream comprises the portion of the electrolytic solution that was caused to flow between the first and second surfaces adjacent to the first sufface. An electrochemical interaction zone is bounded by the first and second surfaces.
The electrolytic solution undergoes electrochemical interactions within the zone, with the electrolytic solution flowing through the interaction zone in the same direction that bubbles generated on the first and second surfaces would travel in the absence of the flow of electrolytic solution.
s8 .~
~ ' ~13~qll -2a-The present invention also comprises an apparatus for generating a mixed oxidant stream including ozone as well as chlorine based oxidants. The apparatusincludes a flow chamber having two subst~nti~lly planar walls which form the anode and cathode of an electrical circuit. A DC electric potential is maintained between the anode 5 and cathode. An electrolytic solution is caused to flow between the anode and cathode surfaces. This stream is subsequently divided into cathode and anode streams. The anode stream provides the mixed oxidant stream in question. The flow rate through the apparatus determines the ratio of the various oxidants in the anode stream. This flow rate is adjusted with the aid of a sensor that measures a parameter which is correlated with ozone production to maintain optimum ozone production. For optimum ozone production to be obtained the zone between the anode and cathode must be defined such that an electrochemical interaction zone bounded by the anode and cathode exists that has a shape such that electrolytic solution caused to flow through said interaction zone has substantially the same residence time in said interaction zone independent of the path 15 taken through the interaction zone.
Brief Description of the Drawin~
Figure 1 is a prospective view of an electrolytic cell according to the present invention.
~.s~5 r ~' .
- -WO 93/18854~ 0 5 11 PCI/US93/01949 Figure 2 is a side view of an electrolytic cell according to the present invention.
sFigures 3 is a cross-sectional view of an electrolytic cell according to the present invention.
Figure 4 is a top view of a cell having a more optimally defined electrochemical interaction zone.
Figure 5 is a block diagrarn of a water purification system according to the present invention.
15~et~iled Description of the lnvention The manner in which an electrolytic cell 10 according to the present invention operates can be more easily understood with references to Figures 1-3.Electrolytic cell 10 includes an anode 12 and a cathode 14 which are separated by 20 an insulating gasket 16 thereby forming a flow charnber 24 through which a salt solution is passed. The salt solution is introduced through an input port 18 andexits through an anode port 20 and a cathode port 22. A DC voltage is maintainedbetween anode 12 and cathode 14 with the aid of a power source 24. Anode l 2 and cathode 14 are preferably constructed from titaniurn. In addition~ anode 12 2s preferably includes a Group VIII metal for the reasons discussed below.
Referring to ~igure 3, the flow of salt solution is divided by an extension of gasket 25 into anode and cathode output strearns which exit through anode port 20 and cathode port 22, respectively. The flow in charnber 24 is laminar in nature.
30 As the salt so~ution traverse the chamber 24, the pH of the solution chan~es. The portion of the salt solution that is adjacent to anode 12 decreases in pH, while the portion ofthe salt solution that is adjacent to cathode 14 increases in pH.
Various oxidants are generated in the salt solution as the solution 35 progresses through the electrolytic cell. The solution leaving anode port includes ozone and various chlorine con~ g oxidants. This solution will be referred to 21~0911 4 .
as the anode stream in the following discussion. The solution leaving the cathode port will be referred to as the cathode stream. The division of the input streamfrom input port 18 into the anode and cathode streams is aided by an extension of gasket 16 which forms a flow separator 2~. As will be explained in more detail 5 below, the shape and location of separator 25 is a significant factor in the concentration of ozone in the anode stream.
The anode stream is added to the water supply to be sterilized. The anode stream is plef~lled because it contains higher concentrations of desired oxidants o and because it has an acidic pH. Regulatory requirements governing drinking water dictate that the final drinking water supply be neutral or acidic. In addition the germicidal effects of the mixed oxidants are increased in acidic environments.
The specific oxidants that are generated in the anode stream as it 5 progresses through the cell depend on the pH of the solution at the corresponding point in the cell and on the material from which the anode is constructed. The concentrations of ozone produced in the electrolytic cell depend much more sensitively on these factors than do the concentrations of the chlorine based compounds. In particular, ozone is produced over a relatively narrow range of pH20 values. At pH values above the ol,Li-.lulll, little ozone is produced. At pH values below the optimum, the ozone is converted to less effective compounds and - radicals.
The ozone production is also dependent on the material from which the 25 anode is constructed. In particular, it is found experimentally that ozone production is catalyzed by Group VIII metals such as platinum, iridium~ rhodium.or ruthenium. In addition, these metals are highly resistant to corrosion and do not dissolve easily. Hence, the preferred embodiment of anode 12 in electrolytic cell 10 is constructed from titanium that has been plated with iridium. However. other 30 combinationc will be al~palel-l to those skilled in the art. In addition. electrolvtes other than NaCI may be used. A nurnber of possible combinations of salts and materials are tliccllcsed in U.S. Patent 4,761,208 discussed above.
In contrast, the production of the chlorine based oxidants is far less 35 sensitive to pH and anode construction. It is this difference in sensitivity which is utilized in the present invention to provide increased ratios of ozone to chlorine WO 93/188~ 3 0 9 1 1 PCr/US93/01949 -s based compounds. In principle, an operating parameter that effects ozone production can be altered until an ozone sensor in the anode stream indicates that optimum ozone production is being achieved. Alternatively, some other measurement that is related to the ozone production may be used in the servo loop.
s For any given salt concentration and flow rate of the salt solution through the electrolytic cell, there is a narrow pH range in which ozone production will be maximi7.~d Hence, either ozone production or pH may be used to run the servo loop. Since pH electrodes are inexpensive and reliable, a servo loop based on p~o provides an attractive alternative to a servo loop based on ozone.
If o~ pH range is generated just before the salt solution reaches the location of separator 25, i.e., in region 27 shown in Figure 3, the ozone production of electrolytic cell 10 will be optimi7.~-1 If the optimum pH range is not obtained 5 by the time the salt solution reaches region 27, too little ozone will be generated.
If, on the other hand, the optimum pH range is reached well before the salt solution reaches region 27, the pH of the salt solution along the anode in region 27 will be significantly below the o~ nuln pH. As a result, the ozone generated in the region of optimum pH will be lost in the below optimum pH conditions in 20 region 27.
It should be noted that separator 2~ is an electrical insulator. As a resulL
further electrolytic reactions of the salt solution at anode 12 and cathode 14 in the regions between the end of separator 25 and ports 20 and 22 are negligible. The 25 anode stream effectively represents a sampling of the salt solution at the end of separator 25. As noted above, the ozone production is related to the pH of the electrolyte at the location of the separator. Hence, it is important that the shape the separator be chosen such that the pH of the electrolyte at the anode surface i~
substantially constant along the edge of separator 25. If this condition is not met.
3() the anode strearn will be derived from regions of differing pH. Those regions that have pH's outside the optimum will contribute less ozone to the anode stream:
hence. Iess than optimal ozone production will be obtained.
The pH at any point in the cell depends on the flow pattern of the 3s electrolytic solution between input port 18 and the point in question. Consider ~e points located along the anode. As the electrolytic solution progresses through ~e electrolytic cell, the pH decreases as noted above. The amount of decrease will depend on the amount of time the electrolyte has spent in contact with the anode.
This, in turn, is related to the transit time of the electrolyte from the point at which it encounters sufficient electric field to undergo significant electrochemical 5 reactions to the point in question. Hence, the optimum shape for the edge of separator 25 is that which guarantees that fluid at each point along the edge of the separator has spend substantially the same time in contact with the anode in that portion of the flow chamber in which significant electrochemical interactions take place, i.e., interactions that significantly change the pH of the electrolyte.
In the pref~..cd embodiment of the present invention, flow chamber 24 is substantially rectilinear in shape with small openings for input port 18 and output ports 20 and 22. Such cell designs are particularly easy to construct at minim~1cost. In this case, the flow within the chamber itself is not rectilinear because of 15 the need for the fluid to "fan-out" from the input port and be recollected at the output ports. A rectilinear flow region, can, however, be defined within this region by introducing a rectiline~r insulator at the input end of the flow charnber.
Such an arrangement is shown in Figure 4 at 150. Figure 4 is a top view of a flow cell acco,..ling to the present invention illustrating the location and shape of two insulating members for limiting the electrochemical interaction area to those regions of the cell in which the flow is rectilinear. At the input end of the flow chamber the inc~ tor 151 may be attached to the electrode which is opposite the input port 160. Insulator 151 serves the function of preventing current flow through the electrolyte in the region of the flow chamber at which the fluid is still fanning out. Insulator 152 is a separator analogous to separator 25 shown above.Insulator 152 divides the flow into anode and cathode streams and shields the portion of the flow in which the fluid is collected into the two streams from electrochemical interactions. The rem~ining region 155 is a region of parallel flow in which the transit time along all paths is essentially the same. This region is not shielded by the inc~ r; hence, the electrochemical reactions described above occur in this region.
Alternatively, the input insulator may be omitted and non-linearities introduced into the shape of separator 25 to assure that the fluid traversing the 35 various portions of the boundary of separator 25 had spent equal time in contact with the anode surface. Alternative insulator designs which provide an -WO 93/18854 PCr/US93/01949 -electrochemical interaction region in which all portions of the electrolyte flo~A
have the same residency time will be appat~ to those skilled in the art.
The goal of the optimization process of the present invention is to assure s that the various structural and opcldling parameters of electrolytic cell 10 are chosen such that the optimum pH range for ozone production occurs at the end of separator 25. This optimization may be accomplished by a servo mech~nism that operates on any of a number of op~lalillg parameters. The preferred parameter isthe flow rate of the salt solution through the cell which may be adjusted by 0 adjusting the pressure of the salt solution at port 18. As the pressure is increased.
the flow rate increases and the drop in pH between input port 18 and region 25 is decreased. Similarly, if the ples~ule is decreased, the salt solution will spendmore time in contact with the anode which results in a decrease in the pH of theanode stream.
Alternatively, the voltage across electrolytic cell 10 may be adjusted to optimize the pH of the anode stream. At higher opel~ling voltages, the rate of reaction also increases thereby reducing the pH of the anode stream.
Unfor~unately~increasing the operating voltage across electrolytic cell 10 results 20 in other problems. In particular, the production of various gaseous products such as H2 and 2 increases with increased voltage. The H2 poses an explosion hazard.In addition, these products are less efficient from a germicidal prospective. The rate at which the coatings on the inner surface of the anode are eroded also increases rapidly with increasing voltage; hence~ the lifetime of the cell is 2~ significantly decreased if the operating voltage is increased. For these reasons.
adjustment of operating voltage to obtain optimum pH in the anode stream is not plefelled.
Similarly, the concentration of salt could be adjusted to optimize the anode 30 stream pH. However, the equipment for providing variable mixing of solution is more complex, and hence, to be avoided.
As noted above, the amount of ozone produced is also determined by the coating material used on the anode. This coating material represents a significant 3s portion ofthe cost of electrolytic cell 10; hence, it is advantageous to minimi7t~
the area that must be plated. The coated area may be minimi7~cl by limiting the WO 93/18854 2 ~ 3 ~ 9 1 ~ -8- PCI/US93/01949 Group VIII catalyst to region 27 shown in Figure 3. This arrangement allows a significantly thicker coating to be provided for the same cost. As a result, an electrolytic cell with increased lifetime is obtained.
s It has been found e~ llentAlly that the orientation of electrolytic cell 10 also effects the ozone content of the anode stream. In particular, if electrolytic cell 10 is mounted vertically with anode port 20 above input port 18, the conc~ 1dlion of-ozone in the anode stream is significantly increased.
o A block diagram of a water purification system 200 utili7ing an electrolytic cell 210 according to the present invention is shown in Figure 4.
Electrolytic cell 210 is supplied with a brine solution from a salt reservoir 212 that provides brine at a pl~;s~we above some minimurn design pressure. Reservoir 212 preferably includes a storage tank that is mounted at a fixed distance above electrolytic cell 210. However, it will be appalellt to those skilled in the art that a tank and pump arrangement will also provide the required functionality. A
control valve 214 is used to control the flow rate of the brine solution throughelectrolytic cell 210. Control valve 214 is operated by controller 210 which is comlec~ed to the output of sensor 215. Sensor 215 measures the ozone concentration in the anode stream leaving port 208 or some other parameter that is correlated with ozone concentration, e.g. pH. The anode stream is combined at a predetermined ratio with water from a drinking water source 216 to generate a purified water stream. This mixing is accomplished with the aid of mixing valve 218.
2s Accordingly, an improved apl~a~ s for generating a mixed oxidant stream suitable for disinfecting water has been disclosed. Various modifications to thepresent invention will become appa~enl to those skilled in the art from the foregoing description and accoll,pallying drawings. Accordingly, the present invention is to be limited solely by the scope of the following claims.
Claims (7)
1. An apparatus for generating a mixed oxidant stream including ozone, said apparatus comprising: anode means comprising a substantially planar first surface; cathode means comprising a substantially planar second surface, said second surface being parallel to said first surface; means for maintaining an electrical potential between said first and second surfaces; means for causing an electrolytic solution to flow between said first and second surfaces and to be subsequently divided into cathode and anode streams, said anode stream comprising the portion of said electrolytic solution that was caused to flow between said first and second surfaces adjacent to said first surface, said flowmeans further comprising means for varying the rate of flow of said electrolyticsolution in response to a control signal; means for defining a electrochemical interaction zone bounded by said first and second surfaces in which said electrolytic solution undergoes electrochemical interactions, said zone being shaped such that electrolytic solution caused to flow through said interaction zone by said flow means has substantially the same residence time in said interactionzone independent of the path taken through said interaction zone; and means for measuring a parameter correlated to the ozone in said anode stream and for generating said control signal so as to maintain the ozone concentration within predetermined limits.
2. The apparatus of Claim 1 wherein said first surface comprises a region comprising a Group VIII metal, said region being located at the edge of said interaction zone such that electrolytic solution passing over said region leaves said interaction region immediately after passing over said region.
3. The apparatus of Claim 1 wherein said measuring means comprises means for measuring ozone.
4. The apparatus of Claim 1 wherein said measuring means comprises means for measuring pH.
5. The apparatus of Claim 1 wherein said interaction region comprises a region in which said electrolytic solution flows from the bottom to the top of acavity.
6. The apparatus of Claim 1 wherein said electrochemical interaction defining means comprises an insulating gasket disposed between said first and second surfaces, said gasket having an opening therein wherein said opening defines at least one boundary of said electrochemical interaction zone.
7. An apparatus for generating a mixed oxidant stream including ozone, said apparatus comprising:
anode means comprising a first surface; cathode means comprising a second surface;
means for maintaining an electrical potential between said first and second surfaces; and means for causing an electrolytic solution to flow between said first and second surfaces and to be subsequently divided into cathode and anode streams, said anode stream comprising the portion of said electrolytic solution that was caused to flow between said first and second surfaces adjacent to said first surface;
means for defining an electrochemical interaction zone bounded by said first and second surfaces in which said electrolytic solution undergoes electrochemical interactions, wherein said electrolytic solution flows through said interaction zone in the same direction that bubbles generated on said first and second surfaces would travel in the absence of said flow of electrolytic solution.
anode means comprising a first surface; cathode means comprising a second surface;
means for maintaining an electrical potential between said first and second surfaces; and means for causing an electrolytic solution to flow between said first and second surfaces and to be subsequently divided into cathode and anode streams, said anode stream comprising the portion of said electrolytic solution that was caused to flow between said first and second surfaces adjacent to said first surface;
means for defining an electrochemical interaction zone bounded by said first and second surfaces in which said electrolytic solution undergoes electrochemical interactions, wherein said electrolytic solution flows through said interaction zone in the same direction that bubbles generated on said first and second surfaces would travel in the absence of said flow of electrolytic solution.
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US857,731 | 1992-03-26 | ||
US07/857,731 US5316740A (en) | 1992-03-26 | 1992-03-26 | Electrolytic cell for generating sterilization solutions having increased ozone content |
Publications (2)
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CA2130911A1 CA2130911A1 (en) | 1993-09-30 |
CA2130911C true CA2130911C (en) | 1999-03-30 |
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CA002130911A Expired - Fee Related CA2130911C (en) | 1992-03-26 | 1993-03-04 | Electrolytic cell for generating sterilization solutions having increased ozone content |
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US (3) | US5316740A (en) |
EP (1) | EP0632746B1 (en) |
JP (1) | JP3051175B2 (en) |
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AR (1) | AR247765A1 (en) |
AT (1) | ATE192944T1 (en) |
AU (1) | AU667525B2 (en) |
BR (1) | BR9306134A (en) |
CA (1) | CA2130911C (en) |
DE (1) | DE69328676T2 (en) |
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HU (1) | HU218057B (en) |
IL (1) | IL104989A0 (en) |
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MY (1) | MY109908A (en) |
NO (1) | NO943412L (en) |
RU (1) | RU2123069C1 (en) |
TW (1) | TW210327B (en) |
WO (1) | WO1993018854A1 (en) |
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- 1992-03-26 US US07/857,731 patent/US5316740A/en not_active Expired - Lifetime
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1993
- 1993-03-04 JP JP5516572A patent/JP3051175B2/en not_active Expired - Fee Related
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- 1993-03-04 KR KR1019940703316A patent/KR100220363B1/en not_active IP Right Cessation
- 1993-03-04 AT AT93907201T patent/ATE192944T1/en not_active IP Right Cessation
- 1993-03-04 EP EP93907201A patent/EP0632746B1/en not_active Expired - Lifetime
- 1993-03-04 AU AU37890/93A patent/AU667525B2/en not_active Ceased
- 1993-03-04 HU HU9402715A patent/HU218057B/en not_active IP Right Cessation
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1994
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- 1994-09-23 FI FI944424A patent/FI944424A/en unknown
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1997
- 1997-01-23 US US08/787,160 patent/USRE36972E/en not_active Expired - Lifetime
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USRE36972E (en) | 2000-11-28 |
EP0632746B1 (en) | 2000-05-17 |
HU9402715D0 (en) | 1995-02-28 |
AR247765A1 (en) | 1995-03-31 |
US5385711A (en) | 1995-01-31 |
NO943412L (en) | 1994-09-14 |
JP3051175B2 (en) | 2000-06-12 |
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