Ozone water delivery system and use method thereof

Abstract

The present application discloses an ozone water delivery system, the ozone water delivery system comprising: at least one contact device in communication with at least one ultrapure water source configured to provide ultrapure water; at least one ultrapure water conduit, the at least one ultrapure water conduit being coupled to the ultrapure water source; the at least one solution is communicated with the contact device and the ultrapure water source through the ultrapure water guide pipe; one or more gas sources, the one or more gas sources containing at least one gas, in communication with at least one of the ultrapure water source, the ultrapure water conduit, and the solution conduit; at least one mixed gas conduit in communication with the gas source and the contact device and configured to provide at least one mixed gas to the contact device; and at least one ozone water output conduit, the at least one ozone water output conduit may be in communication with the contact device.

Description

[0001] This case is a divisional application of the invention patent application with the application date of August 27, 2019, the priority date of August 29, 2018, the application number of 201980054540.9, and the invention name of ozone water delivery system and method of use thereof. CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Patent Application No. 62 / 724,368, filed on August 29, 2018, entitled “Ozonated Water Delivery System and Method of Use,” which is incorporated herein by reference in its entirety. Background Art

[0003] Currently, ozone is used in many applications including semiconductor manufacturing, solar panel processing, sanitary applications, food processing, flat panel processing, etc. In some applications, ozone can be dissolved in deionized water. However, ozone is highly reactive with deionized ultrapure water, which causes ozone to decay in ultrapure water within a few seconds. Some applications such as semiconductor manufacturing applications, solar panels and flat panel manufacturing require high ozone concentrations dissolved in ultrapure water. However, the ozone decay rate increases with the increase in the concentration of ozone dissolved in deionized ultrapure water. Certain applications such as single semiconductor wafer processing require ozone dissolved at randomly varying liquid flow rates, which may result in different residence times in the supply pipeline, with higher ozone attenuation at low liquid flow rates as an additional change in ozone attenuation. In addition, ozone attenuation can be triggered by the presence of hydroxide ions and peroxides, which are usually found in trace amounts in industrial ultrapure water. Therefore, due to the changes in the concentration of these impurities in ultrapure water supplied to different locations, ozone attenuation can be different between manufacturing locations and / or sites.

[0004] In response to this, many techniques have been adopted to control the decay rate of ozone in ozone water. For example, FIG. 1 shows an example of an ozone water delivery system currently used in semiconductor manufacturing applications. As shown, the ozone water delivery system 1 includes a contact device 3 that is fluidly connected to an ultrapure water source 5 (hereinafter referred to as UPW source 5) through an ultrapure water source conduit 7 (hereinafter referred to as UPW source conduit 7). A gas source and / or an ozone generator 9 (hereinafter referred to as a gas source 9) is connected to the contact device 3 through a gas inlet conduit 11. The gas mixture typically contains carbon dioxide (CO2), ozone (O3) and oxygen (O2). One or more valve devices 13 and / or indicators are used to safely separate water from the gas mixture and prevent water, gas or both from flowing back into the gas source 9. During use, a gas mixture from the gas source 9 is contacted with ultrapure water from the UPW source 5 in the contact device 3 using a countercurrent, thereby causing a portion of the ozone from the gas source 9 to dissolve in the ultrapure water. Some carbon dioxide (CO2) in the gas mixture is converted into carbonic acid, which reduces the concentration of hydroxide ions. Carbonate ions remove hydroxyl groups, which effectively reduces the decay rate of dissolved ozone in ultrapure water. Thereafter, dissolved ozone is released or removed from the contact device 3 to form a dissolved ozone output 17 through a dissolved ozone conduit 19. In addition, waste gases 21 such as carbon dioxide (CO2), oxygen (O2) and ozone (O3) can be released from the contact device 3 through a waste gas conduit 23. Although the system in Figure 1 has been proven to be useful, many disadvantages have been identified. For example, the ozone water delivery system shown in Figure 1 allows ozone concentrations between about 25 ppm and 50 ppm. However, it has been proven difficult to obtain an ozone concentration greater than about 50 ppm using the ozone water delivery system 1 shown in Figure 1. Further, an increase in mass transfer efficiency will require a higher (higher or taller) packed column of the contact device 3, thereby requiring a larger working area. In addition, membrane modules are typically used to dissolve gases such as carbon dioxide into ultrapure water or to remove residual oxygen from ultrapure water. Unfortunately, most commercially available membrane modules contain plastics such as polypropylene and / or polyethylene or similar materials that are highly sensitive to oxidants such as peroxides and ozone. Further, carbon dioxide and ozone have different solubilities. Therefore, the concentration of carbon dioxide in the contact device varies greatly in certain flow arrangements. For example, in a countercurrent arrangement within a packed column contact device, it may cause carbon dioxide to dissolve near the inlet of the gas mixture conduit 11 in the contact device 3, while ozone dissolves near the inlet of the UPW conduit 5, thereby reducing the efficiency of forming ozone water. Figure 2 graphically shows the concentration profile of carbon dioxide in a packed column contact device 3 using a countercurrent architecture. The horizontal axis in Figure 2 represents a lateral portion (hereinafter referred to as a column portion) of the packed column that forms the contact device 3. Portion 1 represents the top of the column near the inlet of the UPW source conduit 7 and the outlet of the exhaust conduit 23.Part 20 represents the bottom of the column near the gas inlet conduit 11 and the dissolved ozone conduit 19 .

[0005] In view of the foregoing, there continues to be a need for ozone water delivery systems that are capable of selectively providing ultrapure water having high ozone concentrations. Summary of the invention

[0006] The present application discloses various embodiments of an ozone water delivery system capable of providing a higher amount of ultrapure water having a higher dissolved ozone concentration therein compared to prior art systems. In some embodiments, the ozone water delivery system can be configured to allow adjustment of ozone reactivity and maintain accurate dissolved ozone measurement. More specifically, in one embodiment, the present application discloses an ozone water delivery system, the ozone water delivery system comprising at least one contact device, the at least one contact device being connected to at least one ultrapure water source configured to provide ultrapure water. At least one ultrapure water conduit can be coupled to the ultrapure water source. Further, at least one solution can be connected to the contact device and the ultrapure water source through the ultrapure water conduit. One or more gas sources containing at least one gas can be connected to at least one of the ultrapure water source, the ultrapure water conduit, and the solution conduit. During use, the gas can be used to form at least one solution when reacting with the ultrapure water. At least one mixed gas conduit can be connected to the gas source and the contact device. The mixed gas conduit can be configured to provide at least one mixed gas to the contact device. Finally, at least one ozone water output conduit can be connected to the contact device.

[0007] In another embodiment, the present application discloses an ozone water delivery system, the ozone water delivery system comprising one or more sensors, the one or more sensors being configured to measure various characteristics, concentrations, flow rates, etc. of the ozone water produced by the ozone water delivery system. More specifically, the ozone water delivery system may include at least one contact device, the at least one contact device being connected to at least one ultrapure water source configured to provide ultrapure water. At least one ultrapure water conduit may be coupled to the ultrapure water source. Further, at least one solution may be connected to the contact device and the ultrapure water source through the ultrapure water conduit. One or more gas sources containing at least one gas may be connected to at least one of the ultrapure water source, the ultrapure water conduit, and the solution conduit. During use, the gas may be used to form at least one solution when reacting with the ultrapure water. At least one mixed gas conduit may be connected to the gas source and the contact device. The mixed gas conduit may be configured to provide at least one mixed gas to the contact device. Finally, at least one ozone water output conduit may be connected to the contact device. One or more sensors may be positioned within the ozone water delivery system and used to measure various characteristics of the output ozone water, such as ozone concentration, flow rate, temperature, etc.

[0008] In another embodiment, the present application discloses an ozone water delivery system, wherein the ozone water delivery system includes a plurality of contact devices. More specifically, the present application discloses an ozone water delivery system, wherein the ozone water delivery system has a first contact device and at least a second contact device. At least one ultrapure water source can be configured to provide ultrapure water to the first contact device. At least one ultrapure water conduit can be coupled to the at least one ultrapure water source and the first contact device. At least one solution conduit can be connected to the first contact device and the ultrapure water source through the ultrapure water conduit. At least one gas source containing at least one gas can be connected to at least one of the ultrapure water source, the ultrapure water conduit and the solution conduit. During use, the gas can be used to form at least one solution when reacting with the ultrapure water. The second contact device is connected to the first contact device through at least one first contact device conduit, and the at least one first contact device conduit is configured to transport the ozone water output from the first contact device to the second contact device. At least one mixed gas conduit can be connected to the gas source and the second contact device. The mixed gas conduit can be configured to provide at least one mixed gas to the second contact device. At least one exhaust conduit is in communication with the second contact device and the first contact device, wherein the exhaust conduit is configured to direct a portion of the mixed gas from the second contact device to the first contact device. At least one ozone water output conduit may be in communication with the second contact device.

[0009] The present application also discloses a method for providing ozone water. More specifically, the present application discloses a method for providing ultrapure water with a higher dissolved ozone concentration in a higher amount than is currently available. In one embodiment, the method for providing ozone water includes forming a carbon dioxide aqueous solution containing carbon dioxide dissolved in ultrapure water. The carbon dioxide aqueous solution is flowed to at least one contact device. At least a portion of at least one mixed gas including ozone is flowed to the contact device in which the carbon dioxide aqueous solution flows. At least a portion of the ozone is dissolved in the ultrapure water in the contact device. The carbon dioxide component of the carbon dioxide aqueous solution is used to slow down the ozone decay rate of the dissolved ozone in the ultrapure water and output ozone water from the contact device.

[0010] In another embodiment, the present application also discloses a method for adjusting or regulating ozone reactivity. More specifically, the present application discloses a method for measuring ozone reactivity and controlling the amount of carbon dioxide gas flowing into a first contact device in response thereto. In one embodiment, a second sensor can be used to selectively adjust flow conditions through at least one valve in the ozone water delivery system.

[0011] Other features and advantages of the novel ozone water delivery system disclosed herein will become more apparent upon consideration of the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] The novel aspects of the ozone water delivery system and methods of use as described herein will become more apparent upon review of the following drawings, in which:

[0013] FIG1 shows a schematic diagram of a prior art ozone water delivery system;

[0014] FIG2 shows a graph depicting the concentration profile of carbon dioxide in the prior art packed column contact device shown in FIG1 ;

[0015] Figure 3 A schematic diagram showing an embodiment of an ozone water delivery system having a gas source for providing gaseous carbon dioxide to ultrapure water used in a contacting device;

[0016] Figure 4 A schematic diagram showing another embodiment of an ozone water delivery system having a gas source for providing gaseous carbon dioxide to ultrapure water used in a contacting device;

[0017] Figure 5 A schematic diagram showing another embodiment of an ozone water delivery system having a gas source for providing gaseous carbon dioxide to ultrapure water used in a contacting device;

[0018] Figure 6 A schematic diagram of another embodiment of an ozone water delivery system incorporating a device for measuring ozone reactivity is shown.

[0019] Figure 7 Shows a depiction Figure 3 and 4 a graph showing a concentration profile of carbon dioxide in the contact device shown;

[0020] Figure 8 A schematic diagram showing an embodiment of an ozone water delivery system incorporating multiple contact devices; and

[0021] Fig. 9 A schematic diagram of another embodiment of an ozone water delivery system incorporating multiple contact devices is shown. DETAILED DESCRIPTION

[0022] The present application discloses several embodiments of a novel ozone water delivery system. In one embodiment, the novel ozone water delivery system disclosed herein can be configured to provide ozone water having an ozone concentration greater than about 50 ppm. In another embodiment, the novel ozone water delivery system disclosed herein can be configured to provide ozone water having an ozone concentration greater than about 100 ppm. Optionally, the novel ozone water delivery system disclosed herein can be configured to provide ozone water having an ozone concentration of about 50 ppm or less. Further, the novel ozone water delivery system can be configured to provide ozone water having an ozone concentration greater than about 50 ppm at an ultrapure water flow rate of 20 liters per minute (LPM) or more, but those skilled in the art will understand that the ozone water delivery system disclosed herein can be configured to provide ultrapure water at a flow rate of less than about 20 LPM. In another embodiment, the ozone water delivery system can be configured to provide ozone water having an ozone concentration greater than about 100 ppm at an ultrapure water flow rate of 20 LPM or more. Optionally, the ozone water delivery system can be configured to provide ozone water with any kind of ozone concentration at an ultrapure water flow rate of 2 LPM or greater. The system can optionally be configured to provide a constant ozone concentration at a randomly varying ozone water flow rate between 2 LPM and greater than 20 LPM.

[0023] Figure 3-6 Schematic diagrams of various embodiments of the novel ozone water delivery system are shown. As shown, the ozone water delivery system 30 disclosed herein includes at least one contact device 32. In the illustrated embodiment, a single contact device 32 is used in the ozone water delivery system 30, but those skilled in the art will understand that any number of contact devices may be used. Further, in one embodiment, the contact device 32 includes a packed column architecture. Further, in one embodiment, the contact device 32 includes a packed column filled with tower packing. In another embodiment, the contact device 32 includes a membrane-based device or at least one membrane assembly. The contact device 32 may be fluidically connected to at least one deionized ultrapure water source 34 (hereinafter UPW source 34) via at least one ultrapure water conduit 36 ​​(hereinafter UPW conduit 36), the UPW conduit 36 ​​being configured to transport deionized ultrapure water from the UPW source 34 to the contact device 32. In the illustrated embodiment, at least one ultrapure water and / or reactant inlet 40 may be formed on the surface of the contact device 32. Those skilled in the art will understand that any number of inlets or outlets may be formed on the contact device 32. Although not shown in Figure 3 and 4 Although not shown in the drawings, those skilled in the art will appreciate that the UPW conduit 36 ​​may include one or more controllers, valve devices, flow restrictors, sensors, indicators, flow controllers, etc.

[0024] Reference again Figure 3-6, at least one gas or fluid source 60 (hereinafter referred to as gas source 60) configured to provide one or more types of gases, reactants and / or fluids can be connected to at least one of the UPW source 34, the UPW conduit 36 ​​and / or the contact device 32. In the illustrated embodiment, the gas source 60 is coupled to at least one gas conduit 42, and the at least one gas conduit is coupled to the UPW conduit 36 ​​by at least one coupling member 48. Therefore, the ultrapure water flowing through the UPW conduit 36 ​​can react with at least one gas or fluid in the gas conduit 42 to form at least one reaction solution, and the reaction solution can flow into the contact device 32 via at least one ultrapure water inlet 40. For example, deionized ultrapure water can react with carbon dioxide to produce a carbon dioxide aqueous solution. Further, like the UPW conduit 36, the gas conduit 42 can include one or more controllers, valve devices, restrictors, mass flow controllers, sensors, indicators, flow regulators, etc. on or in communication therewith. For example, in Figure 3 , 4 In the embodiment shown in Figures 6 and 7, the gas conduit 42 includes two (2) valves 44 and one (1) indicator 46 configured to prevent water and or gas from flowing back into the gas source, but those skilled in the art will appreciate that any type of components may be used on the gas conduit 42 for any type of application. Optionally, Figure 5 An alternative embodiment of an ozone water delivery device 30 is shown. As shown, Figure 5 The ozone water delivery device 30 shown includes Figure 3 , 4 6 and 7 show many components of the ozone water delivery device 30. However, Figure 5 The illustrated ozone water delivery device 30 includes a valve 44 positioned on at least one of the UPW conduit 36, the solution conduit 38, or both. Further, at least one (1) valve 44, at least one (1) flow restrictor 50, and at least one (1) check valve 52, as well as at least one control valve 54 may be positioned on the gas conduit 42. In the illustrated embodiment, carbon dioxide is added to the ultrapure water flowing in the UPW conduit 36 ​​upstream of the control valve 54.

[0025] In one embodiment, the gas source 60 can be configured to deliver carbon dioxide (CO2) to the ultrapure water flowing in the ultrapure water conduit 36 ​​before entering the contact device 32 via at least one solution conduit 38 to form a carbon dioxide aqueous solution. During use, the carbon dioxide component of the carbon dioxide aqueous solution can be used to reduce the decay rate of dissolved ozone in the contact device 32 during use. For example, in one embodiment, the gas source 60 and the gas conduit 42 are configured to provide a carbon dioxide flow to the ultrapure water flowing in the UPW conduit 36 ​​at a flow rate of about 0.01 standard liters per minute (hereinafter SLPM) to about 0.5 SLPM. Optionally, the gas source 60 and the gas conduit 42 are configured to provide a carbon dioxide flow to the ultrapure water flowing in the UPW conduit 36 ​​at a flow rate of about 0.005 standard liters per minute (hereinafter SLPM) to 3.0 SLPM or more. In one embodiment, the gas source 60 can be configured to provide a constant gas (e.g., carbon dioxide, etc.) flow to the UPW conduit 36 ​​at a fixed flow rate, regardless of the flow rate of the ultrapure water flowing into the contact device 32. Therefore, the effective content of carbon dioxide in the ultrapure water can be higher at a lower ultrapure water flow rate, thereby resulting in a higher concentration of dissolved ozone in the ultrapure water. In another embodiment, the gas source 60 can be configured to provide a gas (e.g., carbon dioxide, etc.) flow to the UPW conduit 36 ​​at a fixed ratio of ultrapure water to gas. In another embodiment, the gas source 60 and the gas conduit 42 are configured to provide a carbon dioxide flow to the ultrapure water flowing in the UPW conduit 36 ​​at a flow rate of about 0.05 SLPM to about 0.3 SLPM. Optionally, the gas source 60 and the gas conduit 42 are configured to provide a carbon dioxide flow to the ultrapure water flowing in the UPW conduit 36 ​​at a flow rate of about 0.1 SLPM to about 0.2 SLPM, but those skilled in the art will understand that the gas source 60 and the gas conduit 42 can be configured to provide a carbon dioxide flow to the ultrapure water flowing in the UPW conduit 36 ​​at any desired flow rate. Therefore, one or more mass flow controllers 44 and valves 46 can be used to selectively control the rate at which carbon dioxide is introduced into the UPW conduit 36. In alternative embodiments, gas source 60 may be configured to provide nitrogen to gas conduit 42. Optionally, gas source 60 may be configured to provide any type of gas or fluid to at least one of gas conduit 42, UPW source 34, contact device 32, or the like.

[0026] like Figure 3-6 As shown, the gas source 60 can be in communication with the contact device 32 via at least one mixed gas conduit 62 and at least one mixed gas inlet 68. In the illustrated embodiment, a single gas source 60 is in fluid communication with the contact device 32. For example, Figure 3-6The single gas source 60 shown in the figure can be configured to provide a mixed gas consisting of oxygen (O2), ozone (O3) and carbon dioxide (CO2) to the contact device 32. In another embodiment, the mixed gas consists of oxygen (O2), ozone (O3), carbon dioxide (CO2) and less than about 2 ppm of nitrogen (N2), but those skilled in the art will understand that nitrogen (N2) greater than about 2 ppm can be used. Other gases include but are not limited to nitrogen, nitrogen dioxide, and nitrous oxide. In alternative embodiments, multiple gas sources 60 can be coupled to the contact device 32 or otherwise fluidly connected to the contact device. For example, separate sources of ozone (O3) / oxygen (O2) and carbon dioxide (CO2) can be coupled to the gas conduit 62 respectively, so that the mixed gas conduit 62 mixes the mixed gas and transports it from the separate sources to the contact device 32. In one embodiment, the gas source 60 can be connected to at least one ozone generator and / or can include at least one ozone generator, which is configured to provide ozone to the mixed gas conduit 62. During use, the carbon dioxide introduced into the contact device 32 within the mixed gas via the mixed gas conduit 62 has the function of increasing the ozone generation efficiency in the ozone generator as part of the mixed gas source 60, inhibiting the ozone decay of ozone dissolved in water at the mixed gas input region within the contact device 32, while the carbon dioxide component of the carbon dioxide aqueous solution reduces the decay rate of dissolved ozone at the gas outlet side of the contact device 32. Thus, any type of additional gas (e.g., carbon dioxide, nitrogen, nitrogen dioxide, nitrous oxide, etc.) can be used to improve and / or selectively control the efficiency of the process of converting oxygen to ozone within the ozone generator.

[0027] like Figure 3-6 As shown, at least one valve, mass flow controller, indicator, sensor, etc. may be positioned on or in communication with at least one of the gas source 60, the mixed gas conduit 62, or both. For example, Figure 3-6 The illustrated embodiment of the ozone water delivery system 30 includes two (2) valves 64 and one (1) indicator 66, but those skilled in the art will appreciate that any number or valves, mass flow controllers, indicators, sensors, etc. may be coupled to or communicate with the mixed gas conduit 62.

[0028] Reference again Figure 3-6During use, an aqueous solution of carbon dioxide is introduced into the contact device 32 through the solution conduit 38. As described above, the mixed gas from the mixed gas conduit 62 is introduced into the contact device 32. The ozone in the mixed gas reacts with the ultrapure water and dissolves in the ultrapure water to form dissolved ozone (DIO3). The carbon dioxide in the ultrapure water introduced into the contact device 32 through the solution conduit 38 can be used to suppress the decay rate of the newly formed dissolved ozone. Thereafter, the ozone water is released from the contact device 32 at the ozone water output 70 through at least one ozone water conduit 72. In one embodiment, the flow rate of the ozone water from the ozone water output 70 is about 0.2 LPM to about 70 LPM. In another embodiment, the flow rate of the ozone water from the ozone water output 70 is about 3 LPM to about 40 LPM. Optionally, Figure 3 and 4 The illustrated ozone water delivery system 30 may be configured to output about 2 LPM to about 20 LPM of ozone water from the ozone water output 70. Further, waste gas 80 such as oxygen (O2), ozone (O3), carbon dioxide (CO2), and other gases may be removed from the contact device 32 via at least one waste gas conduit 82.

[0029] Figure 4 and 6 A system having at least one processor is shown. Figure 37. As shown, at least one sensor, indicator, valve, etc. may be positioned on the ozone water conduit 72. For example, in the illustrated embodiment, the sensor 74 is coupled to the ozone water conduit 72, but those skilled in the art will appreciate that any variety of other components may be similarly included. For example, in one embodiment, the sensor 74 may be configured to measure the ozone concentration proximate the ozone water conduit 72, but those skilled in the art will appreciate that the various ozone water delivery systems disclosed herein may include one or more sensors 74 positioned at different locations within the ozone water delivery system, the sensors 74 being configured to measure ozone concentration, carbon dioxide concentration, flow rate, temperature, etc. The sensor 74 may be in communication with at least one processor 78 via at least one processor conduit 76. Further, the processor 78 may be in communication with at least one of the UPW source 34, the valve 44, the indicator 46, the gas source 60, the valve 64, and the indicator 66 via the processor conduit 76. Thus, the processor 78 may be configured to receive data from and provide data to at least one of the UPW source 34, valve 44, indicator 46, gas source 60, mass flow controller 64, indicator 66, and sensor 74. Thus, the processor 78 may be configured to allow, limit, and / or otherwise control the flow of ultrapure water, mixed gas, and / or ozone water within the system through sensors, UPW sources, valves, mass flow controllers, gas sources, etc. used throughout the system. During use, the processor 78 may be configured to monitor ozone concentration, water flow rate, and similar characteristics of ozone water, as well as operating characteristics such as pressure within the contact device 32, pressure within the UPW source 34, etc. Further, the processor 78 may be configured to selectively change the performance of the UPW source 34, mass valve 44, indicator 46, gas source 60, valve 64, indicator 66, and sensor 74 accordingly. The pressure in the contact device 32 may be controlled by the processor 78 to an effectively constant value. The pressure of the contact device 32 may be configured to be between 1 bar and 4 bar, such as between 1.8 bar and 2.5 bar, but those skilled in the art will appreciate that the pressure within the contact device 32 may be higher or lower depending on the application. Figure 7 Graphically shows the use of Figure 3 and 4 The CO2 liquid concentration and CO2 gas concentration profiles for the architecture shown. Those skilled in the art will appreciate that Figure 5 and 6The illustrated embodiment will generate similar graphical representations of CO2 liquid concentration and CO2 gas concentration. As shown, the CO2 distribution within the contact device 32 is more uniform than the carbon dioxide concentration profile in the packed column contact device 3 using the prior art countercurrent architecture shown in FIG1. ​​Further, those skilled in the art will understand that due to the principle similarity of the transport process, the architecture containing the membrane contact device is subject to carbon dioxide concentration profile non-uniformity similar to the carbon dioxide concentration profile in the packed column contact device 3 using the prior art countercurrent architecture shown in FIG1.

[0030] Figure 6 An embodiment of an ozone water delivery system including two ozone sensors is shown, but those skilled in the art will appreciate that any number of sensors may be used. In one embodiment, the first sensor 74 may be configured to operate continuously and may cooperate with the controllable valve 212 and the processor 78 to control the ozone concentration in the output ozone water 72. Optionally, in the illustrated embodiment, the ozone water delivery system 30 may include at least a second sensor 204 (e.g., an ozone measuring device). In one embodiment, the second sensor 204 may be configured to control the accuracy of the measuring device 74. In another embodiment, the second sensor 204 may be configured to measure any kind of characteristic of the output of the ozone water delivery system 30. For example, the second sensor 204 may be configured to measure the dissolved ozone concentration in the conduit 72 and cooperate with the processor 78 to compare the ozone concentration measured by the first sensor 74 with the ozone concentration measured by the second sensor 204 and adjust the zero point of the first sensor 74 accordingly when there is a deviation. In one embodiment, at least one valve 213 may be used to selectively control flow conditions within the system, such as after the ozone sensor 204 is filled with fresh ozone water. Optionally, the ozone concentration of the water remaining stagnant in the sensor 204 will be tracked by the controller 78 over time. The decay rate can be calculated from the ozone concentration curve over time. Thereafter, the amount of carbon dioxide supplied can be controlled by the controller 78 based on the measured ozone decay rate so as to achieve the desired ozone reactivity at the treated target surface. In one embodiment, one or more ozone sensors 204 (optical sensors, visible light sensors, IR sensors, UV sensors, etc.) can be used. For example, the ozone sensor 204 can be configured to measure ozone based on visible light absorption. The second sensor 204 can be configured to operate as a reference sensor configured to measure the ozone concentration in the supplied water at a given time. The measurements of the two sensors can then be compared. Therefore, this arrangement allows the continuous operation of the first sensor 74 without interruption due to filling the sensor with water without dissolved ozone to recalibrate the zero point, which is economically beneficial to the entire system due to the high amount of normal operation time.

[0031] Figure 8 and 9 Another embodiment of an ozone water delivery system is shown. As shown, the ozone water delivery system 100 includes a first contact device 102a and at least a second contact device 102b. In one embodiment, the first contact device 102a, the second contact device 102b, or both include a packed column architecture. Optionally, at least one of the first contact device 102a and / or the second contact device 102b need not include a packed column architecture. For example, at least one first contact device 102a and / or the second contact device 102b may include a membrane-based device or at least one membrane assembly. The first contact device 102a may be fluidically connected to at least one ultrapure water source 104 (hereinafter UPW 104) via at least one ultrapure water conduit 106 (hereinafter UPW conduit 106). Similarly, although not shown in Figure 8 and 9 Although not shown in the figure, those skilled in the art will appreciate that one or more controllers, valve devices, sensors, indicators, etc. may be included on the coupling member 106.

[0032] Reference again Figure 8 and 9 , at least one gas source 130 may be in communication with at least one of the UPW source 104, the UPW conduit 106, and / or the contact device 102a via at least one gas conduit 112. In the illustrated embodiment, the gas source 130 is coupled to the at least one gas conduit 112, which is coupled to the UPW conduit 106 via at least one coupling member 118. As in the previous embodiment, the ultrapure water flowing through the UPW conduit 106 reacts with the gas within the gas conduit 112 to form at least one reaction solution. Further, like the UPW conduit 106, the gas conduit 112 may include one or more controllers, valve devices, mass flow controllers, sensors, indicators, etc. thereon or in communication therewith. For example, in the illustrated embodiment, the gas conduit 112 includes two (2) valves 114 and one (1) indicator 116 thereon to prevent water and / or gas from flowing back into the gas source 130; however, those skilled in the art will appreciate that any number of valves, indicators, controllers, etc. may be included on or in communication with the gas conduit 112 for any variety of applications.

[0033] Optionally, the gas source 130 can be configured to deliver carbon dioxide (CO2) to the ultrapure water to form a carbon dioxide aqueous solution before the ultrapure water flowing in the ultrapure water conduit 106 enters the first contact device 102a via the at least one solution conduit 120. It will be understood by those skilled in the art that the gas source 130 and the gas conduit 112 can be configured to provide a carbon dioxide flow to the ultrapure water flowing in the UPW conduit 106 at any desired flow rate. For example, in one embodiment, the gas source 130 and the gas conduit 112 can be configured to provide a carbon dioxide flow to the ultrapure water flowing in the UPW conduit 106 at a constant flow rate independent of the flow rate of the ultrapure water.

[0034] Reference again Figure 8 and 9 , the gas source 130 can be in communication with the second contact device 102b via at least one mixed gas conduit 132. Like the previous embodiments, the gas source 130 can be coupled to, in communication with, or contain at least one ozone generator. In the illustrated embodiment, a single gas source 130 is in fluid communication with the second contact device 102b, but any number of gas sources 130 can be used. Like the previous embodiments, Figure 7 and 8 The gas source 130 shown in the figure can be configured to provide a mixed gas composed of oxygen (O2), ozone (O3) and carbon dioxide (CO2) to the contact device 32. In alternative embodiments, multiple gas sources 130 can be coupled to the second contact device 102b or otherwise connected to the second contact device fluid. For example, separate sources of oxygen (O2), ozone (O3) and carbon dioxide (CO2) can each be coupled to the mixed gas conduit 132, so that the mixed gas conduit 132 mixes the mixed gas and transports it from the separate sources to the second contact device 102b. Figure 7 and 8 As shown, at least one valve, mass flow controller, indicator, sensor, etc. can be positioned on or in communication with the mixed gas conduit 132. For example, Figure 7 and 8 The illustrated embodiment of the ozone water delivery system 100 includes two (2) valves 134 and one (1) indicator 136 configured to prevent water and / or gas from flowing back into the gas source 130, but those skilled in the art will appreciate that any number or valves, mass flow controllers, indicators, sensors, etc. may be coupled to or in communication with the mixed gas conduit 132.

[0035] During use, an aqueous carbon dioxide solution is introduced into the first contact device 102a through the solution conduit 120. In addition, mixed gas from the mixed gas conduit 132 is introduced into the second contact device 102b. Some of the mixed gas is directed from the second contact device 102b to the first contact device 102a through at least one exhaust coupling conduit 164 that is fluidly connected to the first contact device 102a and the second contact device 102b. The mixed gas from the second contact device 102b can be introduced into the first contact device 102a and react with the aqueous carbon dioxide solution in the first contact device 102a, thereby dissolving the ozone in the mixed gas in the aqueous carbon dioxide solution to provide a dissolved ozone / UPW solution. The dissolved ozone / UPW solution in the first contact device 102a can be removed from the first contact device 102a through at least one first contact device conduit 152 and flow into the second contact device 102b, while the exhaust gas 166 is removed from the first contact device 102a through at least one first contact device exhaust conduit 168. In the illustrated embodiment, at least one pump 150 may be used to direct the dissolved ozone / UPW solution from the first contacting device 102a to the second contacting device 102b via a first contacting device conduit 152 .

[0036] Reference again Figure 8 and 9 , the dissolved ozone / UPW solution from the first contact device 102a is directed to the second contact device 102b in the presence of the mixed gas from the gas source 130. Thus, the ozone mixed gas within the second contact device 102b dissolves in the dissolved ozone / UPW solution, thereby resulting in a higher concentration of dissolved ozone 160, which can be output from the second contact device 102b via at least one second contact device output conduit 162. Those skilled in the art will appreciate that, although Figure 7 and 8 The first and second contacting means are shown coupled in series, but the first and second contacting means may be coupled in any desired configuration.

[0037] Optionally, Fig. 9 A system having at least one processor is shown. Figure 81. An alternative embodiment of an ozone water delivery system 100 is shown in FIG. 1. Like the previous embodiments described above, at least one sensor, indicator, valve, etc. can be positioned on the second contact device output conduit 162. For example, in the illustrated embodiment, a sensor 170 is coupled to the second contact device output conduit 162, but any other component known to those skilled in the art, such as a pressure sensor or a level sensor, can be similarly included. The sensor 170 can be in communication with at least one processor 174 via at least one processor conduit 172. Further, the processor 174 can be in communication with at least one of the UPW source 104, the mass flow controller 114, the indicator 116, the gas source 130, the mass flow controller 134, the pump 150, and the indicator 136 via the processor conduit 172. Thus, the processor 174 can be configured to receive data from and provide data to at least one of the UPW source 104, the mass flow controller 114, the indicator 116, the gas source 130, the mass flow controller 134, the indicator 136, and the sensor 170. During use, processor 174 may be configured to monitor dissolved ozone concentration and similar properties of ozone water and selectively change the performance of UPW source 104, mass flow controller 114, indicator 116, gas source 130, mass flow controller 134, pump 150, and sensor 170 accordingly. Pump 150 may be controlled to set the pressure of contact device 102b to 0.1 bar to 1 bar higher than contact device 102a, such as 0.2 bar to 0.7 bar higher, but those skilled in the art will understand that contact device 102b may be operated at any desired pressure. Thus, although not in Fig. 9 102a, but those skilled in the art will appreciate that the pump 150 may be in communication with the processor 174. The pressure in the second contacting device 102b will be controlled to an effectively constant value by the processor 174. The pressure of the second contacting device 102b may be configured to be between 1 bar and 4 bar, such as between 1.8 bar and 2.5 bar.

[0038] The embodiments disclosed herein are illustrative of the principles of the present invention. Other modifications within the scope of the present invention may be employed. Therefore, the apparatus disclosed in this application is not limited to the apparatus exactly as shown and described herein.

Claims

1. An ozone water delivery system, characterized in that: include: a first contact device; at least one ultrapure water source, the at least one ultrapure water source configured to provide ultrapure water to the first contacting device; at least one ultrapure water conduit coupled to the at least one ultrapure water source and the first contacting device; at least one solution conduit, the at least one solution conduit being in communication with the first contacting device and the at least one ultrapure water source through the at least one ultrapure water conduit, wherein at least one solution is provided to the first contacting device through the at least one solution conduit; at least one gas source; at least one gas conduit in communication with the at least one gas source and in communication with at least one of the at least one ultrapure water source and the at least one ultrapure water conduit; at least a second contact device, the at least second contact device being in communication with the first contact device via at least one first contact device conduit, the at least one first contact device conduit being configured to transport ozone water output from the first contact device to the at least second contact device; at least one mixed gas conduit in communication with the at least one gas source and the at least second contacting device, the at least one mixed gas conduit being configured to provide at least one mixed gas to the at least second contacting device; at least one exhaust gas conduit in communication with the at least second contacting device and the first contacting device, the at least one exhaust gas conduit being configured to direct a portion of the at least one mixed gas from the at least second contacting device to the first contacting device; as well as at least one ozone water output conduit, the at least one ozone water output conduit being in communication with the at least second contacting device; wherein the at least one gas source is configured to provide carbon dioxide to at least one of the at least one ultrapure water source, the at least one ultrapure water conduit, and the at least one solution conduit, thereby forming a carbon dioxide aqueous solution; The at least one mixed gas flowing from the at least one gas source to the at least second contacting device through the at least one mixed gas conduit comprises oxygen, ozone and carbon dioxide.

2. The ozone water delivery system according to claim 1, characterized in that: At least one of the first contacting means and the at least second contacting means comprises at least one packed column contacting means.

3. The ozone water delivery system according to claim 1, characterized in that: At least one of the first contacting device and the at least second contacting device comprises at least one packed column contacting device comprising a tower packing therein.

4. The ozone water delivery system according to claim 1, characterized in that: At least one of the first contacting device and the at least second contacting device comprises at least one membrane-based contacting device having at least one membrane module therein.

5. The ozone water delivery system according to claim 1, characterized in that: It further comprises at least one pump, the at least one pump being in communication with the first contact device and the at least second contact device, the at least one pump being configured to pump the ozone water output from the first contact device to the at least second contact device.

6. The ozone water delivery system according to claim 1, characterized in that: The at least one gas source is configured to flow carbon dioxide at a flow rate of 0.01 SLPM to 0.5 SLPM to at least one of the at least one ultrapure water source, the at least one ultrapure water conduit, and the at least one solution conduit.

7. The ozone water delivery system according to claim 1, characterized in that: The at least one mixed gas flowing from the at least one gas source to the at least second contacting device through the at least one mixed gas conduit comprises at least one gas selected from nitrogen, nitrogen dioxide and nitrous oxide.

8. The ozone water delivery system according to claim 1, characterized in that: It further includes at least one of a valve and a flow restrictor positioned on at least one of the at least one gas source, the at least one ultrapure water source, the at least one ultrapure water conduit, the at least one solution conduit, the at least one first contact device conduit, the at least one mixed gas conduit, the at least one exhaust gas conduit and the at least one ozone water output conduit.

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