TW524717B - Oxidative reactor for conversion of sulfite salts to sulfate salts - Google Patents

Abstract

An oxidative reactor, system and method are disclosed that use a fine bubble generator to provide a high rate of oxygen transfer to oxidize aqueous salts to their oxidized forms. A mixer distributes those fine bubbles into the aqueous solution. As the reduced salt reacts with the oxygen, it oxidizes. A washer can optionally prevent the deposition of solids, such as precipitated sulfate salt and/or scale, on the fine bubble generator and aid in removing such solids that form on the generator. The oxidative reactor, system and method can be operated in either continuous or batch modes.

Description

524717 V. Description of the invention (1) This patent application filed US Provisional Application No. 60 / 132,273 filed on May 3, 1999, and US Provisional Application No. 60/149 557 filed on August 18, 1999 No., and the benefits of US Provisional Application No. 60 / 165,956, dated 17, 1999. The present invention relates to an oxidation reactor and method for generating an oxidized salt from a reduced salt. More specifically, the present invention relates to an oxidation reactor capable of providing high-speed oxygen transfer for oxidizing, for example, calcium sulfite, sodium, magnesium, and / or ammonium and iron salts to their oxidized forms, and using the same Reactor method. As the power generation business and production plants increased the use of pollution control equipment to meet emission standards for clean air regulations, the volume of flue gas desulfurization by-products also increased. Those by-products must be disposed of in accordance with the requirements of the Resource Conservation and Recovery Regulations (RCRA). The RCRA requires that waste be disposed of in ponds or fills in accordance with certain standards. It becomes more difficult to dispose of such by-products in their fill or ponds as the accumulation of waste continues to increase. What's more, as lining and groundwater monitoring requirements become more stringent, the cost of treating those by-products as waste quickly rises. As a result, many power generation and production plants are seeking alternative ways to deal with flue gas desulfurization by-products. In particular, those factories are looking for more efficient and cost-effective equipment and methods to convert such by-products into useful recycled materials. Such equipment and methods not only help to avoid the RCRA requirements, but also because the sale of these recycled materials can partially offset the cost of purchasing and operating pollution control equipment. Most FGD processes use a basic absorbent to remove sulfur by-products from combustion. Alkaline earth metals, calcium and magnesium are commonly used in these most common FGD systems. The paper size is applicable to China National Standard (CNS) A4 (210x297). -4 · ----- U ----: ----- ---- r --- Order --------- Line ί Please read the precautions on the back before filling out this page} Printed by the Employee Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 524717

(2) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

And sodium or ammonium compounds as absorbents. In the FGD method, these absorbents form the corresponding sulfites. Most of these FGD methods eventually produce calcium sulfite or calcium sulfate as the final waste product. These waste products may also contain some sodium or magnesium sulfites or sulfates. Occasionally, smaller amounts of ammonium and magnesium sulfites will be produced. However, sulfite can no longer be used during the production process, so its disposal is in the fill, or it is oxidized in situ or elsewhere. Into calcium sulfate. Other sulfites, such as sodium sulfite, ammonium and / or magnesium can also be oxidized. This type of sulfite also appears to be disposed of. However, all dance, town and recorded sulfates have some commercial value associated with them. For many power generation businesses and manufacturing plants, adding pollution control equipment to effectively convert flue gas desulfurization by-products into useful products requires modification of existing pollution control methods. Such modifications of the scrubbing system typically include adding in-situ or elsewhere equipment to oxidize sulfite to sulfate (eg, oxidize calcium sulfite to calcium sulfate (gypsum), and then precipitate the sulfate and / Or dehydration. The equipment currently used elsewhere is a tower with a coarse air bubble diffuser (plurality). Usually oxidation towers are inefficient because they have a large water column (plurality). To generate enough air pressure and volume to generate Bubbles to oxidize water columns require large air compressors. These large compressors generate a large amount of heat, which is transmitted to the water column through the diffuser. When the temperature of the water rises, the solubility of oxygen decreases, thus reducing the efficiency of the oxidation process. Oxidation of sulfite to sulfate in the tower also heats the water column, which further reduces the solubility of oxygen. To counteract these thermal effects, an air / water heat exchanger or a humidifier is used to cool the compressed air before being injected into the tower. Need to use a heat exchanger or humidifier significantly. This paper size applies to Chinese National Standard (CNS) A4 specifications (210 X 297 public love). I --------- install -----: ---- Order ------ II-- (Please read the precautions on the back before filling out this page) 524717 Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (3) The operating cost of this type of equipment has been increased. A relative disadvantage is that the diffuser is easy to block, because scale will be generated around the holes of the diffuser. Especially the diffuser with small holes will soon be blocked and can no longer be operated. To overcome this difficulty, the diffuser is designed to have Large pores. Although large pores are less prone to plugging, they have the disadvantage of producing the large bubbles mentioned above, and their surface to volume ratio is very low. Such large bubbles are inefficient in transferring oxygen to the surrounding liquid. To overcome that difficulty, it is necessary to increase the volume of bubbles passing through the tower, which requires a larger compressor. Another problem with this type of tower design is that when the bubbles rise in the column, the column head pressure of the flow Zhao Jingli changes significantly. As a result, when the bubbles As they rise, they swell and reduce their surface area to volume ratio, reducing the rate of oxygen transfer to the surrounding liquid. The oxidation rate of sulfite to sulfate is also reduced. In summary, current tower designs are extremely energy consuming, as they require a large volume of air to provide sufficient aeration to oxidize sulfites to their sulphate forms. The coarse air bubble diffusers used in those designs cannot Effectively oxidize sulfites, because the surface area to volume ratio of the large bubbles they generate is too small, which results in inefficient oxygen transfer. Furthermore, when changing the design to produce small bubbles, it must be caused by the accumulation of scale. Plugging requires frequent maintenance. To overcome the shortcomings of current tower designs, a reactor is needed that can provide efficient oxidation of sulfite to its sulfur-acid form while preventing scale formation on the aerator. This A reactor should be able to provide a high rate of oxygen transfer through the fine bubbles of oxygen-containing gas. The large surface area to volume ratio of the fine bubbles can enhance the transfer of oxygen to the surrounding liquid, but it can maintain no scale accumulation and interfere with the supply of fine bubbles. versus. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) — ^^^ -------- · line -0 ^-(Please read the precautions on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 524717 A7 ^: ___ B7 Swallowing and Description of Invention (4) According to the present invention, there is an oxidation reactor with a fine bubble generator, which provides high-rate oxygen transfer to oxidize the reduced salt to Its oxidized form. The bubble generator introduces a fine bubble of oxygen-containing gas into a solution containing one or more reducing salts. This solution can be, for example, an aqueous slurry of a reducing salt (eg, calcium sulfite), an aqueous solution of a dissolved sulfite (eg, sulfite or iron sulfate), and / or an equilibrium with a slurry Dissolved salt. A mixer distributes those bubbles into the solution, causing high-rate oxygen to be transferred into the solution. When the reduced salt interacts with oxygen, it is oxidized. Advantageously, a scrubber is selectively used to prevent solids such as sulfates and scale from depositing on the fine bubble generator and to help remove such solids from the generator. The oxidation reactor can be operated in continuous or batch mode. One or several oxidation reactor systems connected in series and / or parallel may be provided to conveniently oxidize the reduced salt and / or remove individual reactors from the production line for maintenance and / or repair. According to another aspect, a method is provided for rapidly forming a salt from a reduced form into its oxidized salt. A flow of fine bubbles of an oxygen-containing gas generated by a fine bubble generator is sent to an aqueous solution containing one or more reducing salts. Bubbles are mixed into an aqueous solution to provide a high rate of oxygen transfer to that solution to support a high rate of oxidation reaction and oxidize the reducing salt to its oxidized form. Advantageously, any solids that accumulate on the fine bubble generator can be selectively removed from that generator when the sulfate is formed, keeping the generator substantially free of such solids. Among the goals disclosed in this article, an oxidation reactor with a fine-bubble generator supports the transfer of oxygen-containing gases into a solution containing reducing salts at a south rate. This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 7 -------------- install -----: ---- order ---- ----- line (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 524717 Α7 _ Β7 V. Description of the invention (5) Among the other objects disclosed, the oxidation reaction apparatus A scrubber is optionally included which prevents solids from depositing on the fine bubble generator and helps to remove such solids formed on the generator. Among other objectives disclosed, the system of an oxidation reactor, which can operate in series or in parallel in a continuous or batch operation, to process reducing salts, so that individual reactors can be removed from the production line for maintenance or repair , You can also adjust the system according to the amount of reducing salt to be processed. Among other objects disclosed, one method of oxidizing sulfite to sulfate is that it transfers oxygen to a monohydrate solution containing suspended sulfite via high speed. Examining the following descriptions, drawings, and scope of applications, other purposes and advantages are obvious to the skilled person. FIG. 1 is a side view of an embodiment of a reactor with a part of a tank wall cut off; FIG. 2 is a side view of an embodiment including a gas transfer mechanism; FIG. 3 is a second embodiment of a reactor with a part of a tank wall cut away Fig. 4 is a side view of a third embodiment of a reactor; Figs. 5a and 5b are flowcharts of a series of reactors; and Fig. 6 is a side view of a reactor embodiment with a part of a side wall cut away . Referring to Fig. 1, there is shown a single tank embodiment of a reactor generally oxidizing a reducing salt to its corresponding oxidation form. The reactor 10 includes a liquid holding tank 15. As shown, the slot 15 is generally rectangular or circular and is delimited by the side wall 12 and the bottom wall 14. The groove 15 may have other shapes. Preferably, the top of the slot 15 is open to accommodate high-speed inflation and to allow liquid evaporation and other bulk paper sizes to comply with Chinese National Standard (CNS) A4 specifications (210 X 297 mm) ---- i-- --r --------- r --- ^ --------- line (Please read the precautions on the back before filling this page) 524717 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Preparation of A7 B7 base, description of the invention (6) Thermal method to cool the reactor. The tank 15 may be made of any material suitable for containing a reducing salt solution and its oxidized form. For example, the tank 15 is made of a chemical resistant material such as stainless steel or glass fiber, which is resistant to gas, sulfite, sulfate, and / or The acid rot name is resistant. The groove 15 can also be constructed with a chemically resistant coating, such as a mild steel covered with an elastomer. Other suitable chemical resistant coatings include rubber, polyurethane, butylene EFLON, (polytetrafluoroethylene) or other materials that are resistant to the effects of gas, sulfite, sulfate, and / or acid corrosion. The groove 15 may also have its dagger, such as, for example, a groove with a concrete bottom and / or side walls. The tank 15 includes one or more holes 20 for feeding a reducing salt into the tank 15 and discharging an oxidized salt from the tank 15. Alternatively, the reduced salt feed can be fed via a tube through the top of the open slot 15. In the illustrated embodiment, the tank 5 has more than one hole 20, including at least one inlet 25 and at least one outlet 300. The inlet 25 provides for the reduction salt to be fed into the tank 15, and the outlet 30 provides for the oxidation salt Drain from slot 15. Each hole 20, including an inlet 25 or an outlet 30, can be positioned at any appropriate position on the slot 15. For example, an inlet 25 described in FIG. 1 is located above the outlet 30. The inlet 25 can also be configured to introduce reducing salts into the tank near the top of the tank 15 or the bottom of the tank 15. Preferably, the at least one inlet 25 and the at least one outlet 30 are positioned substantially at the same height above the bottom of the tank, and in a lower portion of the tank 15, such as below half of the tank. As will be appreciated by those skilled in the art, other methods of feeding reducing salts into the tank 15 and discharging oxidized salts from the tank 15 are within the scope of the present invention. In the illustrated embodiment, the reactor has a dummy bottom plate 40. The fake bottom plate 40 can be perforated to make the water-soluble paper size applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ------------- install -----:- --- Order --------- line (please read the precautions on the back before filling this page) 524717 Printed A7 B7 i 'Invention Note (7) Liquid 35 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Can flow in the tank 15. In other embodiments, the reactor 10 eliminates the dummy floor 40. The tank 15 contains a solution of one or more additional salts, such as, for example, an alkali metal or alkaline earth metal sulfite (for example, sodium or calcium), magnesium and / or ammonium sulfite, and iron sulfate. Such salts can be dissolved and / or suspended in an aqueous solution. For example, in one embodiment, the tank 15 can hold a certain amount of water slurry 35 in which calcium sulfite solids are suspended, which is in equilibrium with the sulfite cleavage dissolved in the solution. The preferred sulfite is suspended solids having about 5 to about 25% (w / v), even if the concentration is slightly higher or lower is within the scope of the present invention. More preferably, the calcium sulfite slurry is about 15. /. To 25% (w / v) suspended solids. Slurry 35 can further include a supersaturated slurry. The concentration of calcium sulfite in the slurry 35 in the tank 15 can be adjusted by introducing water, an aqueous solution of calcium sulfite, another aqueous medium, or solid calcium sulfite. In the tank 15, the pH of the calcium sulfite slurry 35 is preferably acidic, and ranges from about 3 to about 7. In a more preferred embodiment, the pH is between about 4.5 and about 5.5. The pH can be adjusted with any suitable acid, including, for example, sulfuric acid. The pH of the calcium sulfite water slurry 35 can be monitored using any suitable sensor with fluid communication with the tank. The pH of the aqueous solution 35 can also be adjusted or maintained before it is sent to the tank 15. As those skilled in the art will recognize, aqueous solutions can also include other sulfite solutions or slurries. As recognized, 'other salts can also be oxidized in the reactor 10, for example, ferrous iron from smelting waste is oxidized in the reactor 10 to normal iron. Similarly, any reaction that requires dissolved oxygen can usually be applied. In some aspects, the aqueous solution 35 optionally further includes an interfacial activity «— — — — — — — 丨 if hit ΜΗ · II order --------- line · fjing first read the notes on the back before (Fill in this page)

524717 Printed by the Consumers' Cooperative of the Ministry of Economic Affairs and V Hui Property Bureau. Α7 Β7 Real and Invention Description (8) Sexual agents to enhance the transfer of oxygen to that solution. Surfactants can also be added to the aqueous solution 35 to reduce bubble size and / or reduce foaming in that solvent. Suitable surfactants include, for example, sodium silicate or TEFLONB (polytetrafluoroethylene). The reactor 10 further includes a fine bubble generator which receives the incoming gas 66. The gas 66 may be any suitable oxygen-containing gas, such as air. Fine bubbles_ A fine bubble is generated from the gas 66 and those bubbles are introduced into the aqueous solution 35. As used herein, the term "fine bubbles" means that the gas has a large surface area to volume ratio. The large surface area to accumulation ratio provides a high proportion of oxygen transferred into the aqueous solution 35 in the tank 15. Suitable surface area to volume ratios are from about 5 to about 10, even larger and smaller ratios are within the scope of the invention. Suitable bubble sizes range from about 0.6 microns to about 2 microns, although larger and smaller sizes are also within the scope of the present invention. In some embodiments, the temperature of the fine gas bubbles introduced into the aqueous solution is substantially the same as the temperature of the indoor air near the tank. An example of a fine bubble generator is described with reference to Fig. 1 '. The fine bubble generator includes a flow tube 55 and a rotor 60. As used herein, the term rotor may include a rotor, such as a thruster, with slots, holes or teeth in the blade. The rotor 60 may be driven by, for example, a vertically oriented, rotatable drive shaft 72, which is generally centered. The drive shaft 72 is connected to a bearing assembly and drive motor 64. It may also be other suitable mechanisms to drive the rotor 60, and it is also within the scope of the present invention. A selective rotor is surrounded by a disperser 63, such as a porous disperser, which is coaxially aligned with the drive shaft 72, and its role is to shear the bubbles and eliminate the excessive full flow in the tank 15. In other embodiments, the fine bubble generator and I --r I-^ --- 11--I < Please read the precautions on the back before filling this page)

524717 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ____B7 V. Description of Invention (9) Excludes the flow tube 55 and / or the diffuser 63. As recognized by those skilled in the art, the size of the bubbles created by the fine bubble generator is controlled by a number of factors, including the thickness of the rotor blades, the speed of rotation of the rotor 60, the size and depth of the rotor blades, and the selectivity in the diffuser The diameter, area, location of any holes, and the thickness of that diffuser. Optionally, the rotor 60 can have holes and small holes in the rotor blades to increase the bubbles formed by the fine bubble generator. When the rotor 60 rotates, it draws the aqueous solution 35 into the flow tube 55. The flow tube 55 guides the aqueous solution 35 up to the rotor 60. The rotation of the rotor 60 also draws an oxygen-containing gas 65 into the top of the rotor 60. The gas 65 is carried in the aqueous solution 35 due to the establishment of the vortex 66. When the gas 65 is carried into the liquid, bubbles 69 are formed. Those bubbles 69 are further sheared as they pass through the diffuser 63 to form fine bubbles of an oxygen-containing gas. Preferably, the position of the fine bubble generator in the tank 15 is adjustable, such as by raising or lowering the position of the generator in the tank 15 or raising or lowering the liquid level in the tank 15. Withering of the fine bubble generator corresponding to the position of the surface of the aqueous solution 35 facilitates controlling the amount of aeration and / or circulation of the aqueous solution 35. For example, if the rotor 60 is raised toward the surface of the aqueous solution 35, the amount of inflation will increase. Similarly, if the position of the rotor 60 is deeper into the aqueous solution 35, the amount of aeration will decrease and at the same time the amount of circulation of the pulp will increase. In certain aspects of the invention, the gas 65 may be introduced into the rotor 60 via a conduit extending through the drive rod. In the reactor described in Fig. 1, a water storage tower or downpipe 96 feeds the gas 65 into the rotor 60. The gas can also be introduced into the reactor 10 through a separate guide or water pipe (not shown). The gas 65 flows into the fine bubble generator, and can be assisted by any suitable gas transfer mechanism, such as the paper size suitable for the country "(CNb) A4 size coffee 297 public love)---(Please read the note on the back first (Fill in this page again)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 524717 Α7 • ~: ---- Β7 V. Description of the invention (10) For example, a fan, blower, dual-load compressor, hydraulic machine, hydraulic machine, or centrifugal dryer. Gas is injected into the top of the flow tube 55 or the rotor 60. Referring to FIG. 2, the reactor 10 includes a blower 80 and is connected to a gas valve 85 through a line 83. The air pressure provided by the hair dryer 80 is approximately equal to 5-10 feet of water pressure. Other gas transfer mechanisms are also possible, depending on the depth of the rotor 60 and the expected flow of the oxygen-containing gas 66. The rotor 60 further includes a mixer to distribute the fine air bubbles 69 into the aqueous solution 35 in the tank 15 >. When those bubbles 69 are distributed into the aqueous solution 35, they facilitate high-speed oxygen transfer into that solution. Generally, the more thoroughly the fine air bubbles 69 are mixed into the aqueous solution 35, the higher the rate at which oxygen is transferred into the solution. In other embodiments, the mixer may be some other mechanism capable of distributing bubbles into the aqueous solution 35. For example, the mixer may be a separate rotor, a propeller, or other mixing equipment capable of distributing the fine bubbles 69 into the aqueous solution 35. The optional 'mixer can further include a flow tube M, a disperser M, and / or a perforated dummy bottom plate 40 to more uniformly circulate the aqueous solution 35. • Referring to Figure 1, the mixer circulates the aqueous solution and distributes air bubbles into the bath. For example, the mixer can create a circulation path 70, which distributes air bubbles into the aqueous solution and directs the water slurry and air bubbles to the outside and faces the wall of the tank 15. In this example, the reduced salt also flows along the circulation path 70. Skilled people recognize it, and other circulation paths are possible. In certain embodiments, the mixer maintains precipitation of the salt, such as, for example, calcium sulfate in a suspension in aqueous solution 35. Advantageously, the size of the precipitated salt increases as it flows along the circulation path. The mixing apparatus selectively reduces the accumulation of the salt in the aqueous solution 35 on the surface of the aqueous solution 35 so that the distribution of the salt in the aqueous solution 35 is substantially uniform. In another embodiment, the paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 cm) ------------- ^ ----- r --- ^- ------- ^ (Please read the notes on the back before filling out this page) 13 524717 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (u) 'It includes a flow tube and In the fake bottom plate, the aqueous solution 35 flows along the circulation path, passes through the holes in the fake bottom plate, enters the flow tube, and then enters the mixer. The reactor 10 includes a flow diverter to increase the size of the oxidation area by directing the flow of fine bubbles and the aqueous solution 35 into the tank 15 again. Those skilled in the art will recognize that the selection and arrangement of the flow redirector can control the size and position of the oxidized area. In some embodiments, the oxidized area can be 25% larger than the volume of the aqueous solution 35. Referring to Fig. 2, an exhaust hood 75 and a disperser 63 can increase the size of the oxidation area by directing the flow of fine bubbles and the aqueous solution 35 inward and toward the mixer. Referring to Figure 6 'a flow diverter can also include a baffle 300 placed near the fine bubble generator. Such baffle 300 extends at least partly between the fine bubble generator and the groove wall, or the baffle can extend completely from the fine bubble generator to the groove wall. This type of stretcher 300 is optionally usually a vertical device. Flow diverters can selectively create many circulation paths. In other embodiments, a single exhaust hood 75, diffuser 63, or baffle 300 can form a flow diverter. The fine bubble generators are selectively cleaned and kept free of solids, and they may deposit on that generator. Cleaning also prevents solids from settling on the generator, which are generated from the formation and / or precipitation of oxidized salts. In the example shown in Fig. 1, the rotor 60 and the disperser 63 constitute a washer which guides the flow of the aqueous solution 35 onto the fine bubble generator. In operation, the washer directs the flow of the aqueous solution onto the critical surface of the fine bubble generator, which may suffer from solids deposition. That flow prevents solids such as, for example, steel scale, sulfite or sulfate 'from depositing on the generator. On the other hand, the scrubber agitates any salt in the sink to keep it suspended in the aqueous solution, and applies a friction effect on the fine bubble generator to remove any deposited solid paper from the generator. National Standard (CNS > A4 specification (21G X 297 mm) ------- ---- J ---- 1 --------- r --- ^ ----- ---- ^ tow. (Please read the precautions on the back before filling this page) 524717 Α7 Β7

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (12). In other embodiments, the cleaner may be a rotor or other suitable equipment. Referring to Fig. 3, another example of the reactor 10 is described. The reactor 10 includes a tank 200, a rotor 203, and a fixed body 201. The rotor 203 is driven by a hollow drive shaft 205 oriented vertically to horizontally. The drive shaft 205 is connected to a bearing assembly and motor 220. The gas 65 enters the internal cavity of the rotor 203 through the hole 209. In some embodiments, the gas can enter the interior of the rotor shaft through the gas diffuser 21o. In other embodiments, the rotor shaft is without a gas diffuser. A preferred internal cavity is created from a material that is at least partially gas permeable, such as, for example, a porous material. The hole 209 can be connected to any suitable gas transfer mechanism, such as, for example, a fan, blower, dual-load compressor, oil press, hydraulic press, or centrifugal blow dryer, which can provide airflow into the drive shaft 205 66. The rotor 203 and the fixed body 201 constitute a fine bubble generator. The rotation of the rotor 203 creates a vortex, which mixes the gas 65 into the aqueous solution 35. When gas is injected into the vortex from the proximal end 208 of the rotor 205, the gas 66 is carried into the solution and forms a bubble 69. When these bubbles pass through the fixed body 20, they are further sheared to form fine bubbles of oxygen-containing gas. The rotor 203 and the fixed body 201 further constitute a mixer 'to distribute the fine bubbles of the oxygen-containing gas into the aqueous solution 3 5. Optionally, a flow tube (not shown) guides the aqueous solution 35 to the rotor 203 and the fixed body 201 or flows out of the rotor 203 and the fixed body 201. The fine bubble generator is selectively cleaned to remove solids that may have deposited on the generator. The rotor 203 and the fixed body 201 can further constitute a cleaner, which guides the aqueous solution 35 to the critical surface of the generator that may be subject to solid deposition. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm)- ----------- install -----: ---- order --------- line (please read the precautions on the back before filling this page) 524717 Ministry of Economic Affairs wisdom Printed on the A7 B7 by the Consumer Cooperatives of the Property Bureau V. Invention Description (13). That stream prevents solids such as, for example, scale, calcium sulphite and calcium sulphate > from accumulating on the generator. The scrubber also agitates any precipitated sulfate, keeping it suspended in the aqueous solution, and applies a friction effect on the fine bubble generator 'to remove any deposited solids from the generator. In another aspect of the invention, a fluid level controller is optionally included in the reactor 10. This controller monitors the level of the aqueous solution 35 in the tank 15. The surface level of the aqueous solution 35 is detected by one or several sensing elements and a signal is transmitted to a processor. Based on the signal from the sensing element, the controller can adjust the operation of the reactor. For example, the controller can increase or decrease the amount of the aqueous solution entering or leaving the reactor, the speed of the mixer, the amount of aeration, and / or the depth of the fine bubble generator in the aqueous solution. The fluid level controller may also be a foam sensing element that can communicate with a processing unit. When the foam reaches a defined height above the level of the aqueous solution 35, a signal is sent which can trigger the release of a defoamer to reduce the amount of foam. In another aspect of the invention, the reactor 10 can include a tank 15 having any suitable form of fine bubble generator, mixer, washer, and optionally one or more flow diverters. For example, Referring to FIG. 4, the reactor 10 includes a generally rectangular or circular groove 15, or a groove (not shown). The three rotors 60 are driven by a motor 64. Each rotor 60 is optionally surrounded by a coaxially extending diffuser 63 or other flow diverter. The flow tube 5 5 receives the aqueous solution 35 and directs it to the fine bubble generator. The water storage tower 99 receives the oxygen-containing gas 66 from the gas transfer mechanism 80 via the line 112. A reduced salt, such as an aqueous solution or slurry, enters tank 15 through inlet 25 and the oxidized salt is extracted through outlet 30. Other types of reactors 10 are also possible, and it is recognized by the skilled person that the paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love). ---- l · --- Order --------- Line »(Please read the notes on the back before filling in this page) 524717. A7

(14) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. In another aspect, an oxidation reactor system that enables oxidation reactions to oxidize one or more reducing salts to their oxidized form. One or more oxidation reactors can be connected in series and / or in parallel. This arrangement allows individual reactors to be taken off-line for maintenance and / or repair without having to empty the entire system during such maintenance or repair. This system further provides a method for continuous salt processing. An example of a continuous processing system is described with reference to Figs. 5a and 5b. Figure & describes the use of reactors 10 connected in series for the treatment of reducing salts. The reactors are interconnected by a line 102, providing fluid communication between those units. Line 101 connects the first reactor to any suitable reduction source 10 (), such as a slurry or solution containing reducing salts. This source includes a flue gas desulfurized polyester scrubber or other pollution control device that produces any form of reducing salt (e.g., sulfite), including wet and dry forms. Other suitable sources of reducing salts include storage tanks, fills, mineral leachate and the like. Each reactor contained a certain amount of a reducing salt solution. When aqueous salt is moved from one reactor to another, the amount of oxidized salt in the aqueous solution will increase. Those skilled in the art can recognize that by adjusting the transport of oxygen-containing gas in each reactor, the oxidation of the aqueous solution and the residence time of the solution in each reactor, the efficiency of the oxidation reaction process can be controlled. Line 108 connects the last reactor ι0 to another component 110, such as, for example, a dehydration plant, dryer or storage. Suitable dewatering equipment can include, for example, a fluid cyclone or a horizontal ▼ vacuum transitioner. Many dewatering equipment can be connected in series and / or in parallel. For example, 'a fluid cyclone can be used in the first stage of the dewatering process, and then

Read the notes on the back of the page and then re-fill them. • Binding pages. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Optionally, a gas transfer mechanism (not shown) communicates with one or more reactors to provide gas delivery to the reactor 10. Figure 5a also illustrates an example of a flow line and a valve, which can control the flow of the aqueous solution to and from the individual reactor 10. The flow line 105 and the valve 106 provide a way for the aqueous solution 35 to deviate from or flow out of one or more reactors 10. For example, in some cases, it is desirable to bypass individual reactors for maintenance or repair. Similarly, to increase the efficiency of the oxidation process, or to process materials with lower oxidation rates, connect additional reactors to the pipeline to eliminate other reactors. Referring to Figure 5b, a parallel processing system is described. A suitable source of salt 100 ', for example, a flue gas desulfurization scrubber or other pollution control equipment, can be communicated via the line 101 and the reactor 10. Other suitable sources of reducing salts include storage tanks and / or fill. A valve 106 controls the flow of the aqueous solution to each reactor 10. Line 108 provides the discharge of sulfate from each reactor. Line 108 and other components 110 can be used for fluid communication. It can include a dewatering device or storage tank. As described in this example, a gas transfer mechanism 80 is in fluid communication with one or more reactors 10 through line 112 to provide higher speeds for gas transfer to the reactors 10. Those skilled in the art will recognize that the system is not limited to the examples described in Figures 5a and 5b. Other aspects of the invention provide a method for oxidizing salts. A reducing salt, such as, for example, calcium sulfite, is introduced into the tank 15 of the reactor 10. This calcium sulfite is preferably a monohydrate slurry of calcium sulfite. The suspended solids range from about 5% to about 25% (w / v), although higher or lower amounts are also present in the paper of the present invention. Standards apply to China National Standard (CNS) A4 specifications (210 x 297 public love) 18 ---- ^ ----: ------------ 丨 Order -------- · (Please read the notes on the back before filling out this page) 524717 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

Jade and invention description (16) Other reducing salts, such as sodium, magnesium and / or ammonium salts or iron sulfate 'can be introduced into the tank 15 at any suitable concentration, as will be recognized by those skilled in the art. The reduced salt can be selectively from an external reservoir, from a scrubber unit, such as, for example, a lime scrubber with added magnesium, a stripper without magnesium addition, or a limestone-based scrubber, or Import from other sources of reducing salt, such as a storage pond, landfill or mining area. If necessary, the pH of the aqueous solution 35 is adjusted to oxidize and / or precipitate the lialea sulfate to its sulfate form. For example, for a calcium sulfite slurry, the pH can be adjusted in the range of about pH 3 to 7, and more preferably about 4.5 to about 5.5. The pH of the aqueous solution 35 can be adjusted in the tank 15 by adding a suitable acid, such as, for example, sulfuric acid or any suitable base. For certain processing operations, the pH of the aqueous solution 35 is preferably adjusted before it is introduced into the tank 15. In operation ', a stream of fine bubbles of an oxygen-containing gas is delivered into the aqueous solution in the tank 5. For example, referring to the figure, when the rotor 60 rotates, it also sucks the oxygen-containing gas 65 into the water storage tower 90, and the aqueous solution 35 enters the lower end of the rotor 60. The gas 66 is carried in the aqueous solution 35 by the established vortex. When the gas 66 is carried in the aqueous solution 35, bubbles 69 are formed. By the rotation and selectivity of the rotor 选择性, those air bubbles are further sheared through the flow of the aerated aqueous solution 35 through the diffuser 63. Referring to FIG. 3, the rotor 203 and the fixed body 201 can also generate and transport fine air bubbles to the aqueous solution. For example, the rotation of the rotor 203 creates a vortex, which mixes the gas 65 into the aqueous solution 35. When the gas is injected into the vortex from the nearest end 208 of the rotor 203, the gas & When those bubbles pass through the fixed body 201, they are further sheared to form fine bubbles of oxygen-containing gas. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) _____ I ------- ^ --- I L ---- ^ ------- I (Please read first (Notes on the back, please fill out this page) 19

V. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 524717 Description of the invention (17) Bubbles 69 facilitate the transfer of oxygen into the reducing salt in solution 35. When oxygen dissolves in that solution, it interacts with the salt and oxidizes it. For some oxidation processes, precipitation occurs when oxidized salts are formed. For example, when calcium sulfate is produced, calcium sulfate can precipitate if the solution has reached its saturation point. Precipitation can be aided by small particles or crystals that appear in the aqueous solution 35. If the reducing salt in the solution is in equilibrium with the suspended solids, the solids will dissolve when the oxidizing salt precipitates. During its oxidation, both reduced and oxidized salts are dissolved in solution 35. In a batch operation, substantially all reducing salts are oxidized before the oxidized salts are discharged from the reactor. In a continuous processing mode, the conversion efficiency is controlled by the surface area to volume ratio of the fine bubbles, the amount of oxygen introduced, the efficiency of oxygen transfer to the aqueous solution, the resulting partial pressure of oxygen in that solution, and the residence in the reactor time. The mixing of fine bubbles of an oxygen-containing gas with an aqueous solution 35 enhances the oxidation of the reducing salt to its oxidized form. This type of mixing can provide high-speed oxygen transfer into the aqueous sulfite solution 35. For example, in Figure 1, the rotor 60 and the disperser 63 create a circulation path 70 that distributes air bubbles throughout the aqueous solution 35 in the tank 15. Optionally, clean the fine bubble generator to prevent solids from depositing on it and help remove such solids from the generator. For example, a cleaning effect can occur by the circulation path 70 of the aqueous solution 35. The cleaning effect occurs when the aqueous solution 35 and any selected killer salt flow over the critical surface of the fine bubble generator. That stream prevents solids from settling on the generator. More specifically, the salt of any crystal provides friction on the critical surface of the fine bubble generator to remove the deposited or intended paper size. Applicable to China National Standard (CNS) A4 (210 X 297 mm) 丨 丨 丨-丨丨 丨 丨 丨 丨 ...... 丨 丨 丨 丨 丨 丨 丨 丨 丨 (Please read the precautions on the back before filling out this page) 20 524717 A7 ♦ ------- B7_ Jade, DESCRIPTION OF THE INVENTION (18) Any Gu Zhao deposited on the generator. Following reduction of the reduced salt into its oxidized form, the oxidized salt is withdrawn from the reactor 10. In one aspect of the invention, the oxidized salt is difficult to sink. In another aspect of the present invention, the " oxidized salt is dehydrated " such as, for example, in a fluid cyclone, however other dehydration methods are also within the scope of the present invention. The oxidized salt can be advanced to transition drying ' such as ' e.g. A horizontal band true line filter. In addition, the oxidized salt is transferred to the production department or stored for subsequent use or disposal. According to other aspects of the reactor and / or system, as described herein, the method can also be suitably performed. Other embodiments of the present invention are exemplified by the following examples. These examples illustrate the working principles of the present invention, but they are not intended to limit the present invention or the present invention is limited to these examples. example 1 :

The Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs printed magnesium-enhanced lime, non-magnesium-enhanced lime, or limestone air scrubbers to remove sulfur dioxide from a thermal power plant. The flue gas desulfurization process creates calcium sulfite and sends it to the oxidation reactor system. Before calcium sulfite enters the system, it is 0-60% oxidized. In the reactor, the pH of the aqueous slurry of calcium sulfite was about 5.5. The oxidation reactor uses air as a source of oxygen-containing gas to generate fine air bubbles in the range of about 0.6 to about 1.2 microns. Those bubbles are introduced into the calcium sulfite water slurry and oxidize the sulfite to form a calcium sulfate slurry. After a residence time of about 2-6 hours, more than 99% of the calcium sulfite is oxidized to calcium sulfate. Example 2: The blowdown from the flue gas desulfurizer (blowing down) disturbs the animal and sends it into a 21 -------------- installation ---- l · --- order · (Please read the precautions on the back before filling out this page) This paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) 524717 Printed by the Intellectual Property Bureau Staff Consumer Cooperative of the Ministry of Economic Affairs Α7 Β7 Invention Description (19) In a series oxidation reactor, blown air is used as a source of oxygen-containing gas. Oxidation of calcium sulfite was carried out in the aerator and in the reactor. Over 99% of calcium sulfite is oxidized. Example 3: A 3.5 liter reactor contains 16% or 260/0 suspended sulfurous acid solids. Fine air bubbles are generated using air as the source of oxygen-containing gas, and the range is from about 0.6 to about 1.2 microns. The rate of oxygen (in air) feed to the calcium sulfite slurry is about 2 liters per minute, or about 28.5 grams per hour. Oxygen was used to oxidize calcium sulfite to calcium sulphate at a rate of about 23.8 g / hour, which is an efficiency of 83%. Example 4 · A 3.5 liter reactor contained 180 g / L of dissolved ammonium sulfite. Using air as a source of oxygen-containing gas to generate fine air bubbles in the range of about 0.6 to about 1.2 micrometers can produce ammonium sulfate. The reaction rate of ammonium sulfite was 0.51 g / l / min. Example 5 · A 3.5 liter reactor contains 46 g / L of dissolved magnesium sulfite. Using air as a source of oxygen-containing gas to generate fine bubbles, the range is from about 0.6 to about 1.2 micrometers to produce magnesium sulfate. The reaction rate of magnesium sulfite was 1.35 g / l / min. Example 6 Calcium sulfite, such as taken from a landfill or pond, is slurried with water or with materials disturbed from a scrubber in a mixing tank. The resulting slurry is sent to an oxidation reactor. In the reactor, calcium sulfite is oxidized to calcium sulfate, and more than 99% of the calcium sulfite is oxidized to calcium sulfate. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 22 ----.---: ---------- r I--order ------ --- line < Please read the notes on the back before filling this page) 524717 A7 ------- B7 V. Description of the Invention (2) Example 7: Magnesium sulfite, ammonium, and / or sodium An aqueous solution is introduced into the oxidation reactor, which has a fine bubble generator and a mixer. A flow diverter including a baffle guides the aqueous solution toward the inside and toward the mixer, thus forming a circulation path. Sulfate is formed when oxygen from fine bubbles interacts with sulfite. After the oxidation has been substantially completed, the aqueous solution'sulphate is withdrawn from the reactor and sank from that solution. > Having thus described the preferred embodiment of the present invention in detail, it must be understood that the invention as defined by the scope of the appended patent application is not limited to the specific details shown in the above description, and many obvious from them Without departing from the spirit or scope of the invention. ------------- Installation ---- l · --- Order · (Please read the notes on the back before filling in this page) Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 23 524717 A7 _B7_ V. Description of the invention (21) The component numbers are printed on the basis of the printing of 10 ·· reactor 75 ... Air hood 12 ... Side wall 80 ... Hair dryer 14 ... Bottom wall 85 ... Gas valve 15 ... Slot 96 ... Drain pipe 20 ... 101 ... Line 25 ... Inlet 102 ... Line 30 ... Out π 105 ... Line 35 ... Aqueous solution 106 ... Valve 40 ... Fake base plate 108 ... Line 55 ... Flow tube 110 ... Assembly 60 ... Rotor 201 ... Fixed body 63 ... Diffuser 203 ... Rotor 64 ... Motor 205 ... Drive shaft 66 ... Gas 209 ·· 孑 L 69 ·· Bubble 220 ··· Motor 72 ·· Drive shaft 300… Baffle ---- ^ --- U ---------- ^ ---- Order-- ------- Line (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 public love) 24

Claims (1)

The scope of Shen Qing's patent og88 < ABC < Kind of oxidation reactor 'It supports the production and precipitation of calcium sulfate from calcium sulfite, the reactor includes: a tank' with walls and a bottom for containing calcium sulfite sludge An inlet of the slurry is on the tank, and is used to aggregate the water from the water slurry source into the tank. A fine bubble generator is in fluid communication with the water slurry and is a fine bubble containing oxygen gas. Introducing the water into the slurry; a flow diverter in the tank to reduce the rotation of the aqueous solution in the tank; and a mixer in the tank to distribute and maintain the air bubbles into the water flocculation and maintain The water slurry and air bubbles circulate in the tank; whereby a circulation path for the water slurry and air bubbles is created in the tank, an oxidation area is defined in the tank, which occupies a considerable volume of the tank, and The precipitated sulfuric acid words circulate in the circulation path. 2. The reactor according to item 1 of the scope of the patent application, where the gas is air 3. The reactor according to item 2, the scope of the patent application, wherein the temperature at which the air in the fine bubbles is introduced into the slurry and the temperature in the tank The temperature of the adjacent chamber air is substantially the same. 4. The reactor according to item 1 of the scope of patent application, further comprising: a rotor capable of rotating in the groove, which constitutes at least a part of the fine bubble generator and the cleaner. 5. The reactor according to item 4 of the scope of patent application, in which the rotor constitutes the paper size applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ) ____ Order --------- line—. Printed by A8B8C8D8 524717, Consumer Cooperatives of Intellectual Property Bureau of the Ministry of Economic Affairs. 6. Application for patent scope mixer. 6. The reactor according to item 4 of the scope of patent application, wherein the rotor has an internal cavity, at least partly formed of a gas-permeable material, which defines the cavity, and receives pressurized gas in the cavity And form at least part of the fine bubble generator. 7. The reactor according to item 4 of the scope of patent application, further comprising: a fixed body assembly, which defines the flow path of the water slurry around the rotor and constitutes at least part of the mixer. 8. The reactor according to item 1 of the scope of patent application, further comprising: a water storage tower installed above the fine bubble generator for transferring the oxygen-containing gas to the fine bubble generator. 9. The reactor according to item 1 of the scope of patent application, further comprising: a cleaner for cleaning the solids on the fine bubble generator, which is generated during the calcium sulfate generation and precipitation. 10. The reactor according to item 9 of the scope of patent application, further comprising: a flow tube installed below the mixer for guiding the water slurry to the fine bubble generator and the mixer, the communication tube The flow tube constitutes at least part of the flow diverter. Π · The reactor according to item 10 of the scope of patent application, further comprising a fake bottom plate located under the flow tube, so that the flow tube and the false bottom plate together form at least part of the flow redirector. 12. The reactor according to item 1 of the scope of patent application, further comprising: an outlet 'on the tank for discharging the sulfate compound from the tank. The paper size is applicable to the Chinese National Standard (CNS) A4 specification⑵G x 297 meals ) —--- — — — — — — — — — — — — — 丨 IIIIII Order · 1111111 ·-^ (Please read the precautions on the arm surface before filling out this page) Stamped by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Clothing 26 524717 Printed by A8, B8, C8, D8, Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. The scope of the patent application, the entrance and the exit are located at opposite positions around the groove, but basically the same from the bottom of the groove Height; 13. The reactor according to item i of the scope of patent application, wherein the tank has a top 'at least partly communicated with the atmosphere, and the sulfate compound formed by the action of oxygen and sulfite compounds is an exothermic reaction that generates heat, The partially open top can release the gas and heat from the reactor to the atmosphere, which is convenient for adiabatic cooling of the water slurry. 14. According to the reactor in the scope of application for item 1, when the precipitate flows along the circulation path, the size of the sulfate compound in the sink will increase. 15 · An oxidation reactor system for oxidizing salt in an aqueous solution, the system includes: at least one tank having a wall and a bottom for containing the aqueous solution of a reduced salt; at least one inlet On the tank for sending the solution from the solution source into the tank; at least one fine bubble generator which has fluid communication with the solution in order to introduce fine bubbles of an oxygen-containing gas into the solution; and at least A flow diverter in the tank to reduce the rotation of the aqueous solution in the tank; and at least one mixer in the tank to distribute the bubbles into the water in the polymer and maintain the aqueous solution and the bubbles in The tank circulates; therefore, at least one circulation path for the aqueous solution and air bubbles is created in the tank, which defines an oxidation region, occupying a considerable volume of the tank 'and the oxidized salt flows along the at least one circulation path. This paper has been scaled to the National Standard for National Standards (CNS) A4 (210 X 297 g) -T — ι-Γ ---- Φ ------- β -------- -— ^ ---------------- (Please read the precautions before filling in this page) -27 524717 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. Scope of Patent Application 16. The system according to item 15 of the scope of patent application further includes: at least one scrubber which constitutes the source of the aqueous solution. 17. The system according to item 15 of the patent application scope, further comprising: at least one cleaner for cleaning the solids on the fine bubble generator ', which is a result of generating the oxidized salt. 18. The system according to item 15 of the scope of patent application, wherein the temperature at which the gas in the fine bubbles is introduced into the aqueous solution is substantially the same as the temperature of the room air around the at least one tank. 19. The system according to item 5 of the scope of patent application, wherein the aqueous solution is a monohydrate of polysulfite. 20. The system according to item 15 of the scope of patent application, further comprising: at least one dewatering device for removing water from the sulfate discharged from the tank. 21. The system according to item 20 of the application, wherein the at least one dewatering device is a fluid cyclone. 22. The system according to item 20 of the scope of patent application, further comprising: a second dewatering device downstream of the at least one dewatering device. 23. The system according to claim 22, wherein the second dewatering device includes a vacuum filter. 24. A method for generating an oxidized salt from an aqueous solution of a salt, comprising: providing a tank with an inlet; introducing an aqueous solution containing a reducing salt into the tank; feeding the tank through a fine bubble generator The micro-bubble scale of oxygen-containing gas is applicable to the Chinese National Standard (CNS) A4 specification (210 x 297 public love) — — — — — — — — — — I · · IIIIIII · 1111111 · ^^ {Please read first Note on the back, please fill out this page again) 524717 A8B8C8D8 VI. Application for Patent Scope Intellectual Property Bureau, Ministry of Economic Affairs, Employee Consumption Cooperative Prints Clothing Flow; Mix the bubble with the solution, make the bubble distribute into the aqueous solution to provide high speed Oxygen is transferred to the aqueous solution; reducing the rotation of the aqueous solution in the tank; and oxidizing the salt to its oxidized form; and circulating the aqueous solution and the air bubbles in the tank, so that the oxidized salt is substantially uniformly distributed in the The aqueous solution. 25. According to the method in the scope of application for patent No. 24, air is provided as the gas. 26. According to the method of claim 24, the gas is supplied at a temperature substantially equal to that of the air in the chamber adjacent to the tank. 27. The method according to item 24 of the patent application scope, further comprising: adjusting the pH of the aqueous solution to between about 3 and about 7. 28. The method of claim 24, further comprising: providing the aqueous solution from a scrubber. 29. The method according to item 28 of the patent application scope, further comprising: desulfurizing the flue gas in the aerator to form a reducing salt including sulfite. 30. The method according to item 24 of the scope of patent application, further comprising: Cleaning the solids of the bubble generator, which tend to accumulate on the generator. 3 1 · The method according to item 24 of the patent application scope further comprises: · dehydrating the oxidized salt. This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm (please read the precautions on the back before filling out this page) IIIIIII — 111 — — — — · i II Λ. II ί -IIIIIIIIIIII i I · · 29