將離子交換樹脂氧化降解之方法及其裝置
Method and device for oxidative degradation of ion exchange resin
本發明係有關於利用一種流體化床反應之化工程序將離子交換樹脂氧化降解之方法，讓用過之離子交換樹脂失去離子交換特性，並進一步降解其結構，以達最終產物失活與安定化之目的，特別係指針對應用於核能工業中水質淨化處理後之放射性廢離子交換樹脂之安定化技術者。The invention relates to a method for oxidatively degrading an ion exchange resin by a chemical process using a fluidized bed reaction, so that the used ion exchange resin loses its ion exchange characteristics and further degrades its structure to achieve inactivation and stabilization of the final product. The purpose is especially for the stabilization of radioactive waste ion-exchange resins used in the nuclear energy industry after water purification.
離子交換樹脂廣用於去除核設施中放射性液體所含有之放射性離子，然而廢離子交換樹脂富有高活度放射性離子且其主結構為有機體，故不利於長期貯存之安定。IAEA在2002年報告Application of Ion Exchange Processes for the Treatment of Radioactive Waste and Management of Spent Ion exchangers中提及廢樹脂可利用破壞分解及直接固化等處理方式。其中直接固化處理方式分為水泥固化法、瀝青固化法及玻璃固化法，而破壞分解處理方式分為乾式氧化法與濕式氧化法。 水泥固化法操作簡單、成本低廉，缺點是廢樹脂會與水泥固化體內鈣離子進行離子交換，使樹脂結構不穩，吸水後會膨脹龜裂。瀝青固化法具有溶出性佳及體積小優點，但其不耐火、抗壓強度低。而玻璃固化法之設備投資成本高且操作成本也高。 乾式氧化法分為焚化法及熱裂解法，焚化法係將廢樹脂與可燃廢棄物混和燃燒，熱裂解法為無氧下操作溫度在500～750°C分解樹脂。乾式氧化法過程中會生成硫氧化物（SOx）、氮氧化物（NOx）、一氧化碳（CO）、及揮發性有機氣體等有害物質，且亦導致如銫-137（Cs-137）等放射性核種逸散之問題。 濕式氧化法分為超臨界水氧化、電漿氧化及芬頓（Fenton）氧化法。超臨界水氧化需操作在高溫高壓下處理廢樹脂，且設備易被腐蝕。電漿氧化法其成本高，廢樹脂氧化時會有SOx、NOx殘留。本所已發展出利用Fenton氧化法分解離子交換樹脂之技術，其反應裝置係以桶槽攪拌裝置當反應器，離子交換樹脂氧化前需先預處理與預熱成漿狀，反應需加熱至90°C以上使樹脂軟化並加速氧化分解反應，然而反應器內溶液溫度會高於沸點，不利操作與控制，且在氧化時需另外添加藥劑調節溶液pH，步驟較為繁瑣。 另一方面，採用桶槽反應器使反應物（離子交換樹脂）與添加之氧化劑及觸媒反應時，所加入之氧化劑與觸媒進入反應器內隨即受到稀釋 ，因此必須持續加熱以保持反應速率，惟此亦將顯著不利於成本與節能。故，ㄧ般習用者係無法符合使用者於實際使用時之所需。Ion exchange resins are widely used to remove radioactive ions contained in radioactive liquids in nuclear facilities. However, waste ion exchange resins are rich in high activity radioactive ions and their main structure is organisms, which is not conducive to long-term storage stability. IAEA's 2002 report of Application of Ion Exchange Processes for the Treatment of Radioactive Waste and Management of Spent Ion exchangers mentioned that waste resins can be processed by destructive decomposition and direct curing. Among them, direct curing treatment methods are divided into cement curing method, asphalt curing method and glass curing method, and destruction and decomposition processing methods are divided into dry oxidation method and wet oxidation method. The cement curing method has simple operation and low cost. The disadvantage is that the waste resin will undergo ion exchange with the calcium ions in the cement solidified body, which will cause the resin structure to be unstable and expand and crack after absorbing water. The asphalt curing method has the advantages of good dissolution and small volume, but it is not fire resistant and has low compressive strength. The equipment cost of glass curing method is high and the operation cost is high. The dry oxidation method is divided into incineration method and thermal cracking method. The incineration method mixes and burns waste resin with combustible waste. The thermal cracking method decomposes resin at an operating temperature of 500-750 ° C in the absence of oxygen. During the dry oxidation process, harmful substances such as sulfur oxides (SOx), nitrogen oxides (NOx), carbon monoxide (CO), and volatile organic gases are generated, and radionuclides such as cesium-137 (Cs-137) are also caused. The problem of escape. Wet oxidation is divided into supercritical water oxidation, plasma oxidation and Fenton oxidation. Supercritical water oxidation requires operating waste resin under high temperature and pressure, and the equipment is easily corroded. Plasma oxidation method has high cost, and SOx and NOx remain when the waste resin is oxidized. The institute has developed a technology to decompose ion exchange resin by using Fenton oxidation method. Its reaction device is a tank-type stirring device as a reactor. The ion exchange resin needs to be pretreated and preheated to form a slurry before oxidation. The reaction needs to be heated to 90. Above ° C, the resin will be softened and the oxidative decomposition reaction will be accelerated. However, the temperature of the solution in the reactor will be higher than the boiling point, which is unfavorable for operation and control, and it is necessary to add additional chemicals to adjust the pH of the solution during oxidation. On the other hand, when a barrel reactor is used to react the reactant (ion exchange resin) with the added oxidant and catalyst, the added oxidant and catalyst are diluted into the reactor and then diluted, so it must be continuously heated to maintain the reaction rate. , But this will also be significantly detrimental to cost and energy saving. Therefore, ordinary users cannot meet the needs of users in actual use.
本發明之主要目的係在於，克服習知技藝所遭遇之上述問題並提供利用一種流體化床反應之化工程序將離子交換樹脂氧化降解之方法及其裝置，係利用流體使反應器內之離子交換樹脂達流體化均勻混合狀態，且使氧化劑與觸媒（過渡金屬鹽類）在反應器內部以高濃度接觸反應物（離子交換樹脂），利用氧化放熱之原理維持反應速率，並藉由熱交換器將反應環境控制在沸點以下，使整個氧化反應維持在高效率與易操控之狀態下進行者。 本發明之次要目的係在於，提供一種適用於核能工業中水質淨化處理後之放射性廢離子交換樹脂之安定化技術，利用流體化床氧化去活性法處理廢離子交換樹脂，可讓用過之離子交換樹脂失去離子交換特性 ，並進一步降解其結構，以達最終產物失活與安定化之目的者。 為達以上之目的，本發明係一種將離子交換樹脂氧化降解之方法及其裝置，係利用流體化床氧化去活性法處理廢離子交換樹脂，其至少包含下列步驟：步驟一：提供一管柱型反應器，其具有一管柱，該管柱上設有一冷卻水入口、一冷卻水出口、一迴流入口、一迴流出口、一氧化劑入口及一分配器，其中，該冷卻水入口係相對於該冷卻水出口，並且係鄰近該迴流入口，該冷卻水出口係鄰近該迴流出口，該分配器係設置於該迴流入口與該氧化劑入口之間；步驟二：將待處理之離子交換樹脂加入該管柱中，加入水與過渡金屬鹽類進入該管柱，利用迴流或曝氣方式控制該離子交換樹脂形成流體化床；步驟三：將上述管柱型反應器控制其溫度在40°C至沸點以下；以及步驟四：將氧化劑從該管柱下方之氧化劑入口注入，該氧化劑流經該分配器與該離子交換樹脂進行氧化反應，分解破壞該離子交換樹脂原有結構與其離子交換特性，並將該離子交換樹脂分解液化後產物由該管柱下方洩出。 於本發明上述實施例中，該管柱型反應器係為雙套管柱型反應器，更包括一熱交換器，係將所輸出之冷卻水經由該冷卻水入口輸送至該雙套管柱型反應器之外層管柱之中，以及流經該外層管柱之冷卻水係經由該冷卻水出口輸送至該熱交換器之中，將反應環境溫度控制在50°C～90°C之間。 於本發明上述實施例中，該管柱型反應器更包括一反應物進料源，係將待處理之離子交換樹脂、水與過渡金屬鹽類各自經由一管線輸送至該雙套管柱型反應器之內層管柱之中。 於本發明上述實施例中，該管柱型反應器更包括在該管柱內裝設一蛇管，以冷卻水通入該蛇管之中，將反應環境溫度控制在50°C～90°C之間。 於本發明上述實施例中，該離子交換樹脂、水與過渡金屬鹽類係可從該管柱上方、側邊或下方加入於該管柱中。 於本發明上述實施例中，該步驟二係利用迴流方式或從該管柱底下曝氣方式控制該離子交換樹脂形成流體化床。 於本發明上述實施例中，該過渡金屬鹽類係為鐵離子鹽類或銅離子鹽類。 於本發明上述實施例中，該步驟四係以分批次或連續式將該氧化劑從該管柱下方之氧化劑入口注入。 於本發明上述實施例中，該分配器係為多孔性介質。 於本發明上述實施例中，該氧化劑係為雙氧水或過錳酸鉀。The main purpose of the present invention is to overcome the above-mentioned problems encountered in the conventional art and provide a method and a device for oxidatively degrading an ion exchange resin by using a chemical process of a fluidized bed reaction, which uses a fluid to exchange ions in a reactor. The resin is fluidized and uniformly mixed, and the oxidant and the catalyst (transition metal salts) are brought into contact with the reactant (ion exchange resin) at a high concentration in the reactor. The reaction rate is maintained by the principle of oxidative exotherm, and heat exchange is performed. The reactor controls the reaction environment below the boiling point, so that the entire oxidation reaction is maintained in a state of high efficiency and easy operation. A secondary object of the present invention is to provide a stabilization technology for a radioactive waste ion exchange resin suitable for water quality purification treatment in the nuclear energy industry. The waste ion exchange resin is treated by a fluidized bed oxidation deactivation method, which can be used. Ion exchange resins lose their ion exchange properties and further degrade their structure to achieve the purpose of inactivation and stabilization of the final product. In order to achieve the above object, the present invention is a method and a device for oxidatively degrading an ion exchange resin. The method uses a fluidized bed oxidation deactivation method to treat waste ion exchange resin. The method includes at least the following steps: Step 1: Provide a column Type reactor, which has a pipe column provided with a cooling water inlet, a cooling water outlet, a reflux inlet, a reflux outlet, an oxidant inlet, and a distributor, wherein the cooling water inlet is opposite to The cooling water outlet is adjacent to the return inlet, the cooling water outlet is adjacent to the return outlet, and the distributor is disposed between the return inlet and the oxidant inlet; Step 2: Add the ion exchange resin to be treated to the In the column, add water and transition metal salts into the column, and control the ion exchange resin to form a fluidized bed by refluxing or aeration. Step 3: Control the temperature of the above-mentioned column-type reactor to 40 ° C to Below the boiling point; and step four: inject the oxidant from the oxidant inlet below the column, the oxidant flows through the distributor and the ion exchange resin An oxidation reaction, decomposition destroy the original structure of the ion exchange resin to its ion exchange properties, the ion exchange resin is decomposed and liquefied by the escape of the product below the column. In the above embodiment of the present invention, the tubular column type reactor is a double-casing column type reactor, and further includes a heat exchanger, and the output cooling water is transmitted to the double-casing string through the cooling water inlet. In the outer layer of the reactor, and the cooling water flowing through the outer layer is sent to the heat exchanger through the cooling water outlet, and the temperature of the reaction environment is controlled between 50 ° C to 90 ° C. . In the above embodiment of the present invention, the tubular column type reactor further includes a reactant feed source, which transports the ion exchange resin, water and transition metal salts to be processed to the double-casing column type through a pipeline. In the inner tube of the reactor. In the above embodiment of the present invention, the tubular column type reactor further includes a coiled tube installed in the tubular column, cooling water is passed into the coiled tube, and the temperature of the reaction environment is controlled between 50 ° C and 90 ° C. between. In the above embodiments of the present invention, the ion exchange resin, water, and transition metal salts can be added to the pipe string from above, from the side or from below. In the above embodiment of the present invention, the second step is to control the ion exchange resin to form a fluidized bed by using a reflux method or an aeration method from under the tube column. In the above embodiments of the present invention, the transition metal salts are iron ion salts or copper ion salts. In the above embodiment of the present invention, the fourth step is to inject the oxidant from the oxidant inlet below the column in batches or continuously. In the above embodiments of the present invention, the dispenser is a porous medium. In the above embodiments of the present invention, the oxidant is hydrogen peroxide or potassium permanganate.
為充分瞭解本發明之目的、特徵及功效，茲藉由下述具體之實施例，並配合所附之圖式，對本發明做一詳細說明，說明如後： 請參閱『第１圖及第２圖』所示，係分別為本發明實施例之將離子交換樹脂氧化降解之裝置之構造示意圖、及本發明將離子交換樹脂氧化降解之流程示意圖。如圖所示：本發明係一種將離子交換樹脂氧化降解之方法及其裝置，係利用流體化床氧化去活性法處理廢離子交換樹脂，其至少包含下列步驟： 步驟s11：提供一管柱型反應器，本實施例係雙套管柱型反應器１００為例，其具有一外層管柱１１０ａ、及一套設於該外層管柱１１０ａ中之內層管柱１１０ｂ，該外層管柱１１０ａ上設有一冷卻水入口１２０與一冷卻水出口１３０，該內層管柱１１０ｂ上設有一迴流入口１４０、一迴流出口１５０、一氧化劑入口１６０及一分配器１７０；其中，該冷卻水入口１２０係相對於該冷卻水出口１３０，並且係鄰近該迴流入口１４０，該冷卻水出口１３０係鄰近該迴流出口１５０，該分配器１７０係設置於該迴流入口１４０與該氧化劑入口１６０之間。 步驟s12：將待處理之離子交換樹脂從該雙套管柱型反應器１００上方加入該內層管柱１１０ｂ中，加入適量水與過渡金屬鹽類進入該內層管柱１１０ｂ，控制水量達該內層管柱１１０ｂ上方迴流入口１４０，利用迴流方式控制該離子交換樹脂反應時形成流體化床。於本實施例中，該雙套管柱型反應器１００更包括一反應物進料源１８０，係將待處理之離子交換樹脂、水與過渡金屬鹽類各自經由一管線１８１、１８２、１８３輸送至該雙套管柱型反應器１００之內層管柱 １１０ｂ之中。 步驟s13：將上述雙套管柱型反應器１００之外層管柱１１０ａ以冷卻水控制反應溫度在50°C～90°C之間。於本實施例中，該雙套管柱型反應器１００更包括一熱交換器１９０，係將所輸出之冷卻水經由該冷卻水入口１２０輸送至該雙套管柱型反應器１００之外層管柱１１０ａ之中，以及流經該外層管柱１１０ａ之冷卻水係經由該冷卻水出口１３０輸送回該熱交換器１９０之中，俾以將反應環境溫度控制在50°C～90°C之間。 步驟s14：將氧化劑從該內層管柱１１０ｂ下方之氧化劑入口１６０注入，該氧化劑流經該分配器１７０與該離子交換樹脂進行氧化反應 ，分解破壞該離子交換樹脂原有結構與其離子交換特性，待該離子交換樹脂分解液化後，停止該氧化劑進入該內層管柱１１０ｂ中。 步驟s15：反應完成後，由該內層管柱１１０ｂ下方將分解液化後液體產物洩出。如是，藉由上述揭露之流程及其構造構成一全新之將離子交換樹脂氧化降解之方法及其裝置。 鑑於氧化速率與反應溫度、反應物濃度有關，且氧化程序一般均為放熱反應；為有效提昇舊有技術之反應速率與效率，本發明藉由反應器設計與加藥方式改良，提出利用一種流體化床反應之化工程序將離子交換樹脂氧化降解之方法，係利用流體使反應器內之離子交換樹脂達流體化均勻混合狀態，且使氧化劑與觸媒（過渡金屬鹽類）在反應器內部以高濃度接觸反應物（離子交換樹脂），利用氧化放熱之原理維持反應速率，並藉由熱交換器將反應環境控制在沸點以下，使整個氧化反應維持在高效率與易操控之狀態下進行。藉此，本發明特別適用於核能工業中水質淨化處理後之放射性廢離子交換樹脂之安定化技術，可讓用過之離子交換樹脂失去離子交換特性，並進一步降解其結構，以達最終產物失活與安定化之目的。 綜上所述，本發明係一種利用流體化床氧化去活性法處理廢離子交換樹脂，將離子交換樹脂氧化降解之方法及其裝置，可有效改善習用之種種缺點，可利用流體使反應器內之離子交換樹脂達流體化狀態，並在控制之溫度範圍內添加氧化劑與觸媒進行氧化作用，達破壞其原有結構與離子交換特性之目的，進而使本發明之□生能更進步、更實用、更符合使用者之所須，確已符合發明專利申請之要件，爰依法提出專利申請。 惟以上所述者，僅為本發明之較佳實施例而已，當不能以此限定本發明實施之範圍；故，凡依本發明申請專利範圍及發明說明書內容所作之簡單的等效變化與修飾，皆應仍屬本發明專利涵蓋之範圍內。In order to fully understand the purpose, features and effects of the present invention, the following specific embodiments are used in conjunction with the accompanying drawings to make a detailed description of the present invention, as described below: Please refer to "Figure 1 and 2 As shown in the figure, it is a schematic structural diagram of a device for oxidatively degrading an ion exchange resin according to an embodiment of the present invention, and a schematic process of oxidatively degrading an ion exchange resin according to an embodiment of the present invention. As shown in the figure, the present invention is a method and a device for oxidatively degrading an ion exchange resin. The invention uses a fluidized bed oxidation deactivation method to treat waste ion exchange resin. The reactor, in this embodiment, is a double-tube-column-type reactor 100 as an example, which has an outer tube string 110a and a set of inner tube strings 110b arranged in the outer tube string 110a and the outer tube string 110a. A cooling water inlet 120 and a cooling water outlet 130 are provided. The inner pipe column 110b is provided with a return inlet 140, a return outlet 150, an oxidant inlet 160 and a distributor 170. Among them, the cooling water inlet 120 is opposite The cooling water outlet 130 is adjacent to the return inlet 140, the cooling water outlet 130 is adjacent to the return outlet 150, and the distributor 170 is disposed between the return inlet 140 and the oxidant inlet 160. Step s12: Add the ion exchange resin to be treated from above the double-tube column reactor 100 to the inner tube string 110b, add an appropriate amount of water and transition metal salts into the inner tube string 110b, and control the amount of water to reach The reflux inlet 140 above the inner pipe column 110b is controlled by the reflux method to form a fluidized bed when the ion exchange resin reacts. In this embodiment, the double-barreled column reactor 100 further includes a reactant feed source 180, which transports the ion exchange resin, water, and transition metal salts to be processed through a pipeline 181, 182, and 183, respectively. To the inner tubular string 110b of the double-tube tubular reactor 100. Step s13: Control the reaction temperature between 50 ° C and 90 ° C with cooling water at 110a of the outer casing of the double-jacketed column-type reactor 100. In this embodiment, the double-jacketed column reactor 100 further includes a heat exchanger 180, which sends the output cooling water through the cooling water inlet 120 to the outer tube of the double-jacketed column reactor 100. In the column 110a, and the cooling water flowing through the outer tube column 110a is sent back to the heat exchanger 180 through the cooling water outlet 130 to control the reaction environment temperature between 50 ° C to 90 ° C. . Step s14: the oxidant is injected from the oxidant inlet 160 below the inner pipe column 110b, the oxidant flows through the distributor 170 to perform an oxidation reaction with the ion exchange resin, and decomposes and destroys the original structure of the ion exchange resin and its ion exchange characteristics, After the ion exchange resin is decomposed and liquefied, the oxidant is stopped from entering the inner layer column 110b. Step s15: After the reaction is completed, the liquid product decomposed and liquefied is discharged from the bottom of the inner column 110b. If so, a completely new method and device for oxidatively degrading an ion exchange resin are formed by the above disclosed process and structure. In view of the fact that the oxidation rate is related to the reaction temperature and the reactant concentration, and the oxidation process is generally an exothermic reaction; in order to effectively improve the reaction rate and efficiency of the old technology, the present invention proposes the use of a fluid through the improvement of the reactor design and the dosing method. The chemical process of chemical bed reaction method for oxidative degradation of ion exchange resin is to use a fluid to make the ion exchange resin in the reactor fluid and uniformly mixed, and make the oxidant and catalyst (transition metal salts) inside the reactor to High-concentration contact with the reactant (ion exchange resin), the principle of oxidative exotherm is used to maintain the reaction rate, and the reaction environment is controlled below the boiling point by a heat exchanger, so that the entire oxidation reaction is maintained at a high efficiency and easy to operate. Therefore, the present invention is particularly suitable for the stabilization technology of radioactive waste ion exchange resin after water purification treatment in the nuclear energy industry, which can cause the used ion exchange resin to lose its ion exchange characteristics and further degrade its structure to achieve the final product loss. The purpose of living and stabilization. In summary, the present invention relates to a method and a device for treating a waste ion exchange resin by using a fluidized bed oxidation deactivation method, and oxidatively degrading the ion exchange resin, which can effectively improve various conventional defects, and can use a fluid to make the reactor interior The ion exchange resin reaches a fluidized state, and an oxidant and a catalyst are added to perform oxidation within a controlled temperature range, so as to destroy its original structure and ion exchange characteristics, thereby further improving the performance of the present invention. It is practical and more in line with the needs of users. It has indeed met the requirements for the application for invention patents. However, the above are only the preferred embodiments of the present invention, and the scope of implementation of the present invention cannot be limited by this; therefore, any simple equivalent changes and modifications made in accordance with the scope of the patent application and the contents of the invention specification of the present invention , All should still fall within the scope of the invention patent.
雙套管柱型反應器１００ 外層管柱１１０ａ 內層管柱１１０ｂ 冷卻水入口１２０ 冷卻水出口１３０ 迴流入口１４０ 迴流出口１５０ 氧化劑入口１６０ 分配器１７０ 反應物進料源１８０ 管線１８１、１８２、１８３ 熱交換器１９０ 步驟s11～s15Double-jacketed column reactor 100 Outer tube string 110a Inner tube string 110b Cooling water inlet 120 Cooling water outlet 130 Reflux inlet 140 Reflux outlet 150 Oxidant inlet 160 Distributor 170 Reactant feed source 180 Pipeline 181, 182, 183 Hot Exchanger 90 steps s11 ～ s15
第１圖，係本發明實施例之將離子交換樹脂氧化降解之裝置之構造 示意圖。 第２圖，本發明將離子交換樹脂氧化降解之流程示意圖。Fig. 1 is a schematic diagram showing the structure of an apparatus for oxidative degradation of an ion exchange resin according to an embodiment of the present invention. FIG. 2 is a schematic flow chart of oxidative degradation of an ion exchange resin according to the present invention.