1255277 九、發明說明： 【發明所屬之技術領域】 本發明係有關一種廢離子交換樹脂的處理方法，尤指 一種以濕式氧化法減容並利用氫氧化鋇調節濕式氧化反應 液之PH之離子交換樹脂的處理方法，主要應用在核能發電 廠中之各項淨化處理或其它相關領域之淨化處理。 【先前技術】 現行核能發電廠絕大多數是輕水式反應爐⑴ght water reactor)機組，使用輕水做為反應爐的冷卻劑. (C〇〇lant)與中子緩速劑（_trQn mQderat。小捧水中如 果含有溶解的離子存在，不僅會導致腐钱性增加’也會產 產物（activation products)而使機組的放射性劑量 增高，並且會因中子捕择及廏广+ 河丁 r ^里 “ u (neutron capture reactions) ，而降低中子經濟(neutr〇n _⑽y)。為了解決這些潛 ^題’離子交換樹脂在核能發電財有廣泛的用途y包 .反應爐爐水的淨化處理，以提供脫礦物質的補 爐水中污染物’例如由核燃料元件裂縫逸出的；· /產物和分裂產物；降低冷卻劑的含氧量；以及控 ’广7中腐蝕抑制劑與化學添加劑之含量等。又，： Μ脂也被使用於核電廠製程廢水的處理。 又、 增力交換樹脂除7粒狀樹脂外，為了 離子交換子交_脂°粉末狀-是—種十m積約為粒狀離子交換樹脂—百倍，- 、知末，通t用於被覆過濾濾心，除了具 1255277 有離子交換的功能外’尚可用以移除水中懸浮狀的固體微. 粒。 粒狀離子交換樹脂在離子交換能力衰退，或受核種污 染而放射性增高後即須再生。再生數次不能再用後，即被 替換而成為含放射性的廢料。粉末狀離子交換樹脂在使用 -次後即會夾雜多量的固體雜質，因此通常不做再生，使 用-次後即當做廢棄物處理。根據美國f力研究所的统 計，在1982-1985間廢樹脂的產量佔濕性廢料之比例彿 水式反應爐⑽心山心此^⑽核電廠中粉狀廢· 樹脂佔50%，粒狀樹脂伯⑽；星水式反應捧 Pressure Water Reactorw電廠中則粉狀廢樹脂佔 7%，粒狀樹脂佔44%。臺灣則爾核電廢中粉狀廢樹脂約佔 30%’粒狀樹脂約佔11%;PWR核電薇為粉狀廢樹脂約佔心 粒狀樹脂約佔23%。 關於廢離子交換樹脂的處理，早期的處理方式是採取直 接固化，固化劑的材料包括水泥、高分子聚合物或柏油 等；這些固化方法各有優劣，一般而言，高分子聚合物與籲 柏油的固化可以獲得較少的固化體體積，但是高分子聚合 物價格高’操作成本也較高’而柏油則強度低而且具有可 燃性。1 997年3月，日本曾經發生柏油固化操作發生火災 的事件，釀成嚴重的核能事件。水泥固化法操作簡單，費 用低廉，但是由於廢離子交換樹脂仍具有離子交換能力，、. 會與水泥固化體内的㈣子等進行交換反應，影響品質。. 亚且會吸收或釋放水份’發生膨脹、收縮作用，·此種作用 1255277 尤以粒狀離子交換樹脂為麩， 龜裂，使欢厫重妗胃導致固化體膨脹或. 使水㈣化體中廢離子交 糧大限制，導致固化後產生…丄:載-°一) 曰最終處置場一地難求，二=固化體。在今 化已不符經濟效益。置費用…張的情況下’直接固 定化：對廢粒狀離子交換樹脂的處理主要包含減容與安 括兩目的吉其處理方法可分為乾法與濕法兩類，乾法包 、去火直接玻璃固化法及熱解法等；濕法則有酸解 發心午法及超臨界水氧化法等。其中以焚化法的開· 二取’已經有部分國家付之實施。使用焚化時，一般是 木取將廢粒狀離子交換樹脂與其它可燃性廢料混燒的方 仃’以求控制S〇X、，或其它有害氣體的排放。放射 «重的排放控制也是焚化方法需要解決的關鍵問題，除 1月匕有效避免揮發性的碳—14、氣及铯—137等核種的排 放’否則對放射性較高的廢料必須事先進行核種脫除，使 放射性降低後再行焚化。 ⑩ 旧士直接玻璃固化法因為離子交換樹脂的玻璃熔融體在高 酿日寸具有很強的腐蝕作用，材料的腐蝕是最主要的問題， $有夕種玻㈣固化炫融爐技術正在開發中。其中法國Sgn 公司開發的冷壁（cold wall)熔融爐的腐蝕問題較小，自 、:疋隶理t的直接玻璃固化技術，但是商用系統仍未建 立美國$谷融金屬技術公司（Mol ten Metal Technology, MMT) 則開發所謂 Q —CEP 製程（Quantum —Catalytic Extraction 1255277 子父=月曰中可以氣化的成份分解成簡單的氣體，不能氣 化則形成融渣，因此獲得有效的減容與安定化。該 法化產物是—種含有硫1、納等的高活性鐵塊， 須使^別的容器承建造 化 '等廠十刀不㈣。此外，該法產生可觀的硫 虱4軋肢副產物，如何打發也是—個難題。 美國ThermoChem Inc.則研發高溫蒸汽重組⑽⑽1255277 IX. Description of the Invention: [Technical Field] The present invention relates to a method for treating a waste ion exchange resin, and more particularly to a method of reducing the volume by wet oxidation and adjusting the pH of the wet oxidation reaction solution by using cesium hydroxide. The treatment method of ion exchange resin is mainly applied to purification treatment in nuclear power plants or purification treatment in other related fields. [Prior Art] Most of the current nuclear power plants are light water reactors (1) ght water reactors, using light water as the coolant for the reactor. (C〇〇lant) and neutron retardant (_trQn mQderat. If the small amount of water contains dissolved ions, it will not only lead to increased rot, but also the activation products, which will increase the radioactive dose of the unit, and will be due to neutron capture and 廏 ++ 河丁r ^ "u (neutron capture reactions), and reduce the neutron economy (neutr〇n _(10)y). In order to solve these potential problems, ion exchange resins have a wide range of uses in nuclear power generation. Contaminants in demineralized water that provide demineralization, such as those that escape from cracks in nuclear fuel components; / products and splitting products; reduce the oxygen content of the coolant; and control the content of corrosion inhibitors and chemical additives in 'Guangzhou 7' In addition,: Rouge is also used in the treatment of wastewater from nuclear power plant process. In addition, in addition to the 7-grain resin, the force-exchange resin is used for the ion exchange. Ion exchange resin - hundred times, -, know the end, pass t for the coated filter filter, in addition to the function of ion exchange of 1255277 'can still be used to remove suspended solids in water. Granules. Granular ion exchange resin in If the ion exchange capacity declines, or it is contaminated by nuclear species and the radioactivity increases, it must be regenerated. After several times of regeneration, it can be replaced and become radioactive waste. The powdered ion exchange resin will be mixed after use. Solid impurities, so usually do not regenerate, after use - as a waste treatment. According to the statistics of the United States f force research institute, the ratio of waste resin production to wet waste in 1982-1985 is the proportion of the water-based reaction furnace (10) In the nuclear power plant, the powdery waste resin accounts for 50%, and the granular resin (10); in the Star Water-type reaction, the Pressure Water Reactorw power plant accounts for 7% of powdered waste resin and 44% of granular resin. Taiwan The powdery waste resin in the nuclear power waste accounted for about 30% of the 'granular resin'; about 11% of the PWR nuclear power is about 23% of the powdery resin. About the disposal of waste ion exchange resin, early Processing party It is a material that directly cures, and the curing agent includes cement, high molecular polymer or asphalt; these curing methods have their own advantages and disadvantages. Generally, the curing of the high molecular polymer and the asphalt can obtain less solidified body volume, but The high polymer price is high, and the operating cost is also high. The tar is low in strength and flammable. In March, 997, there was a fire in the tar solidification operation in Japan, which caused a serious nuclear energy event. The operation is simple and the cost is low. However, since the waste ion exchange resin still has an ion exchange capacity, it exchanges reaction with the (four) sub-cylinder in the cement solidified body to affect the quality. The sub-and will absorb or release water's expansion and contraction. · This effect 1255277 especially the granular ion-exchange resin is bran, cracking, causing the sputum to swell and cause the solidified body to expand or make the water (four) The waste ion in the body is limited by the grain, which leads to the production after curing...丄:Load-°1) 曰The final disposal site is difficult to find, and the second = solidified body. In this case, it has not been economically beneficial. In the case of the cost of the sheet, the direct immobilization: the treatment of the waste granular ion exchange resin mainly includes the two methods of reducing the volume and the purpose of cleaning. The treatment method can be divided into two types: dry method and wet method. Fire direct glass curing method and pyrolysis method; wet method has acid solution heart-nosed method and supercritical water oxidation method. Among them, the incineration method has been implemented by some countries. When incineration is used, it is generally a method of mixing waste granular ion exchange resin with other combustible wastes to control the emission of S〇X, or other harmful gases. Radiation «heavy emission control is also a key issue that needs to be solved by incineration methods. Except for January, it effectively avoids the emission of volatile carbon-14, gas and cesium-137 and other nuclear species. Otherwise, the radioactive high-level waste must be pre-nucleated. In addition, the radioactivity is reduced and then incinerated. 10 The old glass direct curing method because the glass melt of the ion exchange resin has a strong corrosive effect on the high brewing day, the corrosion of the material is the most important problem, and the technology of the luminescent glass furnace is developing. . Among them, the cold wall melting furnace developed by Sgn Company of France has less corrosion problems, since: the direct glass curing technology of 疋 理 理, but the commercial system has not yet established the US Molten Metal Technology Company (Mol ten Metal) Technology, MMT) develops the so-called Q-CEP process (Quantum - Catalytic Extraction 1255277 sub-father = the components that can be vaporized in the month are decomposed into simple gases, and can not be vaporized to form slag, thus achieving effective volume reduction and stability The legalized product is a kind of high-activity iron block containing sulfur 1, sodium, etc., and it is necessary to make the other containers into a factory, etc. (four). In addition, the method produces considerable sulfur sulphide 4 The product, how to send it is also a difficult problem. American ThermoChem Inc. develops high temperature steam reorganization (10) (10)
=士_1 使離子交換樹脂在高溫裂解（pyr〇lysis) J 同日守措由重組產生可燃氣體則作為燃料。此法也有嚴重之 材枓腐飯問題，前途如何也仍須時間證明。超臨界水氧化 ：(：ur；c—〇xldatlon, SCW0M^^b J“又#使用的向溫、高壓臨界水，於含有離 月旨分解產物(例如硫酸)後，同樣具有高度材: 腐^題十分嚴重’其輯實賴度尚遠。 英國ΑΕΑ Λ司則已發展成功濕式氧化法 2鐵為觸，以雙氧水為氧化劑，以消石灰為二^ 仆^0 C/皿度及ΡΗ 3—4下，進行粒狀廢離子交換樹脂之 c〇2A ^ : 升之離子交換樹脂，㈣耗5〇wt%雙氧水16〇公 消泡劑。 “灰6公斤，以及。.5公斤以下之 廢離子交換樹脂包括陽離子交換型與陰離 種型式，它們具備不同的化學成份，強酸型之陽離子= 1255277 樹脂與強鹼型之陰離子交換樹脂，其以雙氧水進行濕式氧 化的總合反應（〇ver_all reacti〇n)如下所示·· (1) (2)= 士_1 The ion exchange resin is pyrolyzed at the same time. J. The same day, the fuel is produced by recombination to produce combustible gas. This method also has serious problems of glutinous rice, and the future still needs time to prove. Supercritical water oxidation: (: ur; c-〇xldatlon, SCW0M^^b J "#" used to the temperature and high pressure critical water, after containing the decomposed products (such as sulfuric acid), also has a high degree of material: The problem is very serious. The 赖 赖 尚 。 。 ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ ΑΕΑ -4, for the granular waste ion exchange resin c〇2A ^ : liter of ion exchange resin, (4) consumption of 5 〇 wt% hydrogen peroxide 16 〇 public defoamer. "ash 6 kg, and .5 kg of waste The ion exchange resin includes a cation exchange type and an anion exchange type, which have different chemical compositions, a strong acid type cation = 1255277 resin and a strong base type anion exchange resin, and the total reaction of wet oxidation with hydrogen peroxide (〇ver_all Reacti〇n) as shown below (1) (2)
陽離子交換樹脂濕式氧化反應 CsHsSOs + 2OH2O2 8CO2 + 23H2O + H2SO4 陰離子交換樹脂濕式氧化反應 C12H19NO + 31H2〇2 — NH4OH + 12C〇2 + 38H2O 、以上二式顯示，離子交換樹脂氧化時，其中之碳氫化 物成^被氧化變成⑶2肖Μ。此外’根據反應式⑴與 (2)，母一莫耳之陽離子、陰離子交換樹脂所含之碏酸基盘讀 季㈣’則分別被氧化產生一莫耳之硫酸與氫氧化錢。陽 離子又換樹月曰氧化產生的硫酸’除了使溶液的酸度升高 =和雙氧水之同時存在，也使濕式氧化溶液具有高 f =性。㈣腐餘性會隨陽離子離子交換樹脂濕式氧 η化則：：：回。陽離子、陰混合之離子交換樹脂的濕式 :、5日$生硫酸與氫氧化銨’因此尚包括 應，即： π〜/入Cation exchange resin wet oxidation reaction CsHsSOs + 2OH2O2 8CO2 + 23H2O + H2SO4 anion exchange resin wet oxidation reaction C12H19NO + 31H2〇2 - NH4OH + 12C〇2 + 38H2O, the above two formulas show that the ion exchange resin is oxidized, the carbon The hydride is oxidized to become (3) 2 Μ. Further, according to the reaction formulas (1) and (2), the cation of the mother-mon cation and the quaternary acid-based disk read (four)' contained in the anion exchange resin are respectively oxidized to produce one mole of sulfuric acid and hydrogen peroxide. The sulphuric acid produced by the oxidation of the cations and the oxidation of the tree 除了, in addition to increasing the acidity of the solution = and the simultaneous presence of hydrogen peroxide, also makes the wet oxidizing solution have a high f = sex. (4) Corrosion residue will be accompanied by cation ion exchange resin wet oxygen η::: back. The wet type of cation and anion mixed ion exchange resin: 5 days of raw sulfuric acid and ammonium hydroxide' therefore include, ie: π~/in
啊，—讽， ⑶ I 與氯氧化録在濕式氧化廢液中之莫耳比，係 二二二乳化的陽離子、陰離子交換樹脂的莫耳比而 疋“陰離子/陽雜JTL , 子父換树脂的莫耳比為2時，所產生之 將恰如其分合成硫酸録，在反應完成後溶 ί化：二。當莫耳比〉2時，廢液中將有過剩之氫 ‘、I氧化廢液之pH，將會明顯上升；當莫耳比<2 1255277 日守’則會有過剩之硫酸，pH將明顯下降。 ， 為控制濕式氧化反應液的pH，必須以添加酸類或鹼類 來調節，一般常用石灰（氫氧化鈣）或氫氧化鈉來添加，添 加氫氧化鈣會使硫酸轉化形成硫酸鈣，產生以含硫酸鈣為 主，的濕式氧化廢液；此種廢液在固化時，硫酸鈣會與水泥 2之鋁酸三鈣（3CaO . AhO3)作用，緩慢地生成低密度的鈣 恭石（e 11 r i g i t e )，使固化體逐漸膨脹繼而龜裂，是—嚴重 的品質問題。欲降低此種問題，固化體中的廢料荷載 (loading)率必須大幅降低，如此則將導致廢料固化體體積籲 =幅增加。此外，硫酸鈣在廢液中容易結晶，並黏結阻^ 管路’不易輸送，形成操作上的困難。 濕式氧化槽蒸發之蒸汽經冷卻所獲得之凝結水有可 能夾帶核種，也不可避免地會含有少量的有機物，如不加 以處理而致總有機碳（t〇tal 〇rganic carb〇n，t〇c)濃度 過问’可能使凝結水無法排放或再用發生困難。 由前述可知，現行廢離子交換樹脂濕式氧化法的主要 缺點包括··⑴處理時反應液具有很高的腐钱性，材料腐籲 蝕問題嚴重，（2)所產生的廢液以硫酸與硫酸鹽為主要組 成，固化不易，廢液固化產生的固化體體積大，幾乎完全 抵消了離子父換樹脂氧化所得到的減容效果，·⑶濕式氧 化操作的控制不易，反應產生的汽泡容易發生暴騰現象。 為解決上述缺點，發明人經長時間的研究實驗終於研· 發出本發明。 、 1255277 【發明内容】 本發明之一目的係在提供—種廢離子交換樹脂的處理 方法，將離子交換樹脂以濕式氧化法減容。 理本&月之$目的係在提供—種廢離子交換樹脂的處 ~方法，將離子交換樹脂以濕錢化法減容後，再將濕式 氧化殘渣與廢液漿液高效率固化。 > 為達上述目的’本發明係使用硫酸亞鐵為觸媒，並以 又氧水為氧化劑進行離子交換樹脂的分解與氧化，盆 調升反應溶液的pH時佶用养_儿& 〃 Ρ叶使用虱虱化鋇，調降反應溶液的pH丨 時則使用硫酸，請參第⑶，其一較佳實施例之步驟為： ⑴將離子交換樹脂置於硫酸亞鐵溶液中，將溶液攪 拌亚加溫至90〇C以上、彿點以下之溫度； )镧1又氧水於⑴之溶液中，並以硫酸或氫氧化鋇 即溶液pH於適合濕式氧化的範圍； ⑶：力，氧水期間溫度升高到彿點時，讓溶液自然 f並°襄所產生的水蒸汽與C〇2經過冷凝器後， 錄t結水收集’並進行降低其總有機碳（TOC)與核1 ^度之處理後’予以回收再用或排放，⑶2經過 過濾後釋放； 中、天足夠之雙氧水完成濕式氧化反應f ’於溶液 夕：加風氧化鋇，以升高溶液之pH，並使溶液中 ^ 艮形成硫酸鋇，同時使銨根以氫氧化録或 虱乳的型態逸出溶液； (5)將自溶液〆 、出之虱氧化銨或氨氣經過一氨分解 1255277 f介使其分解產生氫氣與氮氣，並使產生之氫氣 與空氣接觸而反應成為H2〇 ; (6)將（4)之漿液添加固化劑並混合均勻，然後靜置令 其硬化。 在本發明方法t，為便於進行濕式氧化反應液的安定 =:調解pH之酸類特別制硫酸，調解邱之驗類特 H气氧化鋇，尤其是採用氫氧化鋇為中和劑，可獲得 4 交‘έ (1)氫氧化鋇可將硫酸與硫酸銨轉化為硫酸 仿、:而1酸鋇為不溶性且比重極高（約4 5)之固體，安定性 二被包埋後可在固化體結構中發揮骨材的功用，不僅 、、二固：容積較小，也可增進固化體的機械強度;⑵ 忧口化版夯生知脹與龜裂的問題，可以 ^仔安定性極佳的固化體；（3)形成之硫酸鋇為堅硬結實之 靜/、不曰沾社塊’容易在溶液中分散，因此容 易、級動輸送，並且容易混合，操作六 對硫酸根的安定化效果佳，對：果4風虱化鋇 液的腐錄也有良好之效果的•絲佳，對降低廢 輸的效率與反應液的Μ控制密切相關。本發明 示，以氯氧化鎖調節濕式氧化反應液PH的效 遂般使賴齡鈉錢氧化鈉為佳，不僅PH控制转 足’使用量也少，對減少最制顧-： 發明的實驗結果，陽離子交換樹脂气=板姆本Ah, - sarcasm, (3) I Mohr ratio recorded in wet oxidation waste liquid with chlorine oxidation, the molar ratio of cations and anion exchange resins of 222 emulsified oxime "anion / cation JTL, sub-family change When the molar ratio of the resin is 2, the resulting mixture will be as purely as the synthesized sulfuric acid, and will be dissolved after the reaction is completed: 2. When the molar ratio is >2, there will be excess hydrogen in the waste liquid, and the I oxidation waste liquid The pH will rise significantly; when Moerby <2 1255277, the pH will be excessively reduced. In order to control the pH of the wet oxidation reaction, it is necessary to add acid or alkali. Adjustment, generally used lime (calcium hydroxide) or sodium hydroxide to add, the addition of calcium hydroxide will convert sulfuric acid to form calcium sulfate, resulting in a wet oxidation waste liquid containing calcium sulfate; the waste liquid is solidified At the same time, calcium sulfate reacts with the tricalcium aluminate (3CaO. AhO3) of cement 2 to slowly form a low-density e 11 rigite, which causes the solidified body to gradually expand and then crack, which is a serious quality problem. To reduce this problem, the waste in the solidified body The loading rate must be greatly reduced, which will result in an increase in the volume of the solidified body of the waste. In addition, calcium sulfate is easily crystallized in the waste liquid, and the bonding resistance is difficult to transport, which makes it difficult to operate. The condensed water obtained by cooling the steam evaporated by the oxidation tank may entrain the nucleus and inevitably contain a small amount of organic matter, such as total organic carbon without treatment (t〇tal 〇rganic carb〇n, t〇c The concentration of the problem may make it difficult for the condensate to be discharged or reused. As can be seen from the foregoing, the main disadvantages of the current waste ion exchange resin wet oxidation process include: (1) The reaction liquid has a high rot, the material The problem of corrosion and corrosion is serious. (2) The waste liquid produced by sulfuric acid and sulfate is the main component, and the curing is not easy. The solidified body produced by the solidification of the waste liquid is large, which almost completely offsets the volume reduction obtained by the oxidation of the ion father. The effect, (3) the control of the wet oxidation operation is not easy, and the bubble generated by the reaction is prone to violent phenomenon. In order to solve the above shortcomings, the inventor finally completed the research and experiment for a long time. The present invention is issued. 1255277 SUMMARY OF THE INVENTION One object of the present invention is to provide a method for treating a waste ion exchange resin by reducing the volume of the ion exchange resin by wet oxidation. In the method of providing a waste ion exchange resin, the ion exchange resin is reduced in volume by wet money, and then the wet oxidation residue and the waste liquid slurry are efficiently cured. The ferrous sulfate is used as a catalyst, and the oxygen exchange water is used as an oxidant to decompose and oxidize the ion exchange resin. When the pH of the reaction solution is raised by the basin, the sputum is used to raise and lower the pH of the reaction solution. Sulfuric acid is used when the pH of the reaction solution is ,. Please refer to (3). The steps of a preferred embodiment are as follows: (1) placing the ion exchange resin in a ferrous sulfate solution, and stirring the solution to a temperature above 90 〇C, The temperature below the point of the Buddha; ) 镧 1 and oxygen water in the solution of (1), and the pH of the solution is suitable for wet oxidation with sulfuric acid or cesium hydroxide solution; (3): force, the temperature rises to the point of the Buddha during the oxygen water Let the solution naturally f and ° After the raw water vapor and C〇2 pass through the condenser, the t-water collection is collected and the total organic carbon (TOC) and the nuclear 1 ^ degree are treated to be recycled or reused. (3) 2 is filtered and released. In the middle of the day, enough hydrogen peroxide to complete the wet oxidation reaction f 'on the solution eve: add wind yttria to raise the pH of the solution, and make the solution sputum barium sulphate, while the ammonium root is recorded as bismuth hydroxide or bismuth The type of the emulsion escapes from the solution; (5) the solution is decomposed from the solution bismuth, bismuth ammonium oxide or ammonia by decomposition of 1255277 f to generate hydrogen and nitrogen, and the generated hydrogen is brought into contact with air to react H2 〇; (6) Add the curing agent to the slurry of (4) and mix well, then let it sit and let it harden. In the method t of the present invention, in order to facilitate the stabilization of the wet oxidation reaction solution =: the acid which is used to adjust the pH, the sulfuric acid is specially prepared, and the qi of the H-type oxidized cerium is mediated by Qiu, especially the cerium hydroxide is used as the neutralizing agent. 4 交 'έ (1) cesium hydroxide can convert sulfuric acid and ammonium sulphate into sulphate imitation: while yttrium acid yttrium is insoluble and very high specific gravity (about 45) solid, stability can be cured after being embedded In the body structure, the function of the aggregate is not only, but also the two solids: the volume is small, and the mechanical strength of the solidified body can be improved; (2) The problem of swelling and cracking of the sorrowful version can be improved. (3) The formed barium sulfate is hard and firm, and it is easy to disperse in the solution, so it is easy to transport, easy to mix, and easy to mix, to stabilize the six pairs of sulfate. Good, right: Fruit 4 sputum sputum sulphur record also has a good effect • Silk Jia, the efficiency of reducing waste is closely related to the control of the reaction liquid. The invention shows that the pH of the wet oxidation reaction liquid is adjusted by the chlorine oxidation lock, so that the sodium oxide of sodium lysine is preferable, and not only the PH control is used, but also the amount of use is reduced, and the reduction is most effective. As a result, cation exchange resin gas = plate Mben
以控制在為佳，控制在丨至3為更佳 I 交換樹脂，PH則以控制在丨.5至4^，控制在2=子5 1255277 ;對含陰離子交換樹脂與陽離子交換 化反應液，PH則以控制在為佳，控制在15‘至式二 更佳。反應液的士九U 3為 兔旦★；； 制在合宜的範圍可以減少雙氧水的消 的實驗結果顯示，以㈣積比的陰、陽混合 換行指而言’將pH控制2左右，每公升混合離子交 的^雙氧水約在3.5〜5公升之間，雙氧水的 /4、' ϋ =千愈低，消耗的雙氧水愈少。 、 =歧料了時，㈣所述反應財 Μ脂進料的多寡，將含右 丁又換 仍麸使用'灭,… #對#1的的硫酸銨’這些硫酸銨( 使用添加虱氧化鋇進行轉化，反應如下： {NH^+BW^NHA〇H + BaS〇A ⑷ 上^反應產生的氫氧化錢在溶液的邱提高到8 始逸出溶液，溫度愈高逸出速率愈快。由於轉 :::發熱反應’添加氣氧化頻會使溫度提有= ^氣的逐出。根據本發明的實驗發現，溫度 愈有利於氨氣的挽屮。产决丄& " 又” PH ,¾呵， 攄石*舻4 在冰加氫氧化鋇進行轉化時，庫根 =根的濃度計算轉化所需的氯氧 =· f硫酸根轉化成硫酸鋇為度，如添加量過多，將= ;有=廢齡㈣，對廢液固化後的固= 鹽為硫酸::及足，因而無法充分轉化硫酸 氣，而㈣化操作時與固化體形成後再產生氨 子衣％财生產生不良影響。 本發明對製程中所產生的氨氣與含總有機碳 1255277 organic carbon，TOC)的冷凝水也加以完善而清潔的處 理’確保不產生二次污染。其中氨氣產生後即被引入—气 分解為，使其在高溫與觸媒（catalyst)接觸下分解為氮氣 與氫氣，其中氫氣在氨分解器出口與空氣接觸被氧化為 後再與氮氣一起被排放，其反應如下： 、 2NH, Δ catalyst +2//, (5) 2//2 +02 2H20 (6) 鎳基觸媒對反應⑷的催化效果甚佳，根據本發明之每 驗結果，將氫氧化鎳粉末擔負於咖或Ah〇3擔體 只 始觸媒，將此觸媒床加熱至^(^時， 婵 :已 時則近乎完全_ 有可㈣發㈣之紐經料賴得之凝結水 不力3 也不可避免地會含有少量的有機物，如 =處理而致其總有機碳（T〇tai啦㈣心如，1 解二;Π，结水無法排放或再聰 输過=交::r凝結水經過降魏處理後，再 結果顯示，本二:脫除其可能含有的核種。實驗 ppmn低 之，稍水TQG含量約在數十至數百 物達成一“係以高級氧化法或添加過氧化人 =過結合臭氧與紫外_，過= 過石瓜酸納等。實驗證明無論使用高級氧 14 1255277 =或添加過氧化物效果均佳，經處理後之凝結水，toc . 之濃度皆可視需要降低至數十甚至數ppm以下，可回收再 用或予排放。 本叙月進行说式氧化廢液的固化所使用的固化劑係特 別调製而成，除了含有水泥與石夕灰（siHca f聽）、飛灰⑴乂 h)爐石知（blast furnace slag powder)等波索蘭材料 (Pozzolanic materials)外，為了確保固化體的長期穩定 性與品質均勻性以及增進操作性，尚另視情況選擇添加矽 酸鹽、石舞酸鹽，以及約、石夕、鎂、紹、鐵與錯等的氧化物籲 或鹽類。因此，本發明所製備之固化體除了具備良好的機 械強度（meChanical strength)、耐康融性（freezing ㈣ thawing resistance)、耐水性（water immersi〇n resistance)外，尚具有優良的長期穩定性以及均勻的品 質。 而本發明針對先前技術之缺點皆有良好的解決對策， 除了免除嚴重的腐I虫問題外，並且具備很高的減容效果， 而且操作控制十分穩定。 _ 為使本毛明此夠被充分瞭解，茲以實施例配合圖式加 以說明。 【實施方式】 本實施例所使用實驗裳置如第2圖所示，其包含—個 4’000ml之玻璃燒杯χ，該燒杯之由一個三孔的玻璃蓋覆 蓋’玻璃蓋之中間孔Α設置有—馬達2帶動之如⑽攪拌 !255277 茱3 ’「孔作為加料口6 ’另-孔則作為出口c，該出口 C與：迴流管4、-_除霧器5及_冷凝管6等聯接。 f式：化所產生之混合氣體由出口 c流出’經過薄膜除霧 裔5時’混合氣體中所含之水霧滴（⑽⑽⑴會被遽除， 成大水滴後’由迴流管4迴流至反應槽7中；水某汽盥 :=通過薄膜除霧器5進入冷凝管時，水蒸汽會被冷 广成水’並被收集於接麵中，再視需要繼續進行 與脫除核種等處理；二氧化碳與其他不可凝之氣 j予以排放^冷凝管之出口處，尚另襄置一供凝結水I 之鐵歧官9 ’需要時開啟鐵氟龍管上之旋塞，即可 將减結水迴流至反應燒杯中，以調節其中之液位，1 〇為 '導t，11為氨分解器，12為加熱器，13為溫度計， V 1 :V 2、V 3為管閥。 ”濕式氧化操作開始時’首先取4〇ml (乾重ΐ8·〇5公克） 陽離子樹脂(Amberlite 200C，Dow Chemical c〇)和 60ml(乾f 19·88公克）陰離子樹脂⑽—術，如㈣及 〇.嶋硫酸亞鐵溶液1，_W，依序放人燒杯内，再加入< 濃=酸，調節溶液之初始pH值為2左右。然後將燒杯置 於電熱板±上加熱及啟動攪拌馬達進行攪拌，當溶液溫度達 到95 C日守，即用定量幫浦（metering p㈣幻將雙氧水 二l2.5m:’min <流量輸入燒杯中Μ吏離子交換樹二化 刀角午。雙氧水開始輸入後’反應溶液即刻升溫至沸點；溫 度維持在98。。至沸點之間；過程中如有發泡產生： 加入適量之消泡劑（Dow Corning Q2-3447)抑制之；並^ 1255277 :;單錢氧化鋇粉末調節溶液，使之介於"η」· ^因蒸發而降低時，心純水補充使保持穩定。 脂以子交換樹脂和60ml陰離子樹 水力m之雙乳水’當最後-批樹脂加完後，將雙氧 至.、弗口點1預定以肖耗量。加料完畢後’反應液仍維持啊 〇. 5小時，使雙氧水充分反應。實驗之全程 =7;，V 15.575 公升… 容積為^ 化鋼。樹脂氧化分解液經調整其 貝接著進 取樣分析T〇C則共計算氧化分解效率。· 485克單/，化廢液中硫酸鹽之轉化。首先添加 維持溫度於t甘 说式乳化廢液，擾掉並 七气卜、 工 使/、中之硫酸銨轉化為硫酸鋇，·添 加虱氧化鋇過裎中古与々汉， 爪敗职，斗 U_ni “ · 將其導入氨分解器 1;:;，。一。r)i〇。該氨分解器以電熱加溫， 二當含錄f作氨的分解觸媒，溫度保持在 料分解為==;_體通過時，其中之氨或氨氧化籲 空氣，風乳’虱氣於出口與空氣接觸時，即與 體所含之：、、二 =Γ。本實驗測得 液中々來m 卿。在此步驟中，濕式氧化廢 酸根被轉化成不溶性的硫酸鋇，録根則 與關。如此所^^存於黎液中，最後並被轉化為n2 . 此所侍到的漿液之pH為ΐ〇· 5。 繼之進行所得到的漿液的固化處理。將漿液加熱趕出- 1255277 多餘的水份，以調節漿液的含水量，使進行固化時水與固t· 化劑的重量具有適當的比例，經此濃縮處理後，所得到的 濃縮漿液容積為734ml，重量為1，208克，1^人 /、甲所含之水 重為576純此濃縮漿液倒入另一混合器中，並於攪拌 下緩慢加入7 5 7克固化劑（使水/固化劑重量比為〇 7 6) 持續攪拌15分鐘使其均勻混合後，將所得之黎液注入直 徑5公分、高度11公分之聚乙烯（PE)模具中，製成圓柱 形固化體。固化體經28天靜置養護後脫模，將: 平，使成直徑5公分、高度10公分，且兩端平整/之樣品，丨 然後再依美國核能管制委員會（USNRC，us Regulatory C〇mmission))之測試方法分別進行抗=強6= 以及凍融（freezing and thawing)等品質測試，實驗條件 及測試結果列於表1與2中。 ' V 表1、粒狀離子交換樹脂之渴式氧介I ^ 固化實驗結果之1 …飞虱化舁濕式氧化廢液之 陽樹 陰樹 脂體 脂體 積 積 (ml) (ml) —1，40 1, 10 0 0 氧化條件 雙氧 水用 量 (ml)Γ5^ 75 消泡 劑用 量 (克） 17. 調整pH 之單水氫 氧化鋇用 量（克） 27 反應IP 離子交 換樹脂 之 T0C(克 L 738.01Preferably, the control is carried out, and the control is carried out at a ratio of 3 to a better I exchange resin, and the pH is controlled at 丨.5 to 4^, controlled at 2 = sub- 5 1255277; for an anion exchange resin and a cation exchange reaction solution, The PH is preferably controlled, and the control is better at 15' to the second. The reaction liquid is not only U 3 is a rabbit dan ★;; the experimental results of reducing the hydrogen peroxide in a suitable range show that the (four) product ratio of the Yin and Yang mixed line change refers to 'pH control 2 or so per liter The mixed hydrogen peroxide is about 3.5~5 liters, and the lower the hydrogen peroxide/4, ' ϋ = thousand, the less hydrogen peroxide is consumed. (=) When the material is out of the way, (4) The amount of the reaction of the fat and fat feed will be changed, and the right glutinous rice will be replaced with the right gluten. The use of 'ammonium sulfate for the #1 of the ammonium sulphate' The conversion is carried out, and the reaction is as follows: {NH^+BW^NHA〇H + BaS〇A (4) The oxidation of hydrogen produced by the reaction is increased to 8 at the beginning of the solution, and the higher the temperature, the faster the rate of escape. Turn:::Thermal reaction'Addition of gas oxidation frequency will cause the temperature to be raised = ^ gas eviction. According to the experiment of the present invention, the temperature is more favorable for the recovery of ammonia gas. Production &"" , 3⁄4 呵, 摅石*舻4 When converting ice and cesium hydroxide, the concentration of root = root is calculated as the chlorine required for conversion = · f sulfate is converted to barium sulphate, if the amount is too much, = ; There is = age (four), the solid = salt after the solidification of the waste liquid is sulfuric acid:: and the foot, so the sulfuric acid gas cannot be fully converted, and (4) the ammonia body is produced after the formation of the solidified body. Adverse effects. The present invention also completes the ammonia gas produced in the process and the condensed water containing total organic carbon 1255277 organic carbon, TOC). Good and clean treatment 'ensicates that no secondary pollution occurs. The ammonia gas is introduced after it is produced - the gas is decomposed into nitrogen and hydrogen under high temperature contact with the catalyst, wherein the hydrogen is in the ammonia decomposer. The outlet is oxidized to be oxidized and then discharged together with nitrogen. The reaction is as follows: 2NH, Δ catalyst +2//, (5) 2//2 +02 2H20 (6) Nickel-based catalyst for reaction (4) The catalytic effect is very good. According to the results of each test of the present invention, the nickel hydroxide powder is carried on the coffee or the Ah〇3 support only the starting catalyst, and the catalyst bed is heated to ^(^, 婵: the time is close Completely _ can be (four) hair (four) of the New Zealand material depends on the condensed water is not strong 3 will inevitably contain a small amount of organic matter, such as = treatment and its total organic carbon (T〇tai (four) heart, 1 solution 2; Π, the water can not be discharged or re-converted ==::r condensed water after the treatment of Wei, the results show that the second: remove the nuclear species it may contain. The experiment ppmn is low, the slightly water TQG content is about Dozens to hundreds of things to achieve a "advanced oxidation method or addition of peroxides = over-bound ozone and ultraviolet _ , over = over the squash, etc. Experiments have shown that regardless of the use of advanced oxygen 14 1255277 = or the addition of peroxide is good, after the treatment of condensed water, toc. The concentration can be reduced to tens or even ppm below It can be recycled or reused. The curing agent used in the curing of the oxidized waste liquid in this month is specially prepared, except for cement and stone ash (siHca f), fly ash (1) 乂h In addition to Pozzolanic materials such as blast furnace slag powder, in order to ensure long-term stability and quality uniformity of the cured body and to improve operability, it is also possible to add citrate and stone dance depending on the situation. Acid salts, and oxides or salts of about, Shi Xi, Magnesium, Shao, Iron and Wrong. Therefore, the cured body prepared by the present invention has excellent long-term stability in addition to good mechanical strength, freezing resistance, water immersi〇 resistance, and Uniform quality. However, the present invention has a good solution to the shortcomings of the prior art, in addition to eliminating the serious problem of rot and insects, and has a high volume reduction effect, and the operation control is very stable. _ In order to make this statement sufficiently understandable, the embodiment is described in conjunction with the drawings. [Embodiment] The experimental skirt used in this embodiment is as shown in Fig. 2, which comprises a 4'000 ml glass beaker, which is covered by a three-hole glass cover and the middle hole of the glass cover is set. Yes - motor 2 drives (10) stirring! 255277 茱 3 '" hole as feed port 6 'addition - hole as outlet c, the outlet C and: return pipe 4, -_ defogger 5 and _ condenser 6 F. Formula: The mixed gas produced by the chemical is discharged from the outlet c. 'When the film is defogged 5', the water mist contained in the mixed gas ((10)(10)(1) will be removed, and after being formed into a large water droplet, 'returned by the return pipe 4' To the reaction tank 7; water steam: = when the membrane mist eliminator 5 enters the condensation tube, the water vapor will be cold and widely formed into water and collected in the joint surface, and then continue to carry out and remove nuclear species, etc. as needed Treatment; carbon dioxide and other non-condensable gases are discharged at the exit of the condensing tube, and another iron condensate for the condensed water I is required. 9 When the ferrule on the Teflon tube is opened, the sluice can be reduced. The water is refluxed into the reaction beaker to adjust the liquid level therein, 1 〇 is 'conducting t, 11 is ammonia , 12 is the heater, 13 is the thermometer, V 1 : V 2, V 3 is the tube valve. “When wet oxidation operation starts, first take 4〇ml (dry weight ΐ8·〇5g) cationic resin (Amberlite 200C) , Dow Chemical c〇) and 60ml (dry f 19·88 grams) anion resin (10) - surgery, such as (four) and 〇. 嶋 ferrous sulfate solution 1, _W, in order to put in the beaker, then add < concentrated = acid Adjust the initial pH of the solution to about 2. Then place the beaker on the hot plate ± heating and start the stirring motor for stirring. When the solution temperature reaches 95 C, keep using the metering p (four) magic hydrogen peroxide 2 l2 .5m: 'min < flow input beaker Μ吏 ion exchange tree cleavage knife noon. After the hydrogen peroxide starts to input, the reaction solution immediately raises the temperature to the boiling point; the temperature is maintained at 98. to the boiling point; Bubble generation: Add appropriate amount of defoamer (Dow Corning Q2-3447) to inhibit it; and ^ 1255277 :; mono-doped cerium oxide powder to adjust the solution to make it lower when "η"· ^ is reduced by evaporation Water replenishment keeps it stable. Lips are exchanged with resin and 60ml anion tree water After the final-batch resin is added, the hydrogen peroxide will be dihydrated to the point of the first point. The feed is still maintained. After the addition, the reaction solution is still maintained. 5 hours, the hydrogen peroxide is fully reacted. The whole process of the experiment = 7;, V 15.575 liters... The volume is ^ steel. The resin oxidative decomposition liquid is adjusted by the shell and then the sampling analysis T〇C is used to calculate the oxidative decomposition efficiency. · 485 g single /, waste liquid Conversion of sulphate. Firstly, the temperature is maintained in the t-gum emulsified waste liquid, and the ammonium sulphate is converted into barium sulphate, and the bismuth sulphate is added to the sputum. Claw defeated, bucket U_ni " · Introduce it into the ammonia decomposer 1;:;,. One. r) i〇. The ammonia decomposer is heated by electric heating, and when the recording f is used as a decomposition catalyst for ammonia, the temperature is kept decomposed into the material ===; when the body passes, the ammonia or ammonia oxidizes to the air, and the wind milk is suffocated. When the outlet is in contact with the air, it is contained in the body: ,, and two = Γ. In this experiment, the liquid was measured in the liquid. In this step, the wet oxidation of the spent acid is converted to insoluble barium sulfate, and the roots are closed. This is stored in the liquid, and finally converted to n2. The pH of the slurry is ΐ〇·5. The resulting slurry is then cured. The slurry is heated to remove - 1255277 excess water to adjust the water content of the slurry so that the weight of the water and the solidifying agent are properly ratiod. After the concentration treatment, the volume of the concentrated slurry obtained is 734ml, weighs 1,208g, 1^人/, the water weight of A is 576 pure. This concentrated slurry is poured into another mixer, and 7 5 7g of curing agent is slowly added under stirring (to make water / The weight ratio of the curing agent was 〇7 6) After continuously stirring for 15 minutes to uniformly mix, the obtained liquid was poured into a polyethylene (PE) mold having a diameter of 5 cm and a height of 11 cm to prepare a cylindrical solidified body. The cured body is demolded after 28 days of standing curing, and will be: flat, made into a diameter of 5 cm, a height of 10 cm, and the ends are flat / sample, and then according to the US Nuclear Regulatory Commission (USNRC, us Regulatory C〇mmission) The test methods are respectively subjected to quality tests such as anti-strong 6= and freezing and thawing. The experimental conditions and test results are listed in Tables 1 and 2. 'V Table 1, thirsty ion exchange resin for thirsty oxygen I ^ curing test results 1 ... 虱 虱 舁 舁 氧化 氧化 之 阳 阳 树 树 树 树 树 树 树 树 体 体 体 体 体 体 体 体 体 体 体 体 体 体 体 1 1, 10 0 0 Oxidation conditions Hydrogen peroxide dosage (ml) Γ 5 ^ 75 Defoamer dosage (g) 17. Adjust the pH of cesium hydroxide monohydrate (g) 27 Reaction IP ion exchange resin T0C (g L 738.01
表2、粒狀離子交換樹脂之濕式氧化與濕式氧化廢液之 固化實驗結果之2 18 1255277 廢液固化結果 IER 體積 /固 化體 體積 比 養護28 天之抗 壓強度 kg/cm2 凍融測 試後之 抗壓強 度 kg/cm2 3. 95 191 242 廢液處理與固化條 件 和單氫化用 中劑水氧鎖 量克 濃縮 濃縮 漿液 漿液 之總 之含 重量 水量 (克） (克） 1，20 8 576 固化劑用量C克 7 由實驗結果顯示，所得之濕式氧化廢液並無固形物; 留’經測定其中所含之取重量為145克，顯示離子: 換樹脂之TOC氧化率為99·8% ;濕式氧化廢液固化後之丨 化體容積為885ml’是原來離子交換樹脂總容積（3,5咖 的1/3.95;依每國核子管制委員會（刪c)規定的測試: 之固化體抗壓強度為19—2，减融測試後之4 壓強度為242kg/cm2,均遠高於USNRC之TechnicsTable 2: Results of curing test of wet oxidation and wet oxidation waste liquid of granular ion exchange resin 2 18 1255277 Solidification result of waste liquid IER volume/solidified body volume ratio 28 days of compressive strength kg/cm2 freeze-thaw test Post-compressive strength kg/cm2 3. 95 191 242 Waste liquid treatment and curing conditions and single hydrogenation medium water oxygen lock gram concentrated concentrated slurry slurry Total weight (g) (g) 1,20 8 576 The amount of curing agent C gram 7 The experimental results show that the obtained wet oxidizing waste liquid has no solid content; the retention 'measured contains 145 g of the weight, showing the ion: the TOC oxidation rate of the resin is changed to 99·8 %; the volume of the deuterated body after curing of the wet oxidation waste liquid is 885ml' is the total volume of the original ion exchange resin (1/3.95 of 3,5 coffee; according to the test of each national nuclear control committee (deletion c): curing The compressive strength of the body is 19-2, and the compressive strength after the reduction test is 242kg/cm2, which is much higher than the Technics of USNRC.
Position on waste Form 以及斿阈盾 Λ 及我國原此會放射性物料$ 理局之「低放射性廢料體〇 月且口口貝規章巳」之要求，顯示呈 良之機械強度、耐候性與耐水性。 /、 ^ 比較例1 : =較例主要是使用先前技術所使用的中和劑 =料《化鈉較本㈣的方法與先前技㈣ 1255277 重複實施例1的步驟，但 在濕式氧化時調節反應液 弓取代氳氧化鋇. 汕以驅出氨氣。1中在 彳及“濕式氧化廢液的 仍保持於u…間/固=應:， PH也調節提高為9.。3至9 〇5=化:液的濃縮浆液 相同的條件Μ吏固化時濃 ^木用與貫施例1 间,/π 守辰纟f目漿液的含水量與實施例丨相 1中：：：:重量比也相同。實驗結果如表3與4所示， ;=龜化時反應液…消耗的氯氧化妈重量 ^2克’是使用氳氧化鋇時⑵克）的25倍，以 h十异則為接近9 @ ’顯示使用氫氧化 制 使用氣氧化㈣I有效。在濕式氧化廢液的處 品質方面，固化體經根據USNRC規定的方法進行靜置Μ 天後與康融測試後之抗壓強度，結果均顯示固化體不具備 日:顯的機械強度；固化體之比重為186,為使心氧：鋇 時固化體比重（2. 22)的84%;固化體體積為98〇ml，則是 使用氫氧化鋇時（885 ml)的U倍。顯示其無論在濕式氧《 化操作的pH控制、固化體品質，以及減容效率等各方面， 皆不如本發明之方法。 表3、粒狀離子交換樹脂之濕式氧化與濕式氧化廢液之 固化實驗結果之3 ,_氧化條件 氧化結果 (¼樹 陰樹 雙氧 消泡 調整pH 反應前離 溶液 有機 脂體 脂體 水 劑用 的 子交換樹 中之 碳氧 積 積 用量 量 Ca(OH) 脂 T0C 化率 (ml) (ml) (ml) (克） 2用量 T0C(克） (克） (%) 20 1255277 廢液處理與 條件 中和 濃縮 劑 後漿 Ca(0 液之 H)2 總重 用量 量 (克） (克） 56. 8 .... 1 066— 縮漿之水 濃後液含 量克 比較例2 : 固化 廢液固化條件與結果 化用 固劑 量克 固化體體積m 固 化 體 比 重 融試之壓度C 凍測後抗強以？ __k I護天抗強cm I養28之壓度kg/2 ER積固體積匕 I體/化體tPosition on waste Form and 斿 盾 盾 Λ Λ Λ Λ Λ Λ 我国 我国 我国 我国 我国 我国 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性 放射性/, ^Comparative Example 1 : = The comparative example mainly uses the neutralizing agent used in the prior art = "Sodium Sodium (4) and the previous technique (4) 1255277. The procedure of Example 1 is repeated, but is adjusted during wet oxidation. The reaction liquid bow replaces the ruthenium osmium oxide. 汕 to drive out the ammonia gas. 1 in the 彳 and "wet oxidation waste liquid is still maintained between u ... / solid = should:, PH is also adjusted to increase to 9. 3 to 9 〇 5 = chemical: the same conditions of the liquid concentrated slurry Μ吏 curing Between the time and the application of Example 1, the water content of the /π 守辰纟目 slurry is the same as the weight ratio of the Example:::: The experimental results are shown in Tables 3 and 4; = The reaction solution of the turtle is consumed... The weight of the chlorine-oxidized mom is 2 times less than that of the bismuth oxide bismuth (2) gram, and the difference is h when it is close to 9 @ '. It is shown that the gas is oxidized by using the oxidizing gas. In terms of the quality of the wet oxidation waste liquid, the solidified body was subjected to the compressive strength after the test in accordance with the method specified by USNRC, and after the test, the results showed that the solidified body did not have the day: significant mechanical strength; The specific gravity of the solidified body was 186, which was 84% of the specific gravity (2.22) of the cured body at the time of cardio oxygen: 钡; the volume of the solidified body was 98 〇ml, which was U times when cesium hydroxide was used (885 ml). It is not as good as the method of the present invention in terms of pH control of the wet oxygenation process, quality of the solidified body, and volume reduction efficiency. Table 3, granular The results of the experimental results of the wet oxidation and wet oxidation waste liquid of the sub-exchange resin 3, _ oxidation condition oxidation results (1⁄4 tree yin tree deoxygenation defoaming adjustment pH reaction before the reaction of the organic fat body water agent sub-exchange Carbon and oxygen accumulation in the tree Ca(OH) Lipid T0C Rate (ml) (ml) (ml) (g) 2 Dosage T0C (g) (g) (%) 20 1255277 Waste liquid treatment and condition neutralization Concentrate post-slurry Ca (0 liquid H) 2 total weight (g) (g) 56. 8 .... 1 066 - water content after sizing, gram content, comparative example 2: curing solidification conditions And the pressure of the solidified dose of solidified body volume m solidified body, the pressure of C is measured after the freeze test, and the resistance is strong. __k I 护天抗抗强cm I I 28 pressure kg/2 ER accumulation solid body I body /Chemistry t
1，40 0 2, 10 0 00 15 68. 2 737. 94 29. 6 9 ----1 79. 5 1 L—-~---- -----1 L 表4、粒狀離子交換樹脂之濕式氧化與濕式氧化廢液之 固化實驗結果之4 復比較例1的程序，但使用_H溶液為中和劑， 只^結果列於表5貞6中。此實驗所產生的硫酸鹽為 隨’係一水溶性高且十分活潑的化合物。$ 了在固化 時能把Na2S〇4有#容$ # m π a p 有效女疋化，因此除採用與實施例丨相同的 ，本件（貝駟1)外，並且另特別增加一實驗 ::液:終將其中之含水量由-克增加為= 劑作用形成較十二溶解狀態與固化 N感= (低水溶性）的硫酸鹽，避免 應，而^ Π、Όθθ被包埋於固化體中’無法進行安定化反 〜於固化體接觸水份或遭受溫、濕度變化發生 1255277 化0 實驗1在調節濕式氧化溶液pH時，消耗NaOH 68·7 克’疋使用氫氧化鋇（27克）時的2· 54倍，以莫耳數計算 則為12倍’顯不以NaOH調節PH的效果同樣不如氫氧化 鋇；產生的固化體容積為967m丨，比實施例丨（叩5 ml)多 約10% ;固化體靜置28天後之抗壓強度為55 kg/cm2，遠 低於貫施例1的191 kg/cm2;凍融測試後之抗壓強度為 32· 4 kg/cm。同樣顯示無論pH的控制、固化效率與固化 體品質等各方面皆不如實施例1優良。 實驗2所使用的Na0H為881克，消耗量比實驗工 還高；固化體靜置28天後之的抗壓強度為155 kg/cm2， 雖比實驗1優良’但㈣比實施例！所得之結果差；滚融 測试後之抗壓強度為1G8.5 kg/cm2，同樣比實驗！優良， 但仍遠低於實施例1的固化體；產生的固化體容積為 1，3〇〇以’比實驗1約多出1/3，比實施例1使用氫氧化 鋇時多出約1 / 2。 以上的實驗比較，證實本發明的方法無論在濕式氧々 的反應條件控制，以及濕式氧化廢液固化體的減容应固 體品質等各方面，皆比先前的技藝獲得更優良的結果/1,40 0 2, 10 0 00 15 68. 2 737. 94 29. 6 9 ----1 79. 5 1 L—-~---- -----1 L Table 4, granular ions The results of the curing experiment of the wet oxidation and wet oxidation waste liquid of the exchange resin were the same as those of the comparative example 1, but the _H solution was used as the neutralizing agent, and only the results are shown in Table 5贞6. The sulfate produced in this experiment is a highly water-soluble and very active compound. $ can be used to cure Na2S〇4 with ##m π ap effective female sputum, so except for the same as the example ,, this piece (Beiyu 1), and another special addition: an experiment: : Finally, the water content is increased from -g to = the agent forms a sulfate which is more than the twelve dissolved state and the solidified N sense = (low water solubility), avoiding the need, and ^ Π, Ό θθ are embedded in the solidified body 'Cannot be stabilized and reversed~ The solidified body is exposed to moisture or subjected to temperature and humidity changes. 1255277. 0 Experiment 1 When adjusting the pH of the wet oxidation solution, NaOH 68·7 g is consumed. 疋 Use barium hydroxide (27 g) The time is 2.54 times, and the number of moles is 12 times. The effect of not adjusting pH with NaOH is also inferior to that of barium hydroxide; the volume of solidified body produced is 967 m丨, which is more than the example (丨5 ml). About 10%; the compressive strength of the cured body after standing for 28 days was 55 kg/cm2, which was much lower than the 191 kg/cm2 of the first embodiment; and the compressive strength after the freeze-thaw test was 32·4 kg/cm. It was also shown that the control of pH, the curing efficiency, and the quality of the cured body were not as excellent as in Example 1. The Na0H used in Experiment 2 was 881 g, and the consumption was higher than that of the experimenter; the compressive strength after the solidified body was allowed to stand for 28 days was 155 kg/cm2, although it was superior to Experiment 1 but (4) than the example! The result is poor; the compressive strength after the rolling test is 1G8.5 kg/cm2, which is also better than the experiment! It is excellent, but still far lower than the cured body of Example 1; the volume of the solidified body produced is 1,3〇〇, which is about 1/3 more than that of Experiment 1, and about 1 more than that of Example 1 when using barium hydroxide. / 2. As a result of the above experimental comparison, it was confirmed that the method of the present invention achieves superior results in comparison with the prior art, regardless of the control of the reaction conditions of the wet oxygen oxime and the solidification of the wet oxidized waste liquid solidified body.
表5、粒狀離子交換樹脂之濕錢化與濕式 固化實驗結果之5 H 實 氧化條件 1255277 驗 號 次 ----- 陽樹 脂體 積 (ml) τ—-- 陰樹 脂體 積 (ml) ———__ 雙氧 水用 量 (ml) 消泡 劑用 量 (克） 調整 pH 的 NaOH 用量 (克） 反應前 離子交 換樹脂 T0C(克 ) 參 溶液 中之 T0C (克） 有 機 碳 氧 化 率 (°/〇) 1 ΐΓ40~ 0 2, 10 0 2, 10 0 17, 5 00 21 68. 7 737. 94 30. 2 7 80· 77 2 ιΤΐο 0 17, 5 00 12. 9 R 88. 1 737. 94 20. 7 93Γ 44 —-~-—--- _L 1 ( 表6、粒狀離子交換樹 固化實驗結果之6 件 〃 丨旨之濕式氧化與濕式氧化廢液之 廢液固化條件與結果 實 驗 號 次 和 中 劑 量 用 克 縮漿之重 濃後液總 量克 後之量} 縮液水克 濃漿含彳 固化體體積Kmll) 固化劑用量C克} 固 化 IER 體積 /固 化體 體積 比 養護 28天 之抗 壓強 度 kg/c m2 康融 測試 後之 抗壓 強度 kg/cm 比 重Table 5, results of wet-moisture and wet-cure experiments of granular ion exchange resin 5 H Real oxidation conditions 1255277 Test number----- Yang resin volume (ml) τ--- Anion resin volume (ml) — ——__ Hydrogen peroxide dosage (ml) Defoamer dosage (g) Adjusting pH NaOH dosage (g) Pre-reaction ion exchange resin T0C (g) T0C (g) in the reference solution Organic carbon oxidation rate (°/〇) 1 ΐΓ40~ 0 2, 10 0 2, 10 0 17, 5 00 21 68. 7 737. 94 30. 2 7 80· 77 2 ιΤΐο 0 17, 5 00 12. 9 R 88. 1 737. 94 20. 7 93Γ 44 —-~-—--- _L 1 (Table 6, 6 results of the solidification test of the granular ion exchange tree 固化 The conditions and results of the solidification of the waste liquid of the wet oxidation and wet oxidation waste liquid The amount of the liquid in the middle dose is the weight of the concentrated liquid. The amount of the liquid is condensed and the volume of the solidified body is Kmll. The amount of curing agent is Cg} The volume of the cured IER volume/solidified body is 28 days of curing. Compressive strength kg/c m2 Compressive strength kg/cm after Kangrong test
1255277 由以上的說明可知，本製程的技術不僅減容效率高,， 超’產生的最終廢料固化體品質優良’並且符合清潔處理 的要求。 以上的實驗比較，證實本發明方法無論在濕式氧的反 件控制，以及濕式氧化廢液固化體的減容與固化體畀 質等各方面，皆比先前的技藝獲得更優良的結果。 以上所述者，僅為本發明之部分實施例，當不能用以 限定本發明可實施之範圍，依上文所揭示之内容，本發明 確可達到發明之預期目的，提供一種廢離子交換樹脂的處# 理^法’能將廢離子交換樹脂α濕式氧化法減容以及將濕 f虱化殘渣與廢液高效率固化，可供產業上利用，爰依法 提出發明專利申請。 μ【圖式簡單說明】 乐圖為本發明之實施流程示意圖 第2圖為實施本發明之實驗裝置 2馬達 4迴流管 6冷凝管 8接受瓶 1 0導管 1 2加熱器 【主要元件符號說明 丄玻璃燒杯 3 Teflon攪拌葉 5除霧器 7反應槽 9鐵氟龍管 L 1 氨分解器 24 1255277 1 3溫度計 A中間孔 B加料口 C 出口 V 1、V 2、v 3 管閥1255277 It can be seen from the above description that the technique of the present process not only has high volume reduction efficiency, but also has excellent quality of the final waste solidified body produced and meets the requirements of cleaning treatment. The above experimental comparisons confirmed that the method of the present invention achieves superior results in terms of reverse control of wet oxygen, reduction of volume of the wet oxidation waste solidified body, and solidification of the cured body, as compared with the prior art. The above is only a part of the embodiments of the present invention, and when it can not be used to limit the scope of the present invention, the present invention can achieve the intended purpose of the invention and provide a waste ion exchange resin. The #理法 method can reduce the volume of the waste ion exchange resin α wet oxidation method and solidify the wet f slag residue and the waste liquid, and can be used for industrial use. μ [Simplified description of the drawings] Le diagram is a schematic flow chart of the implementation of the present invention. Fig. 2 is a schematic diagram of the experimental apparatus for implementing the present invention. 2 Motor 4 return tube 6 Condensation tube 8 Accepts bottle 10 Catheter 1 2 heater [Main component symbol description丄Glass beaker 3 Teflon stirring blade 5 defogger 7 reaction tank 9 Teflon tube L 1 ammonia decomposer 24 1255277 1 3 thermometer A intermediate hole B feeding port C outlet V 1, V 2, v 3 pipe valve