412433 第87113497號|利申請案 中文說明書修正頁(88年12月） 五、發明説明（7) (C)三磺酸羥胺： ON(S〇3)33- 有用之磺物酸（或無機酸）包括如：鹽酸及硫酸》在鹽酸 使用之例，其被使用佔約0·2到2.0%重量之濃度至廢水中。 礦物酸的添加被認為酸化廢水至pH為2或以下。 當鹽酸和硫酸以各自添加至同一濃度來比較時，經酸分 解步驟後之廢水的COD值上並沒有明顯的差異。然而，鹽 酸是合適的。例如，因為它產生較少量的污泥並抑制其生 成。 此廢水以蒸汽加熱直到溫度達9 5到130°C。在加熱後， 維持溫度一段時間約2到4小時，在此間連二硫酸與n - S成 份依下列分解： (a) 連二硫酸（S2062.)—S042- + S02 (b) N-S 成份—N20 + mS042· + nH+ 反應完成後，已接受酸解處理之廢水接下一段處理（在 第一種處理程序中為絮凝沉澱步驟A，或在第二種處理程 序中為絮凝沉澱步驟C )。 (2)絮凝沉澱步驟A ^ _ , 翅濟部中央標準局員工消費合作社印製 修正 ftft. 12 J 4 補充 A7 B7 - n I - i I— I - - - . - I m HI...... I— (讀先M讀背面之注意事項再填寫本頁) 絮凝沉澱步驟A為調整已經酸分解涉驟處理之廢水到pH 10到1 1，以轉化廢水中的鎂成為氫I化鎂，且以絮凝物之 形式沉澱’並分離由絮凝物及被其捕捉之重金屬成份所形 成的沉澱物。 調整pH可使用如氳氧化鈉之鹼劑輔助。 當pH調整至1 〇到1 1時’廢水中原有之鎂與重金屬（如， 短與叙）以下列反應形成虱乳化鎮與重金屬之氫氧化物。 -10- 本紙張尺度適用中國國家搮準（CNS.) A4規格（210X297公釐） 經滅部中央標"局员工消费合作社印製 412433 A7 ___B1 五、發明説明（1 ) 發明背景 1.發明領域 本發明關於一種由作爲燃燒重油或其他類似物所產生廢 氣的冷卻及除塵，並以石灰-石膏法吸收並除去廢氣中的 硫氧化物之濕式廢氣脱硫系統（更特別的是，—種油煙混 合式的脱硫系統）中排放出來的廢水的處理方法。 2 ·相關技藝描述 燃料如重油之燃燒產生的廢氣以依石灰-石膏爲基礎之 脱硫系統處理。因此，排出的廢水中含C〇D成份（也就是 一些化學需氧性的成份）如連二硫酸及氮-硫成份（以下簡 稱爲"N-S成份”）與重金屬成份。 爲處理廢水中的C0D成份，通常使用絮凝沉殿程序、生 物分解程序、吸附程序及其他類似之法。然而，因廢水中 的無機COD成份（也就是連二硫酸及N-S成份）非常困難並 且不能滿意的僅以這些處理程序移去。 因爲如此，這些無機的COD成份中，連二硫酸可以酸分 解程序來分解之。酸分解程序包含添加一種礦物酸，並且 將廢水維持在預設溫度下以進行下述反應將連二硫酸分解 成硫酸根離子與二氧化劑。此程序使連二硫酸的移去成爲 可行且較簡單。 S2062-—S042-十 so2 酸分解程序已被詳述，如日本專利揭示Nos_ 252526/W8 及47493/·89。 -4 . - .. ———- ···._·_ ------一― 本纸银尺度適用中國國家標準（CNS )以规格（210X2W公兌） {讀先閱讀背面之注意事項再填寫本頁) 訂 第87113497號專村申請案 中文說明書修正頁(88年12月） A7 B7 五、發明説明（ 修ΐϋΧ 11 經濟部中央標準局員工消费合作杜印製 沙濾步驟所使用之濾床可用如：300 mm之支撐砂礫層、 600 mm沙層、與600 mm無煙煤層組成。其常用之過遽線 速度（LV)範圍為7到15 m/h流下。 (8)活性碳吸附步驟 經沙〉慮步驟所排放已沙遽之水引進此活性碳吸附步驟， 其中，水流經填充塔内的活性碳床。本步驟中，由工業廢 水引起之有機COD成份多半可藉吸附至活性碳而被移除。 廢水經活性碳吸附處理後做為最終處理之水，其可被排 放或再利用。 範例 範例1 (第一種處理程庠） 範例1以圖1來說明。如圖1所示，本程序用以處理廢氣 脫硫廢水’其中含：酸分解步驟1，絮凝沉澱步驟A 2、絮 凝沉澱步驟B 3、沙濾步驟7如活性碳吸附步驟8。脫硫廢 水10依這些步驟成功地被處理。甚至，這些步驟可再加上 厚化步驟5和脫水步驟6，以處理由絮凝沉澱步驟A 2與絮 凝沉澱步驟B 3所產之污泥。以下詳細敘述本程序。 _ / 首先，為處理重油燃燒廢氣之脫硫系統所排放出的脫硫 廢水1 0被引入酸分解步驟1。如圖所示，此酸分解步螺J 包含：礦物酸混合槽1 a，蒸汽混合槽1 b、分解槽1 c和中 和槽1 d。 在礦物酸混合槽1 a中，礦物酸（鹽酸）2 2被加至脫硫廢水 1 〇中。鹽酸被加入並混合至給定濃度0.2%重量。混合後， 廢水之pH成為2或更低。然後，於蒸汽混合槽1 b中，廢水 -14 本紙張尺度適用中國國家標隼（CNS ) A4規格（2tOX 297公釐） ^^^1 d It HF — tt^^i m ·^n^— ^^^1 ^^^1 ^^^1—* 3. ,1' (請先M讀背面之注意Ϋ項再填寫本頁) A7 412433 B7 ' - I ~ — . I ii. I _, 1' - —*·*— — *~* 五、發明説明（2 ) 更甚，諸知的N-S成份分解程序含亞硝酸鈉分解程序及 次氣酸鈉分解程序。在這之中，沒有應用酸分解程序處理 N - S成份的例子被提出來。 亞硝酸鈉分解程序包含添加NO,對N-S成份莫耳比率範 圍由1到2的亞硝酸鈉（NaN02)至廢水中，在pH爲2或以下 及溫度爲4 5 °C或以上之條件下分解N-S成份。然而，亞硝 酸納是昂貴的。 此外，因油煙混合式的廢氣脱硫系統排放之廢氣脱硫廢 水通常是弱酸性的，需以大量的酸調整其pH到2或以下。 然後於反應完成後需大量的驗來中和廢水或使之成弱鹼 性。 另一方面，次氣酸鈉分解程序包含添加NaCIO對N-S成份 莫耳比率範圍由3.0到5，0的次氯酸鈉（NaCIO)至廢水中，然 後在溫度爲4 0 C或以上’滞留時間不小於1小時且合適地 不小於2小時條件下進行反應。 在此程序中，在其他N-S成份中之三績酸巍胺依下列反 應分解。412433 No. 87113497 | Amendment page of the Chinese specification of the application (December 88) 5. Explanation of the invention (7) (C) Hydroxylamine trisulfonate: ON (S〇3) 33- Useful sulfonic acid (or inorganic acid ) Include, for example, hydrochloric acid and sulfuric acid "in the use of hydrochloric acid, which is used to the concentration of about 0.2 to 2.0% by weight to the wastewater. The addition of mineral acid is considered to acidify wastewater to a pH of 2 or below. When hydrochloric acid and sulfuric acid were respectively added to the same concentration for comparison, there was no significant difference in the COD value of the wastewater after the acid decomposition step. However, hydrochloric acid is suitable. For example, because it produces a smaller amount of sludge and inhibits its production. This wastewater is heated with steam until the temperature reaches 95 to 130 ° C. After heating, maintain the temperature for a period of about 2 to 4 hours, during which the disulfuric acid and the n-S component are decomposed according to the following: (a) Disulfuric acid (S2062.) — S042- + S02 (b) NS component—N20 + mS042 · + nH + After the reaction is completed, the wastewater that has been subjected to acid hydrolysis treatment is subjected to the next stage of treatment (flocculation sedimentation step A in the first treatment program, or flocculation precipitation step C in the second treatment program). (2) Flocculation sedimentation step A ^ _, printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Development, amended ftft. 12 J 4 Supplement A7 B7-n I-i I-I---.-I m HI .... .. I— (Read the first M and read the notes on the back, then fill out this page) Flocculation and sedimentation Step A is to adjust the wastewater that has been acid-decomposed to pH 10 to 11 to convert the magnesium in the wastewater into magnesium hydride And precipitate in the form of flocs' and separate the precipitates formed by the flocs and the heavy metal components captured by them. Adjusting the pH can be assisted by an alkaline agent such as sodium hydroxide. When the pH is adjusted to 10 to 11, the original magnesium and heavy metals (e.g., short and long) in the waste water react with the following to form lice emulsification ball and heavy metal hydroxides. -10- This paper size is applicable to China National Standard (CNS.) A4 (210X297 mm) Printed by the Central Standard of the Ministry of Economic Affairs " Printed by the Bureau's Consumer Cooperatives 412433 A7 ___B1 V. Description of the invention (1) Background of the invention 1. Invention FIELD OF THE INVENTION The present invention relates to a wet exhaust gas desulfurization system for cooling and dust removal of exhaust gas generated by burning heavy oil or the like, and absorbing and removing sulfur oxides in the exhaust gas by a lime-gypsum method (more specifically, a kind of Treatment method of wastewater discharged from oil fume mixed desulfurization system). 2 · Description of related technologies Exhaust gas from the combustion of fuels such as heavy oil is treated in a lime-gypsum-based desulfurization system. Therefore, the discharged wastewater contains COD components (that is, some chemical aerobic components) such as disulfuric acid and nitrogen-sulfur components (hereinafter referred to as " NS components ") and heavy metal components. For COD components, flocculation and sedimentation procedures, biological decomposition procedures, adsorption procedures, and other similar methods are usually used. However, the inorganic COD components (ie, disulfuric acid and NS components) in wastewater are very difficult and unsatisfactory. The treatment program is removed. Because of this, among these inorganic COD components, even disulfuric acid can be decomposed by an acid decomposition program. The acid decomposition program includes adding a mineral acid and maintaining the wastewater at a preset temperature to perform the following reaction. Decomposition of dithionic acid into sulfate ion and oxidant. This procedure makes removal of dithionic acid feasible and simpler. S2062-—S042-deca so2 acid decomposition procedure has been detailed, as disclosed in Japanese Patent Nos_252526 / W8 And 47493 / · 89. -4.-.. ———- ··· ._ · _ ------ 一 ― The silver standard of this paper applies the Chinese National Standard (CNS) to the specifications (210X2W denomination) { Read the precautions on the back before filling in this page) Order the revised page of Chinese manual No. 87113497 for the village application (December 88) A7 B7 V. Description of the invention (Repair X 11 Central Government Bureau of the Ministry of Economic Affairs Consumer Cooperative Printing The filter bed used in the sand filtration step can be composed of: a 300 mm supporting gravel layer, a 600 mm sand layer, and a 600 mm anthracite coal layer. Its commonly used linear velocity (LV) ranges from 7 to 15 m / h. (8) Activated carbon adsorption step: The activated carbon adsorption step is introduced into the activated carbon adsorption step through the sand> consideration step, where water flows through the activated carbon bed in the packed tower. In this step, organic COD components caused by industrial wastewater Most of them can be removed by adsorption to activated carbon. Wastewater is treated with activated carbon as the final treated water, which can be discharged or reused. Example 1 (First treatment process 庠) Example 1 is shown in Figure 1 For illustration, as shown in Figure 1, this procedure is used to treat waste gas desulfurization wastewater 'which includes: acid decomposition step 1, flocculation sedimentation step A 2, flocculation sedimentation step B 3, sand filtration step 7 such as activated carbon adsorption step 8. Desulfurization wastewater 10 These steps were successfully processed. Furthermore, these steps can be combined with thickening step 5 and dehydration step 6 to treat the sludge produced by flocculation sedimentation step A 2 and flocculation sedimentation step B 3. This procedure is described in detail below. _ / First, the desulfurization wastewater 10 discharged from the desulfurization system for treating heavy oil combustion exhaust gas is introduced into acid decomposition step 1. As shown in the figure, this acid decomposition step snail J contains: mineral acid mixing tank 1 a, steam Mixing tank 1 b, decomposition tank 1 c, and neutralization tank 1 d. In the mineral acid mixing tank 1 a, mineral acid (hydrochloric acid) 2 2 is added to the desulfurization wastewater 10. Hydrochloric acid was added and mixed to a given concentration of 0.2% by weight. After mixing, the pH of the wastewater becomes 2 or lower. Then, in the steam mixing tank 1 b, the waste water-14 paper size is applicable to the Chinese National Standard (CNS) A4 specification (2tOX 297 mm) ^^^ 1 d It HF — tt ^^ im · ^ n ^ — ^ ^^ 1 ^^^ 1 ^^^ 1— * 3., 1 '(please read the note on the back before filling this page) A7 412433 B7'-I ~ —. I ii. I _, 1 ' -— * · * — — * ~ * V. Description of the Invention (2) Furthermore, the well-known NS component decomposition program contains a sodium nitrite decomposition program and a sodium hypoxia gas decomposition program. Among them, an example in which the N-S component is not processed by an acid decomposition program is proposed. The decomposition procedure of sodium nitrite includes the addition of NO, and the molar ratio of NS to sodium components (NaN02) ranging from 1 to 2 into the waste water. It is decomposed at a pH of 2 or below and a temperature of 45 ° C or above. NS ingredients. However, sodium nitrite is expensive. In addition, the exhaust gas desulfurization waste water discharged from the oil-smoke mixed exhaust gas desulfurization system is usually weakly acidic, and its pH needs to be adjusted to 2 or below with a large amount of acid. After the reaction is completed, a large number of tests are needed to neutralize the wastewater or make it weakly alkaline. On the other hand, the sodium hypogenite decomposition program includes adding sodium hypochlorite (NaCIO) with a molar ratio of NaCIO to NS components ranging from 3.0 to 5,0 to the wastewater, and then at a temperature of 40 ° C or above, the residence time is not less than 1 The reaction is carried out for hours and suitably not less than 2 hours. In this procedure, tris (aminopyridyl) amine in other N-S components is decomposed according to the following reaction.
60N(S03)广 + 18 CIO· + 10H2O -^4NO + 2N03' + 18HS04 + 18C1' + H+ + 3〇2 例如’如存有約6,000 mg/L的胺離子時，會消耗大量的 次氣酸鈉，造成化學品費用增加。更甚之，將會導致處理 效率明顯降低。 此次亂故納分解程序已被詳述，如日本專利揭示 -5- 本紙張尺度適用中國國家榡準（CMS ) Λ4規梏（210X2们公棼]~~ C讀先閱讀背面之注意事項再填寫本頁) I裝- 訂 經漪部中央標津局員工消费合作社印聚 經满部中央標準局貝工消費合作社印製 412433 a7 B7 — ——一 ---------------* 五、發明説明（3 ) 59026/，92 中》 當脱硫廢水含有連二硫酸與N-S成份二者，依慣用之處 理程序處理，那些成份必需分開處理。依此，造成操作程 序複雜及可觀的設備花費之缺點。 再者爲處理廢水中的重金屬成份，通常會施予一絮凝沉 澱程序’此程序於廢水中加入消石灰或硫酸鋁以造成沉搬 而分離之。雖此處理程序可幾乎完全移除重金屬，某些重 金屬仍不可避免的存在廢水中。因爲如此，需使用—些額 外方法以滿足嚴格的排放標準。 甚至此慣用絮凝沉澱程序也結合使用螯合劑（也就是， 一種高分子的重金屬捕捉劑）添加之程序，以形成補捉了 重金屬之微絮凝物然後與絮凝沉;殿污泥一起分離β然而， 爲達成希望的處理效能’昂貴的螯合劑必需大量添加。需 要可觀花費的化學品爲一個缺點。 發明概要 本發明的一個目的是提供一個有效而滿意的處理由作爲 燃燒重油廢氣中硫氧化物吸收及移除用的濕式廢氣脱硫系 統排放出來的廢水中所含的無機C〇D成份（如：連二硫酸 及N-S成份）、重金屬（錳及鎘）及有機c〇D成份之移除程 序’並且克服爲處理這些成份慣用之程序中之缺點。 依本發明所提供之第一種用於處理由作爲燃燒重油廢氣 中硫氧化物吸收及移除用的濕式廢氣脱硫系統排放出來的 廢氣脱硫廢水之程序，其中包含： (a)添加礦物酸至此廢水中，並在酸性條件下加熱廢水以 本紙狀度適财_家料（CNS) 一-I ^^1 i-·· b -I— i n^i If «^0^ Jn ^^1 -='5 f謂先閲讀背面之注意事項再填穹本頁} 412433 A7 ---—___K7 五、發明説明（4 ) " 解廢夂中所含之連二硫酸與氮-硫成份的酸分解步驟： (b)調整已經酸分解程序之廢水至pH 1〇到丨丨、使廢水中 的鎂轉化成氫氡化鎂以絮凝物之形式沉殿、並且分離由絮 凝物及被其補捉之重金屬成份所形成之沉澱物，之絮凝沉 澱;步驟A ;及 (C)添加螯合劑和鐵組合物至已經絮凝沉澱步驟A之廢水 中調整此廢水至pH 6-8以形成重金屬螯合物和氫氧化鐵之 絮凝 >几殺物’並且分離由氫氧化鐵絮凝物和被其補捉之重 金屬整合物所形成之沉澱物的絮凝沉澱步驟B。 此一程序甚可包含 (d) 使已經絮凝沉澱步驟b後的廢水至沙濾處理並且由此 廢水中移除懸浮物之沙濾步驟；及 (e) 使已經沙濾步驟後的廢水與活性碳接觸，藉以移除吸 附至活性碳的有機COD成份之活性碳吸附步驟。 依本發明所提供之第二種用於處理由作爲燃燒重油廢氣 中硫氧化物吸收及移除用的濕式廢氣脱硫系統排放出來的 廢氣脱硫廢水之程序，其中含： (a) 添加礦物酸至此廢水中，並在酸性條件下加熱廢水以 分解廢水中所含之連二硫酸與氮-硫成份的酸分解步騍； 經满部中央標卒局貝工消費合作社印製 ^^1 ft - - -I n I - II - I I 彳 乂-4 (請先閱讀背而之注意事項再填汽本頁) (b) 添加螯合劑至已經酸分解步驟之廢水中、調整此廢水 至pH 8到1 〇以形成重金屬螯合物、添加鐵組合物至此廢水 中' 維持此廢水在pH 8到1 0以沉澱氫氡化鐵絮凝物、及分 離由氫氧化鐵絮凝物及被其補捉之重金屬螯合物所形成之 沉澱物之絮凝沉澱步驟C。60N (S03) + 18 CIO · + 10H2O-^ 4NO + 2N03 '+ 18HS04 + 18C1' + H + + 3〇2 For example, if there is about 6,000 mg / L of amine ion, a large amount of sub-acid acid will be consumed Sodium, causing increased chemical costs. What's more, it will result in a significant reduction in processing efficiency. The messy breakdown procedure has been detailed, as disclosed in Japanese Patent -5- This paper size applies to the Chinese National Standard (CMS) Λ4 Regulations (210X2 men's public address) ~~ C Read the precautions on the back before reading (Fill in this page) I Pack-Printed by the Central Consumers' Cooperative of the Ministry of Standards and Printing of the Ministry of Printing and Printing, printed by the Central Standards Bureau of the Ministry of Standardization, and printed by the Shellfish Consumer Cooperative of the Ministry of Standardization, 412433 a7 B7 — —— 一 ------------ --- * V. Description of the Invention (3) 59026 /, 92 "When the desulfurized wastewater contains both disulfuric acid and NS components, the components must be treated separately according to conventional processing procedures. According to this, the disadvantages of complicated operating procedures and considerable equipment costs are caused. Furthermore, in order to treat the heavy metal components in the wastewater, a flocculation sedimentation process is usually applied. This process adds slaked lime or aluminum sulfate to the wastewater to cause separation and separation. Although this process can remove heavy metals almost completely, some heavy metals are unavoidably present in wastewater. Because of this, additional methods are needed to meet stringent emission standards. Even this conventional flocculation sedimentation process is combined with a chelating agent (that is, a polymer heavy metal capture agent) addition process to form microflocculates that capture heavy metals and then settle with flocculent sedimentation; however, β To achieve the desired processing efficiency, 'expensive chelating agents must be added in large amounts. The need for considerable expenditure of chemicals is a disadvantage. SUMMARY OF THE INVENTION An object of the present invention is to provide an effective and satisfactory treatment of inorganic COD components (e.g., waste water) discharged from a wet exhaust gas desulfurization system for absorbing and removing sulfur oxides in a heavy oil exhaust gas, such as : Removal procedures of even disulfuric acid and NS components), heavy metals (manganese and cadmium) and organic coD components' and to overcome the shortcomings in the procedures commonly used to deal with these components. The first procedure for treating waste gas desulfurization waste water discharged from a wet exhaust gas desulfurization system for absorbing and removing sulfur oxides in a heavy oil exhaust gas according to the present invention includes: (a) adding mineral acid At this point, the waste water is heated under acidic conditions to make the paper suitable for paper_ 家 料 (CNS) 一 -I ^^ 1 i- ·· b -I— in ^ i If «^ 0 ^ Jn ^^ 1- = '5 f means read the precautions on the back before filling in this page} 412433 A7 -------___ K7 V. Description of the invention (4) " The acid containing dithionine and nitrogen-sulfur components in the waste solution Decomposition steps: (b) Adjust the wastewater that has been subjected to the acid decomposition process to pH 10 to 丨 丨, convert the magnesium in the wastewater into magnesium hydride and sink it in the form of flocs, and separate the flocs and catch them Precipitate formed by heavy metal components, flocculation precipitation; step A; and (C) adding chelating agent and iron composition to the wastewater that has been flocculated and precipitated, and adjusting the wastewater to pH 6-8 to form heavy metal chelate And ferric hydroxide flocculation > several killers' and separated from the iron hydroxide flocculant and its catch Flocculation precipitation step the formed precipitate was B. Integration of the genus This procedure may even include (d) a sand filtration step for flocculating the wastewater after the sedimentation step b to a sand filtration process and removing suspended matter from the wastewater; and (e) making the wastewater and activity after the sand filtration step Carbon contact is an activated carbon adsorption step to remove organic COD components adsorbed to the activated carbon. A second procedure for treating waste gas desulfurization wastewater discharged from a wet exhaust gas desulfurization system for absorbing and removing sulfur oxides in a heavy oil exhaust gas according to the present invention, comprising: (a) adding mineral acid So far, the wastewater is heated under acidic conditions to decompose the acid decomposition step of dithionic acid and nitrogen-sulfur components contained in the wastewater; printed by the Shellfish Consumer Cooperative of the Central Bureau of Standardization of the People's Republic of China ^^ 1 ft- --I n I-II-II 彳 乂 -4 (Please read the precautions before filling this page) (b) Add the chelating agent to the wastewater that has been subjected to the acid decomposition step, and adjust the wastewater to pH 8 to 10 to form a heavy metal chelate, add an iron composition to the wastewater ', maintain this wastewater at pH 8 to 10 to precipitate hydrogenated hydrogenated iron flocculants, and separate the heavy metals from the iron hydroxide flocculants and their capture Flocculation precipitation step C of the precipitate formed by the chelate.
本紙張尺度適用中國國家標準（CNS ) Λ4规格（210x_2<mUM «2433 A7 ------- --- B7 五、發明説明（5 ) ~ — 此一程序甚可包含 (c) 使已經絮凝沉澱步驟c後的廢水至沙濾處理，並由此 廢水中移除懸浮物之沙濾步驟；及 (d) 使已經沙濾步驟後的廢水與活性碳接觸，藉以移除吸 附至活性碳的有機COD成份之活性碳吸附步驟。 #則逑依照本發明作爲廢氣脱硫廢水處理之用的第一種與 第種程序，其酸分解步驟可使用添加〇.2到2.0%重量之鹽 酸至廢氣脱硫廢水中，然後加熱此廢水至9 5到ι3〇χ;之严 度。 '皿 _前述依照本發明作爲廢氣脱硫廢水處理之用的第—種與 第一種程序，其螯合劑可使用一種含氨荒酸鹽或硫赶基團 並作爲其螯合基團之組合物。 本發明之程序具有以下功效： 於酸分解步驟中，不僅難以被分解之連二硫酸而且連由 N S成伤產生之cod成份都能被分解並且高效率的移除。 那些不能使用慣用之絮凝沉澱程序滿意移除之重金屬如 Μ及鎘，可以幾乎完全被移除。 經满部中央標率局貝工消t合作社印製 ·r * . ：——1-------¾I. Γΐί先閱讀背面之ίΐ意事¾再填寫本頁} 變化多端的成份可使用與廢水中各種成份相關之處理步 驟以系統化結合之多階段處理程序非常有效的移去，因此 COD與各㈣金屬的排放標準値《規定可被適時的達成。 系列步驟所需之設備大小可以被減少，並且此設備的花 費能明顯的被減少。 避免各種化學品的消耗浪費可明顯的減少各類化學品之 花費。 本紙張尺度適用中國國家椋準（0邮）如规格（2丨〇><2^^.. A7 B7 412433 五、發明説明（6 a示説明 圖！爲描述本發明之第—種處理程序之流程圖； 圖2爲解釋本發明之帛—種或第二 步驟的簡圖； 圖3爲解釋本發明之第—種 簡圖· 種慝理程序中絮凝沉澱步驟A纪 圖4爲解釋本發明之第—種虛 簡圖. 種處理私序中絮凝沉澱步驟B的 圖5爲描述本發明之第二種處理程序之流程圖；及 圖6爲解釋本發明之第二種虚 _ 種處理私序中絮凝沉澱步驟C的 間圖。 項的詳纟 依本發明作爲非煙脱疏廢水處理程序所含之各步骤依序 如下所述。須瞭解在本發明之第一種與第二種處理程序中 相同的步驟只解釋一次。 (1)酸分解步騣 酸分解步驟爲：添加礦物酸到廢水中、並且在酸性條件 下加熱其廢水以分解存於廢中之連二硫酸與氮· 步驟。 脱硫廢水中所含因脱硫器中s〇2氧化形成之連二硫酸 (S2〇62 )與因S〇2及Ν〇χ反應形成之N-S成份以本發明之程序 處理。後者之N-S成份主要有下列組合物。 (a) 單績酸經胺： H0NHS03_ (b) 二續酸經胺： H0N(S03)22- -9- 本紙張尺度適用中阐國家標埤((他）八4規格（2丨0\ 297公釐） (讀先閱讀背面之注意事項再填寫本頁) % 412433 第87113497號|利申請案 中文說明書修正頁(88年12月） 五、發明説明（7) (C)三磺酸羥胺： ON(S〇3)33- 有用之磺物酸（或無機酸）包括如：鹽酸及硫酸》在鹽酸 使用之例，其被使用佔約0·2到2.0%重量之濃度至廢水中。 礦物酸的添加被認為酸化廢水至pH為2或以下。 當鹽酸和硫酸以各自添加至同一濃度來比較時，經酸分 解步驟後之廢水的COD值上並沒有明顯的差異。然而，鹽 酸是合適的。例如，因為它產生較少量的污泥並抑制其生 成。 此廢水以蒸汽加熱直到溫度達9 5到130°C。在加熱後， 維持溫度一段時間約2到4小時，在此間連二硫酸與n - S成 份依下列分解： (a) 連二硫酸（S2062.)—S042- + S02 (b) N-S 成份—N20 + mS042· + nH+ 反應完成後，已接受酸解處理之廢水接下一段處理（在 第一種處理程序中為絮凝沉澱步驟A，或在第二種處理程 序中為絮凝沉澱步驟C )。 (2)絮凝沉澱步驟A ^ _ , 翅濟部中央標準局員工消費合作社印製 修正 ftft. 12 J 4 補充 A7 B7 - n I - i I— I - - - . - I m HI...... I— (讀先M讀背面之注意事項再填寫本頁) 絮凝沉澱步驟A為調整已經酸分解涉驟處理之廢水到pH 10到1 1，以轉化廢水中的鎂成為氫I化鎂，且以絮凝物之 形式沉澱’並分離由絮凝物及被其捕捉之重金屬成份所形 成的沉澱物。 調整pH可使用如氳氧化鈉之鹼劑輔助。 當pH調整至1 〇到1 1時’廢水中原有之鎂與重金屬（如， 短與叙）以下列反應形成虱乳化鎮與重金屬之氫氧化物。 -10- 本紙張尺度適用中國國家搮準（CNS.) A4規格（210X297公釐） 4ί2433 Α7 -~~— _____Β7 五、發明説明（8 ) 重金屬（氫氧化物被吸附及包含至氫氧化鎂形成之絮凝物 中以產生沉澱物。 I:--------衣------訂 (請先聞讀背面之注意事項再填寫本頁} U) Mg2+ + 20H- —Mg(OH)2 (b) Mn2+ + 20H'^Mn(OH)2 (e) Cd2+ + 20H'->Cd(0H)2 在含這些絮凝物的懸浮物中固體物質在沉澱槽内被分 離，由此造成之上層澄清液續於下一步驟處理。（第一種 處理程序爲絮凝沉澱步驟B )。This paper size applies the Chinese National Standard (CNS) Λ4 specification (210x_2 < mUM «2433 A7 ------- --- B7 V. Description of the invention (5) ~ — This procedure may even include (c) Flocculating the wastewater after the sedimentation step c to a sand filtration process and removing the suspended matter from the wastewater by the sand filtration step; and (d) contacting the wastewater after the sand filtration step with activated carbon to remove the adsorbed carbon Step of activated carbon adsorption of organic COD components. # 则 逑 According to the first and first procedures of the present invention for the treatment of waste gas desulfurization wastewater, the acid decomposition step can use the addition of 0.2 to 2.0% by weight of hydrochloric acid to the waste gas In the desulfurization wastewater, the wastewater is then heated to a degree of 95 to 305. The dish is the first and the first procedures used for the treatment of waste gas desulfurization wastewater according to the present invention, and a chelating agent may be used. A composition containing an ammonium salt or a sulfur driving group as its chelating group. The procedure of the present invention has the following effects: In the acid decomposition step, not only the disulfuric acid that is difficult to be decomposed but also the NS wounds are produced. Cod ingredients can be decomposed and efficient Removal of heavy metals. Those heavy metals such as M and cadmium that cannot be satisfactorily removed using conventional flocculation and sedimentation procedures can be removed almost completely. Printed by the Central Bureau of Standards and Technology Co., Ltd. · r *. —1 ------- ¾I. Γΐί Read the ΐImplementation on the back ¾ and then fill out this page} Variety of ingredients can be used in a systematic and multi-stage process with various processing steps related to various ingredients in wastewater Effectively removed, so the COD and emission standards of various metals «regulations can be reached in a timely manner. The size of the equipment required for a series of steps can be reduced, and the cost of this equipment can be significantly reduced. Avoid various chemicals Consumption and waste can significantly reduce the cost of various chemicals. This paper size is applicable to China's national standards (0 post) such as specifications (2 丨 〇 > < 2 ^^ .. A7 B7 412433 V. Description of the invention (6 a Illustrative diagram! A flowchart describing the first kind of processing procedure of the present invention; FIG. 2 is a diagram explaining the second or second step of the present invention; FIG. 3 is a diagram illustrating the first kind of the present invention. Flocculation sedimentation step Fig. 4 is a diagram explaining the first kind of virtual diagram of the present invention. Fig. 5 is a flowchart describing the second kind of processing procedure of the present invention; and Fig. 6 is an explanation of the present invention. Interval diagram of step C of flocculation and sedimentation in the second kind of private treatment sequence. The details of the items according to the present invention as a non-smoke dewatering wastewater treatment procedure are as follows. The first step is the same as that in the second treatment procedure, and is explained only once. (1) Acid decomposition step The acid decomposition step is: adding mineral acid to the waste water, and heating the waste water under acidic conditions to decompose the waste. Lithium disulfuric acid and nitrogen · steps. The disulfuric acid (S2 062) formed by the oxidation of so2 in the desulfurizer contained in the desulfurization wastewater and the N-S component formed by the reaction of S02 and NOx are treated by the procedure of the present invention. The latter N-S component mainly includes the following composition. (a) Monoamine acid amines: H0NHS03_ (b) Dibasic acid amines: H0N (S03) 22- -9- The national standard ((he) 8 4 (2 丨 0 \ 297) in this paper is applicable in the standard of this paper (Mm) (Read the precautions on the back before you fill in this page)% 412433 No. 87113497 | Chinese Version Correction Page of the Application (December 88) 5. Description of the Invention (7) (C) Hydroxylamine Trisulfonic Acid: ON (S〇3) 33- Useful sulfonic acids (or inorganic acids) include, for example, hydrochloric acid and sulfuric acid. Examples are used in hydrochloric acid, which are used in wastewater at a concentration of about 0.2 to 2.0% by weight. Minerals The addition of acid is considered to acidify the wastewater to a pH of 2 or below. When hydrochloric acid and sulfuric acid are added at the same concentration to compare, there is no significant difference in the COD value of the wastewater after the acid decomposition step. However, hydrochloric acid is suitable For example, because it produces a smaller amount of sludge and inhibits its production. This wastewater is heated with steam until the temperature reaches 95 to 130 ° C. After heating, the temperature is maintained for a period of about 2 to 4 hours, and even here Disulfuric acid and n-S components are decomposed as follows: (a) Disulfuric acid (S2062.) — S042- + S02 (b) NS component After the N20 + mS042 · + nH + reaction is completed, the wastewater that has been subjected to acid hydrolysis treatment is subjected to the next stage of treatment (the flocculation sedimentation step A in the first treatment program, or the flocculation sedimentation step C in the second treatment program). (2) Flocculation sedimentation step A ^ _, printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Development, amended ftft. 12 J 4 Supplement A7 B7-n I-i I-I---.-I m HI .... .. I— (Read the first M and read the notes on the back, then fill out this page) Flocculation and sedimentation Step A is to adjust the wastewater that has been acid-decomposed to pH 10 to 11 to convert the magnesium in the wastewater into magnesium hydride And precipitate in the form of flocs' and separate the precipitates formed by the flocs and the heavy metal components captured by them. Adjusting the pH can be assisted by alkali agents such as sodium hydroxide. When the pH is adjusted to 10 to 11 'The original magnesium and heavy metals (eg, short and Syria) in the wastewater form the following reactions to form lice emulsified towns and heavy metal hydroxides. -10- This paper size is applicable to China National Standard (CNS.) A4 (210X297 mm) ) 4ί2433 Α7-~~ — _____ Β7 V. Description of the invention (8) Heavy metals (hydrogen The compound is adsorbed and contained in the floc formed by magnesium hydroxide to produce a precipitate. I: -------- Cloth -------- Order (Please read the precautions on the back before filling this page } U) Mg2 + + 20H- —Mg (OH) 2 (b) Mn2 + + 20H '^ Mn (OH) 2 (e) Cd2 + + 20H'-> Cd (0H) 2 in a suspension containing these floes The solid material is separated in the sedimentation tank, which causes the upper clear liquid to continue processing in the next step. (The first treatment procedure is the flocculation sedimentation step B).
(3)_絮凝沉澱步驄R 絮凝沉澱步驟B爲添加螯合劑及鐵組合物至已經絮凝沉 澱步驟A之廢水中，並調整其]3只至6到8以形成重金屬螯合 物並且形成氫氧化鐵之絮凝沉澱物，且分離由氫氧化鐵絮 凝物及被其捕捉之重金屬螯合物所形成之沉澱物的處理步 碟。 至於其螯合劑’可使用一種含有氨荒酸鹽基團（-NH-CSzNa)或硫赶基團（-SNa)作爲其螫合基團液狀高分子重金 屬捕捉劑。螯合劑通常添加量爲1 〇到丨，〇〇〇 mg/L，以形成 捕捉重金屬之微絮凝物。 至於其鐵組合物’可使用如氣化鐵及硫酸鐵之絮凝劑。 例如，使用氣化鐵時，於中性pH範圍内進行下列反應形成 氫氧化鐵。此氫氧化鐵是形成絮凝物之形式，並且前述捕 捉重金屬之微絮凝物被吸附並包含於這些絮凝物内以產生 沉澱物。(3) _Flocculation precipitation step 骢 R flocculation precipitation step B is to add chelating agent and iron composition to the wastewater which has been flocculated precipitation step A and adjust it] 3 to 6 to 8 to form heavy metal chelate and hydrogen A flocculent precipitate of iron oxide, and a processing step for separating a precipitate formed by the floc of iron hydroxide and the heavy metal chelate captured by it. As the chelating agent ', a liquid polymer heavy metal trapping agent containing an ammonium salt group (-NH-CSzNa) or a sulfur driving group (-SNa) as its chelating group can be used. Chelating agents are usually added in an amount of 10 to 1,000 mg / L to form microflocculates that capture heavy metals. As for the iron composition ', flocculants such as gasified iron and iron sulfate can be used. For example, when using vaporized iron, the following reactions are performed in a neutral pH range to form iron hydroxide. This iron hydroxide is in a form of forming flocs, and the aforementioned micro-flocs for capturing heavy metals are adsorbed and contained in these floes to generate a precipitate.
FeCl3 + 〇Η· —Fe(OH)3 -11 - 本紙張尺度遶用中國國家榇埤（（’NS ) Λ4規格（210X297公釐） 412433 A7 B7 五、發明説明（9) 此鐵組合物添加量约1 00到500 mg/L之鐵量。 . .m - - I — ^^1 I - . - i— ^^1 • e (請先鬩讀背面之注意事項再填寫本頁) 本步驟中’如聚丙締醯胺之陽離子高分子之絮凝劑是適 於添加的’以形成粗絮凝物並增加可分離性。 包括這些絮凝物之懸浮物内之固體物質在沉殿槽内被分 離，其上層澄清液續以下階段步驟處理（即於第一種處理 程序中的沙濾步驟）。 結合螯合劑與鐵組合物之使用使得高度移除重金屬離子 成爲可行，並明顯減少螯合劑之用量。FeCl3 + 〇Η · —Fe (OH) 3 -11-This paper scale uses the Chinese national standard (('NS) Λ4 size (210X297 mm) 412433 A7 B7 V. Description of the invention (9) This iron composition is added The amount of iron is about 100 to 500 mg / L. .M--I — ^^ 1 I-.-I— ^^ 1 • e (Please read the precautions on the back before filling this page) This step The 'flocculant of cationic polymers such as polypropylene amidamide is suitable to be added' to form coarse flocs and increase separability. The solid matter in the suspension including these flocs is separated in the sink chamber, The upper clarification liquid is processed in the following steps (that is, the sand filtration step in the first processing procedure). The combination of the chelating agent and the iron composition makes it possible to highly remove heavy metal ions, and significantly reduces the amount of chelating agent.
(4)絮凝沉澱步驟C 絮凝沉澱步驟C爲添加螯合劑至已經酸處理步職後之廢 水中’並調整廢水pH至8到1 0以形成重金屬螯合物、添加 鐵組合物至此廢水、維持廢水在pH 8到1 〇以形成氫氧化鐵 絮凝沉澱物，且分離由氫氧化鐵絮凝物與被其捕捉之重金 屬螯合物所形成之沉澱物的步骤。 此螯合劑可使用與前述之絮凝沉澱步驟B中所用之螯合 劑相同。螯合劑通常的使用量爲1 〇到！，〇〇〇 mg/L。 其pH的調整可以鹼劑（如：氫氧化鈉）輔助之，如必要時 可使用礦物酸（如：鹽酸）。當廢水被調整至pH 8到1 〇時， 造成微絮凝物捕捉大量的鎘。 此鐵組合物可使用前述絮凝沉澱步驟B中所用之相同 物。此鐵組合物通常的使用量爲約100到5〇〇 mg/L之鐵。 此廢水可藉添加鹼劑（如：氫氧化鈉）維持pH 8到1 〇。 在維持廢水之pH於8到1 〇時，發生與前述絮凝沉澱步騍 B相同^反應以沉澱氫氧化鐵之絮凝物。前述之微絮凝物 -12- 本紙張尺㈣则，1¾¾:料(rNS ) Λ4規297公釐) 412433 A7 五、發明説明（1〇) 與任何未捕捉之重金屬（如：^被吸附並包含_ 物内生，沉殿。在本步骚中，使用與前述之絮凝沉擬步驟 :相同之高分子的絮凝劑以形成粗絮凝物並且增加分離 在含絮凝物之懸浮物中的固體物料沉殿槽内被分離， 所形成之上層澄清液續以下階段步驟處理（即：第二種 理程序中之沙濾步驟）。 (5) 厚化步驟 在厚化步#中’由第_ #處理程序之絮凝沉搬步锻A與 B，和由第二種處理程序之絮凝沉澱步驟匚，而來之廢水 的/亏泥以厚化器濃縮並固體物分離排放。污泥之濃縮，通 常由1到2 %重量於厚化步驟後被提昇至5 %重量。被分離 的水回到前一步驟（在第一種處理程序爲絮凝沉澱步驟 A，在第二種處理程序爲絮凝沉澱步騍c )，再併同由酸分 解步驟而來之廢水再處理之。污泥接著脱水步驟。 (6) 脱水步驟 在脱水步驟中’已濃縮之污泥以脱水器再脱水，並以渡 餅排放。在本步驟中，壓濾機、壓帶機、螺旋傾析機或^ 似之物可做爲脱水器之用。例如，若使用壓濾機時，污泥 之含水量可被減少至不大於7〇%之重量。 (7) 沙濾步騾 於沙遽步驟中’由第一種處理程序之絮凝沉澱步驟B， 或由第二種處理程序之絮凝沉澱步驟C，而來之上層澄、青 液中所仍殘留的懸浮物質以沙濾處理予以分離並移除。 -13- 本紙張尺度洎用中國围家標绛（（、NS ) Λ4規格（2】〇Χ 297公嫠） (諳先閱讀背面之注意事項再填寫本頁) '衣 .11 第87113497號專村申請案 中文說明書修正頁(88年12月） A7 B7 五、發明説明（ 修ΐϋΧ 11 經濟部中央標準局員工消费合作杜印製 沙濾步驟所使用之濾床可用如：300 mm之支撐砂礫層、 600 mm沙層、與600 mm無煙煤層組成。其常用之過遽線 速度（LV)範圍為7到15 m/h流下。 (8)活性碳吸附步驟 經沙〉慮步驟所排放已沙遽之水引進此活性碳吸附步驟， 其中，水流經填充塔内的活性碳床。本步驟中，由工業廢 水引起之有機COD成份多半可藉吸附至活性碳而被移除。 廢水經活性碳吸附處理後做為最終處理之水，其可被排 放或再利用。 範例 範例1 (第一種處理程庠） 範例1以圖1來說明。如圖1所示，本程序用以處理廢氣 脫硫廢水’其中含：酸分解步驟1，絮凝沉澱步驟A 2、絮 凝沉澱步驟B 3、沙濾步驟7如活性碳吸附步驟8。脫硫廢 水10依這些步驟成功地被處理。甚至，這些步驟可再加上 厚化步驟5和脫水步驟6，以處理由絮凝沉澱步驟A 2與絮 凝沉澱步驟B 3所產之污泥。以下詳細敘述本程序。 _ / 首先，為處理重油燃燒廢氣之脫硫系統所排放出的脫硫 廢水1 0被引入酸分解步驟1。如圖所示，此酸分解步螺J 包含：礦物酸混合槽1 a，蒸汽混合槽1 b、分解槽1 c和中 和槽1 d。 在礦物酸混合槽1 a中，礦物酸（鹽酸）2 2被加至脫硫廢水 1 〇中。鹽酸被加入並混合至給定濃度0.2%重量。混合後， 廢水之pH成為2或更低。然後，於蒸汽混合槽1 b中，廢水 -14 本紙張尺度適用中國國家標隼（CNS ) A4規格（2tOX 297公釐） ^^^1 d It HF — tt^^i m ·^n^— ^^^1 ^^^1 ^^^1—* 3. ,1' (請先M讀背面之注意Ϋ項再填寫本頁) ^12433 A7 "一 ‘ _ B7 _ _ 五、發明説明（12) 以蒸汽2 1加熱直到9 5 °C。在其後，廢水引入分解槽1 c中 保持溫度並於其中反應2小時。前述之鹽酸濃度、反應溫 度與反應時間是那些基於本處理程序之系列實驗結果中發 現可有效分解其COD成份的。連二硫酸與N-S成份於此操 作中被分解後，廢水被引入中和槽1 d，其pH已使用鹼劑 2 3來輔助預設調整至約中和之程度（即：約7 )。鹼劑2 3， 使用氫氧化鈉是因爲其不可能形成任何固體物質。預設中 和不僅爲保護下一步驟所用之設備，也同時爲易於下一階 段pH調整，因其僅需調整較小範圍即可。廢水丨丨經酸分 解處理後以絮凝沉澱步驟A 2處理。 如圖3所示，絮凝沉澱步驟A2含：pH調整槽2a、絮凝槽 2 b及沉;殿槽2 c。 於pH調整槽2 a中’已經酸分解處理後之廢水〗1，以注 入含氫氧化鈉之驗劑2 3來調整其pH至1 0.3。然後，於絮凝 槽2 b中，高分子之絮凝劑2 5被加入，以形成含氫氧化鎂 與重金屬氫氧化物之粗絮凝物。高分子絮凝劑2 5，可使用 如聚丙烯醯胺之陽離子絮凝劑。含此類絮凝物之懸浮物被 引入冰殿槽2 c進行固-液分離。所得之上層澄清水（即，經 絮凝沉;殿處理後之水A 12)續已絮凝沉澱步驟β 3處理，同 時絮凝沉;殿之污泥A 12 s續送至厚化步驟5處理。 如圖4所示，絮凝沉澱步驟B3含：絮凝槽3a、反應槽讪 及沉殿槽3 c。 於絮凝槽3a中，60 mg/L之絮凝劑26與1〇〇 mg/L之鐵組 合物（氣化鐵）24被加入已經絮凝沉殿處理後之水A 12中。 -15- 本紙張尺廋適用中國國家標,(「NS ) Μ規格（210'/297公着厂-- -----------衣------訂 (請先閱讀背面之注意事項再填寫本頁) 412433 A7 _______B7 五、發明説明（13) -I -- Ϊ— - I -- - I I - n n n I (請先閲讀背面之注意事項再填寫本頁〕 然後，以礦物酸（鹽酸）2 2輔助劑（氫氧化鈉）2 3輔助調整 至pH 7.4。再之後於反應槽3 b中，加入高分子絮凝劑2 5以 形成含重金屬成份之氫氧化鐵粗絮凝物。如絮凝劑2 6使用 Epofloc L-l (Miyoshi Oil & Fat Co·，Ltd.製造）。鐵組合物 2 4可使用硫酸鐵或類似物以取代氣化鐵。含這些絮凝物之 懸浮物引入沉澱槽3 c進行固-液分離。所得之上層潑清液 (即已經絮凝沉澱處理後之水B 13)續以沙濾步驟7處理， 同時絮凝沉澱之污泥B 13s被送至厚化步驟5處理之。 絮凝沉澱之污泥A 12s與絮凝沉澱之污泥B 13s被引入厚 化步驟5，厚化器結合並允許於其t沉澱。因此之結果污 泥濃度由1到2 %童量被提升至5 %重量。厚化後被分離出 來的水15 w回到絮凝沉澱步驟A 2，同時厚化後的污泥15s 更進一步於脱水步驟6中脱水然後以濾餅16 s排出本系統 之外。厚化後的污泥15 s以壓縮機當成脱水器來脱水，可 得到含水量不大於70%重量的濾餅。被移除的水16w回到 絮凝沉澱步驟A 2。 在沙濾步驟7中，由絮凝沉澱步驟B 3排放來的上澄清液 (即經絮凝沉澱步驟處理後之水B 13)流經以沙爲介質的單 層沙濾器。此上澄清液殘留的固體物質被分離並移去。然 而，可理解此處並不限沙濾法，常用之快速壓濾法亦可被 使用。本步驟中，濾床之形式（即，單層或多層）可考慮懸 浮物之性質（如：粒徑）來決定之。更者，所用之濾介質可 由沙 '砂礫、無煙煤與相似之物中選出適用之物。流經濾 床之沙濾後的水1 7移至後續之活性碳吸附步驟8並處理 -16- •才中國國家標>Λ4· g〇x297公釐) ~ A7 B7 412433 五、發明説明（14) 之。 連續床被前懸浮物阻塞時，以水逆洗滤床以 1^--------表------訂 {請先閱讀背面之注意事項再填寫本頁) ’、，屯積之懸浮物固體。逆洗磨水17w回到絮凝沉殿步驟 A 2並處理之。 :在活性碳吸时驟8中，沙隸之廢水17流經含有粒狀 活性碳床（塡无塔（未示出）。則由工業廢水所造成之有機 咖成份可藉吸附至活性碳多半被移除。所用之活性碳可 爲粒狀或粉狀。 當活性碳床行連續吸附處理時被雜質所阻塞時，以水逆 洗活性碳床以移除這些雜質。逆洗之廢水1 8 w回到絮凝沉 澱步驟A 2。 經活性碳吸附處理後由活性碳處理步驟8所排出之水調 整其pH至7.0。則可得最終處理後之水18。 範例2 (第二種虛理裎庠、 ^"~郐中欢"4^只1消於合竹"4*,!^ 圖5說明範例2 (第二種處理程序）之各步驟。如圖5所 示’範例2的程序包括酸分解步驟1、絮凝沉澱步驟c 4、 沙遽步驟7與活性碳吸附步騍8。脱硫廢水1 0可成功地依 這些步驟處理。再者，這些步驟更可加上厚化步驟5與脱 水步騾6以處理絮凝沉澱步驟c 4產生之污泥。 範例2中，以絮凝沉澱步驟C 4來取代範例1中所使用的 絮凝沉澱步驟A 2與絮凝沉澱步驟B 3。 與範例1相似，脱硫廢水1 0由作爲燃燒重油生成廢氣之 處理所用的脱硫系统排出，並被引進酸分解步驟1中’以 分解廢水中的連二硫酸及N-S成份。之後’此已經酸分解 -17- 本紙張尺度洎用肀國围家標蜱（rNS ) Λ4規格（210X297公釐） 412433 at 一 ____B7 五、發明説明（15) 處理之水1 1引至絮凝沉澱步驟C 4。 如圖6所示’此絮凝沉澱步驟c 4包含反應槽4 a、pH調整 槽4 b、絮凝槽4 c及沉澱槽4 d。 反應槽4 a中，60 mg/L之螯合劑（Epofloc L-1 (商標名）； Miyoshi Oil & Fat Co.，Ltd·製造）2 6被加進此已經酸分解處 理之水中1 1。然後，以驗劑（氫氧化鈉）2 3輔助調整pj-j至 8_8以形成含重屬成份之微絮凝物沉澱。之後，於pH調整 槽4 b，100 mg/L的鐵组合物（氣化鐵）2 4被加進PH調整槽 4 b中。然後，藉前述之鹼劑2 3的輔助使pH維持在前述之 値，以形成吸附並含有前述重金量成份之微絮凝物之氫氧 化鐵絮凝物沉澱。隨後，於絮凝槽4 c中，高分子絮凝劑 2 5被加入含有這些絮凝物之懸浮物中，以形成粗絮凝物及 相似之物。最後，含這些絮凝物之懸浮物引至沉澱槽4 d進 行固-液分離。所得之上澄清液（即：已經絮凝沉澱處理之 水C 14)以後續之沙濾步驟7處理。絮凝沉澱污泥C 14s被移 至厚化步驟5繼續處理。 與範例1相似，絮凝沉澱處理後之水C 14成功的於沙濾 步驟7和活性碳吸附步驟8處理，跟著調整pH至pH 7.0。則 可得最終處理之水18。 範例1與範例2所述處理程序之結果列於表1。 -18- 本紙張尺^5^]肀國®家橾-^ ( (，NS > Λ4規栝（210X297公釐） (請先閲讀背面之注項再填寫本頁) i衣. 丁 ，va 412433 A7 _ B7 五、發明説明（16) 表1 未處理之脱硫廢 水之品質 已處理之水的品質 範例1 範例2 溫度 V 49 48 49 PH _ (弱酸性） 7.2 7.1 鎂(Mg) mg/L 11800 3400 5500 T-COD mg/L 170 13 12 s2o6-cod mg/L 80 <10 <10 NS-COD mg/L 50 <10 <10 !孟(Μη) mg/L 40 <10 <10 鎘（Cd) mg/L 0.6 <0.05 <0.05 (註）T-COD : COD成份總量。 S206-C0D ··連二硫酸之量。 NS-COD : N-S成份之量。 -19- t請先閱讀背面之注意事項再填寫本頁) 訂 本紙張尺度適用中國國家標嗱（（’NS ) Λ4規栳（210X297公釐）(4) Flocculation precipitation step C Flocculation precipitation step C is to add a chelating agent to the wastewater after the acid treatment step and adjust the pH of the wastewater to 8 to 10 to form a heavy metal chelate, add an iron composition to the wastewater, and maintain Wastewater is at a pH of 8 to 10 to form a ferric hydroxide flocculent precipitate, and a step of separating the precipitate formed from the ferric hydroxide flocculant and the heavy metal chelate captured by the ferric hydroxide flocculant. As the chelating agent, the same chelating agent used in the aforementioned flocculation precipitation step B can be used. Chelating agents are usually used in quantities of 10 to! , 0.00 mg / L. The pH adjustment can be assisted by alkaline agents (such as sodium hydroxide), and mineral acids (such as hydrochloric acid) can be used if necessary. When the wastewater is adjusted to a pH of 8 to 10, the microflocculants cause a large amount of cadmium to be captured. This iron composition can be the same as used in the aforementioned flocculation precipitation step B. This iron composition is usually used in an amount of about 100 to 500 mg / L of iron. This wastewater can be maintained at a pH of 8 to 10 by adding an alkaline agent (such as: sodium hydroxide). When the pH of the wastewater is maintained at 8 to 10, the same reaction as in the aforementioned flocculation and precipitation step (B) occurs to precipitate flocs of iron hydroxide. The aforementioned microflocculant-12- Rule of this paper, 1¾¾: material (rNS) Λ4 gauge 297 mm) 412433 A7 V. Description of the invention (10) and any uncaptured heavy metals (such as: ^ is adsorbed and contains _ Endogenous matter, Shen Dian. In this step, the same high-molecular flocculant as in the previous flocculation and sedimentation step is used to form coarse flocs and increase the sedimentation of solid materials separated in the floc-containing suspension The inside of the hall is separated, and the upper clarified liquid formed is continued in the following steps (that is, the sand filtration step in the second type of processing procedure). (5) The thickening step is processed by thickening step # 中 '由 第 _ # The flocculation and sedimentation process of the process is forged A and B, and the flocculation and sedimentation process of the second treatment process is used. The wastewater / depleted sludge is concentrated by a thickener and the solids are separated and discharged. The sludge concentration is usually concentrated by 1 to 2% by weight is increased to 5% by weight after the thickening step. The separated water is returned to the previous step (the flocculation sedimentation step A in the first processing procedure and the flocculation sedimentation step in the second processing procedure) c), and then re-treated with the wastewater from the acid decomposition step. Sludge (6) In the dewatering step, the 'concentrated sludge is dewatered by a dehydrator and discharged as a cake. In this step, a filter press, a belt press, a spiral decanter, or ^ Similar objects can be used as dehydrators. For example, if a filter press is used, the moisture content of the sludge can be reduced to not more than 70% by weight. (7) The sand filtration step is used in the sand filtration step ' From the flocculation sedimentation step B of the first processing procedure, or from the flocculation sedimentation step C of the second processing procedure, the suspended matter remaining in the upper layer and the green liquor is separated and removed by sand filtration treatment. -13- This paper uses the Chinese standard ((, NS) Λ4 size (2) 0 × 297 mm) (谙 Please read the precautions on the back before filling this page) 'yi.11 No. 87113497 Revised page of the Chinese manual for the village application (December 88) A7 B7 V. Description of the invention (repaired X 11 The consumer cooperation of the Central Standards Bureau of the Ministry of Economic Affairs Du printed sand filter steps used in the filter bed can be used, for example: 300 mm support grit Layer, 600 mm sand layer, and 600 mm anthracite seam. It is commonly used The linear velocity (LV) ranges from 7 to 15 m / h. (8) The activated carbon adsorption step is introduced into the activated carbon adsorption step through the sand> condensation step, in which the water flows through the activity in the packed tower. Carbon bed. In this step, most of the organic COD components caused by industrial wastewater can be removed by adsorption to activated carbon. The activated carbon is treated as the final treated water, which can be discharged or reused. Example 1 (the first treatment process 庠) Example 1 is illustrated in Figure 1. As shown in Figure 1, this procedure is used to treat waste gas desulfurization wastewater 'which includes: acid decomposition step 1, flocculation sedimentation step A 2, flocculation sedimentation Step B3, sand filtration step 7 such as activated carbon adsorption step 8. The desulfurized waste water 10 is successfully processed in these steps. Furthermore, these steps can be combined with thickening step 5 and dehydration step 6 to treat the sludge produced by flocculation sedimentation step A 2 and flocculation sedimentation step B 3. This procedure is described in detail below. _ / First, the desulfurization wastewater 10 discharged from the desulfurization system for treating heavy oil combustion exhaust gas is introduced into the acid decomposition step 1. As shown in the figure, this acid decomposition snail J includes: a mineral acid mixing tank 1 a, a steam mixing tank 1 b, a decomposition tank 1 c, and a neutralization tank 1 d. In the mineral acid mixing tank 1a, a mineral acid (hydrochloric acid) 2 2 is added to the desulfurization wastewater 10. Hydrochloric acid was added and mixed to a given concentration of 0.2% by weight. After mixing, the pH of the wastewater becomes 2 or lower. Then, in the steam mixing tank 1 b, the waste water-14 paper size is applicable to the Chinese National Standard (CNS) A4 specification (2tOX 297 mm) ^^^ 1 d It HF — tt ^^ im · ^ n ^ — ^ ^^ 1 ^^^ 1 ^^^ 1— * 3., 1 '(Please read the note on the back before filling this page) ^ 12433 A7 " 一' _ B7 _ _ V. Description of the invention (12 ) Heat with steam 2 1 until 9 5 ° C. After that, the waste water was introduced into the decomposition tank 1 c while maintaining the temperature and reacted therein for 2 hours. The aforementioned hydrochloric acid concentration, reaction temperature, and reaction time are those found in the series of experimental results based on this processing procedure that can effectively decompose its COD component. After the disulfuric acid and N-S components are decomposed in this operation, the wastewater is introduced into the neutralization tank for 1 d, and the pH has been adjusted with an alkali agent 2 3 to a preset neutralization level (ie, about 7). Alkali agent 2 3, sodium hydroxide is used because it is impossible to form any solid matter. The preset neutralization is not only to protect the equipment used in the next step, but also to facilitate the pH adjustment of the next stage, because it only needs to adjust a smaller range. The wastewater is treated with acid flocculation and sedimentation step A2. As shown in FIG. 3, the flocculation sedimentation step A2 includes: a pH adjustment tank 2a, a flocculation tank 2b, and a sink; and a temple tank 2c. In the pH adjusting tank 2a, the wastewater having been subjected to acid decomposition treatment 1 is adjusted to a pH of 10.3 by injecting sodium hydroxide-containing test agent 23. Then, in the flocculation tank 2b, a polymer flocculant 25 is added to form a coarse flocculant containing magnesium hydroxide and a heavy metal hydroxide. As the polymer flocculant 25, a cationic flocculant such as polyacrylamide can be used. Suspensions containing such floes were introduced into the ice hall 2c for solid-liquid separation. The obtained upper clear water (i.e., flocculation and sedimentation; water A 12 after the treatment of the temple) is further subjected to the flocculation and sedimentation step β 3, and is simultaneously flocculated and settled; the temple sludge A 12 s is continuously sent to the thickening step 5 for treatment. As shown in FIG. 4, the flocculation sedimentation step B3 includes a flocculation tank 3a, a reaction tank 讪, and a sink chamber 3c. In the flocculation tank 3a, 60 mg / L of the flocculant 26 and 100 mg / L of the iron composition (gasified iron) 24 were added to the water A 12 which had been treated by the flocculation sink. -15- The size of this paper is applicable to the national standard of China, ("NS" M specifications (210 '/ 297 public works factory -------------- clothing ------ order) Read the notes on the back and fill in this page) 412433 A7 _______B7 V. Description of the invention (13) -I-Ϊ--I--II-nnn I (Please read the notes on the back before filling this page] Then, Mineral acid (hydrochloric acid) 2 2 auxiliary agent (sodium hydroxide) 2 3 was used to adjust the pH to 7.4. Then, in the reaction tank 3 b, a polymer flocculant 25 was added to form a coarse flocculation of iron hydroxide containing heavy metal components. For example, Epofloc Ll (manufactured by Miyoshi Oil & Fat Co., Ltd.) is used as the flocculant 26. Iron composition 24 can be replaced with iron sulfate or the like. Suspended matter containing these flocculants is introduced. The sedimentation tank 3c is subjected to solid-liquid separation. The obtained upper layer of liquid (ie, the water B 13 that has been flocculated and precipitated) is continuously treated with the sand filtration step 7, and the flocculated and precipitated sludge B 13s is sent to the thickening step. 5 treatment. The flocculated sediment sludge A 12s and the flocculated sediment sludge B 13s are introduced into the thickening step 5. The thickener is combined and allowed to settle at t. As a result, the sludge concentration was increased from 1 to 2% to 5% by weight. The separated water 15 w returned to the flocculation sedimentation step A 2 after thickening, and the thickened sludge 15s was further dehydrated. Dehydration in step 6 is then discharged out of the system with filter cake 16 s. Thickened sludge 15 s is dewatered with a compressor as a dehydrator to obtain a filter cake with a water content of not more than 70% by weight. The water 16w returns to the flocculation sedimentation step A 2. In the sand filtration step 7, the upper clarified liquid discharged from the flocculation sedimentation step B 3 (that is, the water B 13 after the flocculation sedimentation step) flows through the sand-containing medium. Sand filter. The solids remaining in the clear liquid are separated and removed. However, it is understood that the sand filtration method is not limited here, and the commonly used rapid pressure filtration method can also be used. In this step, the form of the filter bed (Ie, single or multiple layers) can be determined by considering the nature of the suspended matter (such as particle size). Furthermore, the filter medium used can be selected from sand, gravel, anthracite, and the like. Flow through the filter The sand filtered water 17 of the bed is moved to the subsequent activated carbon adsorption step 8 and treated -16- • China National Standard > Λ4 · g〇x297 mm) ~ A7 B7 412433 V. Description of the invention (14). When the continuous bed is blocked by the front suspension, the filter bed is backwashed with water to 1 ^- ------- Table ------ Order {Please read the precautions on the back before filling this page) ',, the suspended solids accumulated. Backwash mill water 17w back to the flocculation sink hall step A 2 and deal with it. : In step 8 of activated carbon adsorption, the waste water 17 of the sand cherries flows through the bed containing granular activated carbon (without a tower (not shown). Organic coffee components caused by industrial wastewater can be adsorbed to activated carbon by most Removed. The activated carbon used can be granular or powdery. When the activated carbon bed is blocked by impurities during continuous adsorption treatment, the activated carbon bed is backwashed with water to remove these impurities. Wastewater from backwashing 1 8 w Return to the flocculation precipitation step A 2. After the activated carbon adsorption treatment, the water discharged from the activated carbon treatment step 8 adjusts its pH to 7.0. The final treated water 18 can be obtained. Example 2 (Second virtual treatment)庠, ^ " ~ 郐 中 欢 " 4 ^ only 1 disappears in harmony " 4 *,! ^ Figure 5 illustrates the steps of Example 2 (the second processing procedure). As shown in Figure 5, 'Example 2 The procedure includes acid decomposition step 1, flocculation sedimentation step c 4, sandy step 7 and activated carbon adsorption step 8. Desulfurization wastewater 10 can be successfully treated according to these steps. Furthermore, these steps can be added with thickening steps 5 and dehydration step 6 to treat the sludge produced in the flocculation sedimentation step c 4. In Example 2, the flocculation sedimentation step C 4 is used. Instead of the flocculation sedimentation step A 2 and flocculation sedimentation step B 3 used in Example 1. Similar to Example 1, the desulfurization wastewater 10 is discharged from the desulfurization system used for the treatment of exhaust gas from burning heavy oil, and is introduced into the acid decomposition step 1 'To decompose dithionic acid and NS components in wastewater. After this' has been acid-decomposed -17- This paper size uses the national standard tick (rNS) Λ4 specification (210X297 mm) 412433 at ____B7 V. Description of the invention (15) The treated water 11 is led to the flocculation sedimentation step C 4. As shown in FIG. 6 'this flocculation sedimentation step c 4 includes a reaction tank 4 a, a pH adjustment tank 4 b, a flocculation tank 4 c, and a sedimentation tank 4 d. In the reaction tank 4a, 60 mg / L of chelating agent (Epofloc L-1 (trade name); Miyoshi Oil & Fat Co., Ltd.) 2 6 is added to the water which has been subjected to acid decomposition treatment 1 1. Then, use the test agent (sodium hydroxide) 2 3 to help adjust pj-j to 8_8 to form microflocculation precipitates containing heavy components. After that, in a pH adjustment tank 4 b, 100 mg / L iron composition (Gasified iron) 2 4 is added to the pH adjusting tank 4 b. Then, the pH is adjusted by the aid of the aforementioned alkali agent 2 3 Hold the above-mentioned maggots to form iron hydroxide flocculent precipitates that adsorb and contain the micro-flocculants of the aforementioned heavy gold content. Then, in a flocculation tank 4c, a high-molecular flocculant 25 is added to the suspension containing these flocculants In order to form coarse flocs and similar materials, finally, the suspensions containing these flocs are led to a sedimentation tank for 4 d for solid-liquid separation. The resulting clear liquid (ie, water C 14 which has been flocculated and precipitated) ) Follow the subsequent sand filtration step 7. The flocculated sediment sludge C 14s is moved to the thickening step 5 to continue processing. Similar to Example 1, the water C 14 after the flocculation precipitation treatment was successfully treated in the sand filtration step 7 and the activated carbon adsorption step 8 and then adjusted to pH 7.0. The final treated water 18 is obtained. The results of the processing procedures described in Examples 1 and 2 are shown in Table 1. -18- This paper ruler ^ 5 ^] ® 国 ® 家 橾-^ ((, NS > Λ4 gauge (210X297 mm) (Please read the note on the back before filling this page) i clothing. Ding, va 412433 A7 _ B7 V. Description of the invention (16) Table 1 Quality of untreated desulfurized wastewater Quality of treated water Example 1 Example 2 Temperature V 49 48 49 PH _ (weak acidity) 7.2 7.1 Magnesium (Mg) mg / L 11800 3400 5500 T-COD mg / L 170 13 12 s2o6-cod mg / L 80 < 10 < 10 NS-COD mg / L 50 < 10 < 10! Meng (Μη) mg / L 40 < 10 < 10 Cadmium (Cd) mg / L 0.6 < 0.05 < 0.05 (Note) T-COD: the total amount of COD components. S206-C0D ·· the amount of even disulfuric acid. NS-COD: the amount of NS components.- 19- t Please read the notes on the back before filling in this page) The size of the paper used for this edition applies to the Chinese national standard (('NS) Λ4 Regulations (210X297 mm)