201245054 • ·. * 六、發明說明： 【發明所屬之技術領域】 本發明含重金屬鹼性污泥資源化處裡方法，係屬環境保護技術領域， 為一具體可行將含重金屬驗性污泥資源化處理之方法。 【先前技術】 隨著工業的發展，含重金屬污泥之產量每年增加，而此些含重金屬污 泥之主要來源為電鍍業與印刷電路板製造業，以及其他製程中使用重金屬 之工業，其所含重金屬可包含鉻、鐵、鎳、銅、鋅、錯、録與汞等，以及 可溶性鹽類。 通常含重金屬廢水之處理方法，如含有六價鉻，會先以還原劑將六價 鉻還原成三價路，再以鹼中和後’得到含重金屬之鹼性污泥；若是處理電 鑛業之含重金屬廢水，一般則常見燒驗沉澱法與石灰沉澱法，其中燒驗沉 澱法成本較高，但污泥量少，處理污泥等後續問題較容易，而石灰沉澱法 雖然成本低，但污泥量大，處理污泥問題較為棘手。而不論何種行業之污 泥，產出後均以水泥等固化劑固化後，以衛生掩埋作為最終處置方法，此 一模式不僅處理成本高，浪費土地資源，亦將污泥中之重金屬資源完全浪 費，且含有重金屬二次溶出造成二次污染之風險，不符合現代資源用續再 利用之環保處理方式。 然而污泥中各種重金屬組成複雜’且單一金屬濃度往往偏低，如前述 電錄業以石灰沉澱法處理’則會產生大量含重金屬之硫酸約（CaS〇4)，污泥 量相當大’但當中所含重金屬濃度卻相對偏低，因此若要能妥善資源回收 再利用，確實需要相當之技術。 201245054 Λ 近來電錢污减理技術，已贿從無害化轉換朗時考慮無害化與資 源化’目前常㈣是氨喊法，錢水將污泥中__等錢溶出'，、而 難處理的鐵與鉻仍存污泥中。氨回收法之處理程序繁複，且僅能分離 出銅鋅鎳之混合金屬，若欲得到單一金屬，還需以其他方法進行分離，且 氣浸液之液固比相當大’達到12:1，因此需要相當大容積之設備進行處理， 成本甚高，另外浸出造量亦高，可達原始污泥量之5〇%，渣中仍含絡等重金 屬，還需進一步無害化或資源化處理，整體而言實用性欠佳大量推廣不 易。 因此必須採用-套既能集中處理，同時能系統化進行資源綜合利用之 新技術，將所有不同組成之含重金屬電鑛污泥，進行資源化處理和綜合利 用，使之全部資源化而不再產生二次污染。 【發明内容】 本發明一種含重金屬鹼性污泥資源化處裡方法，其處理石灰驗性污泥 的方法是先用硫酸溶液溶解含重金屬鹼性污泥，分離出含氧化石夕（Si〇2)的 酸不溶物，再以超音波處理酸溶液’使重金屬離子與氫氧化鈣脫離，然後 加鹼，以控制溶液之pH值’使硫酸辦(CaS〇4)沉澱分離，處理氫氧化納（Na〇H) 鹼性污泥沒有分離硫酸鈣（CaS〇4)之問題，固液分離可以得到重金屬之液 體部分以及含硫酸弼（CaS〇4)固體部分’液體部分先用硫酸亞鐵處理，使 重金屬離子均勻分布在硫酸亞鐵溶液中，再加鹼調整pH值為8〜9，通入壓 縮空氣氧化，部分亞鐵形成鐵，最後形成鐵氧晶體，並製成具有多種用途 之添加料。固體部分中的硫酸#5(CaS0〇,作為製水泥以及石膏板之添加料。 201245054 硃 ·. 提供-鑛含重金屬污泥資源化之處理方法，使之全部麵化，而無 產生二次污染之問題，包括步驟如下： 步驟1 :超音波處理。 用10〜30%硫酸溶液溶出含重金屬鹼性污泥中含有重金屬。如含重金 屬驗性污泥為含重金屬之石灰污泥，經固液分離後，會有含氧化石夕 (Si〇2)之酸浸渣以及酸浸液b，如含重金屬鹼性污泥為含重金屬 之氫氧化鈉（NaOH)污泥，即無酸浸渣，僅有酸浸液a ; 所得之酸浸液A或酸浸液B，處理時間為2〜30分鐘，反應溫度 為30〜80°C，超音波之頻率為20~500KHz。 步驟2 :酸侵液B加入驗溶液，使固、液分離。 將重量百分》農度為5~30%之驗溶液加入，如是含重金屬之石灰污泥 所得之酸浸液B中，控制溶液之PH值介於1. 〇〜3. 〇，硫酸鈣（CaS〇4) 會沉澱分離，固液分離後，可得液體部分B和固體部分硫酸鈣 (CaS〇4) 〇 步驟3:液體部分B加入硫酸亞鐵溶液，得液體部分c ; 固體部分硫酸鈣（CaSOO則，步驟1的氧化矽（si〇〇酸浸渣及 步驟3的硫酸鈣（CaS〇4)混和脫水。 液體部分B加入重量百分濃度1〇〜30%之硫酸亞鐵溶液，加入量 以硫酸亞鐵(FeS04).硫酸辞（7也0 )乾基計算，為重金屬離子總 量的15〜30倍，酸性條件下反應15〜30分鐘，得液體部分c ; 所得到的固體部分，和步驟(1)的含氧化矽（Si〇2)酸浸潰，以 及步驟(3)的硫酸妈（CaSOO脫水混合後’可製成水泥添加料，或 是石膏板添加料；如是含重金屬之氫氧化鈉（NaOH)污泥，就沒 有含氧化矽（Si〇2)酸浸渣和硫酸釣（CaSOO (硫酸鈣渣），可直 接加入硫酸亞鐵製成鐵氧晶體。 步驟4:液體部分c加入驗液，形成含重金屬的鐵氧晶體。 將重量百分濃度5〜30%之鹼液加入步驟(4)處理後之液體部分c，並 控制溶液之pH值介於8〜9之間，反應溫度50~9(TC，用通壓縮空氣 方式，將1/3〜2/3之二價鐵氧化成三價鐵，氣液比為2〜8:1，反應 201245054 時間為20分鐘〜2小時，形成含重金屬的鐵氧晶體β 有關本發明之詳細說明及技術内容，現配合圖式說明如下： 【實施方式] 請參閱第1騎示，圖中見悉，係本發明—種含重金屬驗性污泥資源 化處裡方法之步驟流程，首歧行Α步驟1 :『超音波處理』； 用10〜30%硫酸溶液溶出含重金屬鹼性污泥中含有重金屬。如含重金屬 驗性污泥騎重金屬之石灰污泥，_液分離後，會有含氧切⑶⑹之 酸和查以及酸浸液B，如含重金屬紐污泥為含重金屬讀氧化納（議） 污泥，即無酸浸渣，僅有酸浸液Λ ; 所得之酸浸液Α或酸浸液Β，處理時間為2〜30分鐘，反應溫度為 30〜8(TC，超音波之頻率為2〇~500KHz。 再進行B步驟2 :『酸侵液B加入鹼溶液，使固、液分離』； 將重量百为濃度為5~30%之驗溶液加入，如是含重金屬之石灰污泥所得 之酸浸液B中，控制溶液之pH值介於L 〇〜3· 〇，硫酸的（CaS〇4)會沉澱分 離，固液分離後，可得液體部分B和固體部分硫酸約（CaS〇4); 再進行C步驟3 :『液體部分B加入硫酸亞鐵溶液，得液體部分c ;固 體部分硫酸#5 (CaS〇4)則’步驟1的氧化矽（si〇2)酸浸渣及步驟3的硫 酸舞（CaS〇4)混和脫水』； 液體部分B加入重量百分濃度1〇〜30%之硫酸亞鐵溶液，加入量以硫酸 亞鐵(FeS04) ·硫酸鋅（7迅0 )乾基計算，為重金屬離子總量的15~30倍， 酸性條件下反應15〜30分鐘，得液體部分c;所得到的固體部分，和步驟（1) 的含氧化矽（SiOO酸浸渣，以及步驟⑶的硫酸弼（cas〇4)脫水混合後， 可製成水泥添加料，或是石膏板添加料；如是含重金屬之氫氧化鈉（Na0H) 污泥，就沒有含氧化矽（SiOz)酸浸渣和硫酸弼（CaSOO (硫酸鈣渣），可 201245054 直接加入硫酸亞鐵製成鐵氧晶體； 而進^ D步驟4 :『液體部分C加入驗液，形成含重金屬的鐵氧晶體』； 將重量百分濃度5〜30%之驗液加入處理後之液體部分c，並控制溶液之 pH值介於8〜9之間，反應溫度50~9(rc，用通壓縮空氣方式，將1/3〜2/3 之二價鐵氧化成三傾’氣祕為2〜8:卜反糾間為2Q分鐘~2小時，形 成含重金屬的鐵氡晶體。 然，處理電鑛業含重金屬廢水最常用之方法是加入氫氧簡或氫氧化 納，使廢水中重金屬生成氫氧化物’形成含重金屬污泥沉澱，因此一般而 言，處理時採用稀酸特別是稀硫酸脉解污泥當中所含之有價重金屬，如 果以稀硫酸溶解電鍍污泥，其溶解反應如下：201245054 • ·· * VI. Description of the invention: [Technical field of invention] The method for recycling heavy metal alkaline sludge in the invention belongs to the technical field of environmental protection, and is a specific feasible and feasible crude sludge-containing sludge resource. The method of processing. [Prior Art] With the development of industry, the output of heavy metal-containing sludge is increasing every year, and the main sources of such heavy metal-containing sludge are electroplating industry and printed circuit board manufacturing, as well as industries using heavy metals in other processes. The heavy metals may include chromium, iron, nickel, copper, zinc, erroneous, recorded and mercury, and soluble salts. Generally, the treatment method of heavy metal-containing wastewater, such as containing hexavalent chromium, firstly reduces the hexavalent chromium to a trivalent road with a reducing agent, and then neutralizes the alkali to obtain an alkaline sludge containing heavy metals; In the case of heavy metal-containing wastewater, it is common to use the precipitation method and the lime precipitation method. The method of burning and sedimentation is costly, but the amount of sludge is small, and subsequent problems such as sludge treatment are easier, while the lime precipitation method is low in cost but dirty. The amount of mud is large, and the problem of sludge treatment is more difficult. Regardless of the sludge of any industry, after curing with cement and other curing agents, the sanitary burial is used as the final disposal method. This model not only has high processing cost, wastes land resources, but also completes heavy metal resources in the sludge. Waste, and the risk of secondary pollution caused by secondary dissolution of heavy metals, does not meet the environmental treatment of modern resources for continued reuse. However, the composition of various heavy metals in the sludge is complex and the concentration of single metal tends to be low. If the above-mentioned electro-recording industry is treated by lime precipitation method, a large amount of heavy metal-containing sulfuric acid (CaS〇4) will be produced, and the amount of sludge is quite large. The concentration of heavy metals contained in them is relatively low, so if you want to properly recycle and reuse resources, you need a considerable amount of technology. 201245054 Λ Nearly call for money pollution reduction technology, has been considered harmless and resourceful when it comes to harmless conversion. At present, (four) is ammonia shouting method, money water will dissolve the sludge in the __ and other money, and it is difficult to handle The iron and chromium are still stored in the sludge. The ammonia recovery method has complicated processing procedures and can only separate the mixed metal of copper, zinc and nickel. If a single metal is to be obtained, it needs to be separated by other methods, and the liquid-solid ratio of the gas immersion liquid is relatively large, reaching 12:1. Therefore, a considerable volume of equipment is required for processing, the cost is very high, and the leaching capacity is also high, up to 5% of the original sludge amount, and the slag still contains heavy metals such as collateral, and further harmless or resource treatment is required. Overall, the lack of practicality is not easy to promote. Therefore, it is necessary to adopt a new technology that can not only concentrate on processing, but also systematically carry out comprehensive utilization of resources, and resource-process and comprehensively utilize all heavy metal-containing ore sludges of different compositions to make them fully resourced. Produce secondary pollution. SUMMARY OF THE INVENTION The present invention relates to a method for recycling a heavy metal alkaline sludge. The method for treating lime sludge is to first dissolve a heavy metal alkaline sludge with a sulfuric acid solution, and separate the oxide containing oxidized stone (Si〇). 2) The acid insoluble matter is treated by ultrasonic treatment of the acid solution 'the heavy metal ion is separated from the calcium hydroxide, and then the alkali is added to control the pH value of the solution to precipitate the sulfuric acid (CaS〇4), and the sodium hydroxide is treated. (Na〇H) Alkaline sludge does not have the problem of separating calcium sulfate (CaS〇4). Solid-liquid separation can obtain liquid part of heavy metal and solid part containing barium sulfate (CaS〇4). Liquid part is treated with ferrous sulfate first. The heavy metal ions are evenly distributed in the ferrous sulfate solution, and the alkali is adjusted to have a pH of 8 to 9. The compressed air is oxidized, part of the ferrous iron is formed into iron, and finally ferrite crystals are formed, and the additive is prepared for various uses. . Sulfuric acid #5 (CaS0〇 in the solid part, as an additive for cement and gypsum board. 201245054 Zhu·. Providing a treatment method for the recycling of heavy metal sludge containing ore, so that it is fully surfaced without secondary pollution The problem includes the following steps: Step 1: Ultrasonic treatment. Dissolve heavy metal containing heavy metals in 10~30% sulfuric acid solution. For example, heavy metal containing sludge is a heavy metal-containing lime sludge, solid-liquid After separation, there will be acid leaching slag containing oxidized stone (Si〇2) and acid leaching liquid b. For example, the heavy metal-containing alkaline sludge is a heavy metal-containing sodium hydroxide (NaOH) sludge, that is, no acid leaching residue. Only the acid immersion liquid a; the obtained acid immersion liquid A or the acid immersion liquid B, the treatment time is 2 to 30 minutes, the reaction temperature is 30 to 80 ° C, and the frequency of the ultrasonic wave is 20 to 500 kHz. Step 2: Acid attack Liquid B is added to the test solution to separate the solid and liquid. Add the test solution with the weight percentage of 5~30%, such as the acid immersion liquid B obtained from the lime sludge containing heavy metals, and control the PH value of the solution. 1. After 〇~3. 〇, calcium sulphate (CaS〇4) will precipitate and separate, after solid-liquid separation, the available liquid Body part B and solid part calcium sulphate (CaS 〇 4) 〇 Step 3: Liquid part B is added to the ferrous sulphate solution to obtain liquid part c; solid part of calcium sulphate (CaSOO, step 1 of cerium oxide (si bismuth leaching) The slag and the calcium sulfate (CaS〇4) in step 3 are mixed and dehydrated. The liquid portion B is added to a ferrous sulfate solution having a concentration of 1 〇 30% by weight, and the amount is added with ferrous sulfate (FeS04). The dry basis calculation is 15 to 30 times the total amount of heavy metal ions, and the reaction is carried out under acidic conditions for 15 to 30 minutes to obtain a liquid portion c; the obtained solid portion, and the cerium oxide containing the step (1) (Si〇2) Acid leaching, and the sulfuric acid mother of step (3) (after CaSOO dehydration mixing can be made into cement additive or gypsum board additive; if it is heavy metal sodium hydroxide (NaOH) sludge, there is no cerium oxide (Si〇2) acid leaching residue and sulfuric acid fishing (CaSOO (calcium sulphate slag), which can be directly added into ferrous sulfate to form ferrite crystals. Step 4: Liquid part c is added to the test liquid to form ferrite crystals containing heavy metals. Adding 5 to 30% by weight of the alkali liquid to the liquid portion c after the treatment of the step (4), and The pH value of the solution is between 8 and 9, and the reaction temperature is 50 to 9 (TC, 3% to 2/3 of ferrous iron is oxidized to trivalent iron by means of compressed air, and the gas-liquid ratio is 2 ~8:1, reaction 201245054 time is 20 minutes to 2 hours, forming a ferrite crystal containing heavy metal β. The detailed description and technical contents of the present invention are as follows: [Embodiment] Please refer to the first riding As shown in the figure, the present invention is a step-by-step process of a method for the determination of a heavy metal-containing laboratory sludge, the first step of the operation: "ultrasonic treatment"; the dissolution of the heavy metal base with 10 to 30% sulfuric acid solution The sludge contains heavy metals. For example, if heavy metal test sludge is used to ride heavy metal lime sludge, after _ liquid separation, there will be oxygen cut (3) (6) acid and check and acid immersion liquid B, such as heavy metal new sludge for heavy metal containing sodium oxide (review) Sludge, that is, no acid leaching residue, only acid leaching liquid; obtained acid leaching liquid or acid leaching liquid, the treatment time is 2~30 minutes, the reaction temperature is 30~8 (TC, the frequency of ultrasonic wave is 2〇~500KHz. Then proceed to step B2: “Aciding liquid B to add alkali solution to separate solid and liquid”; adding a test solution with a weight of 5~30%, such as lime sludge containing heavy metals. In the acid immersion liquid B, the pH of the control solution is between L 〇 〜 3 · 〇, and the sulphuric acid (CaS 〇 4) is precipitated and separated, and after the solid-liquid separation, the liquid portion B and the solid portion of the sulfuric acid are obtained (CaS 〇 4); Then proceed to C step 3: "Liquid part B is added to the ferrous sulfate solution to obtain liquid part c; solid part sulfuric acid #5 (CaS〇4) is 'Step 1 of cerium oxide (si〇2) acid leaching residue and Step 3 of the sulfuric acid dance (CaS〇4) mixed dehydration 』; liquid part B is added to the weight percentage concentration of 1 〇 30% ferrous sulfate solution, the amount added Ferrous acid (FeS04) · Zinc sulfate (7 x 0) dry basis calculation, 15 to 30 times the total amount of heavy metal ions, 15 to 30 minutes under acidic conditions, the liquid part c; the obtained solid part, and Step (1) containing cerium oxide (SiOO acid leaching residue, and step (3) of barium sulfate (cas〇4) dehydrated and mixed, can be made into cement additives, or gypsum board additives; such as heavy metal containing sodium hydroxide (Na0H) sludge, there is no cerium oxide (SiOz) acid leaching residue and barium sulphate (CaSOO (calcium sulphate slag), can be directly added to ferrous sulfate to form ferrite crystals in 201245054; and step 4: "liquid Part C is added to the test solution to form a ferrite crystal containing heavy metals"; a liquid concentration of 5 to 30% of the test liquid is added to the liquid portion c after the treatment, and the pH of the solution is controlled to be between 8 and 9, and the reaction is carried out. Temperature 50~9 (rc, using ventilating air, oxidizing 1/3~2/3 of ferrous iron into three-dip's gas secret is 2~8: Bu anti-correction is 2Q minutes~2 hours, forming Heavy metal iron sputum crystals. Of course, the most common method for treating heavy metal containing wastewater in electric mining is to add hydrogen hydroxide or sodium hydroxide. The formation of hydroxides in heavy metals in waste water to form precipitates containing heavy metal sludge. Therefore, in general, the valuable heavy metals contained in the sludge are treated with dilute acid, especially dilute sulfuric acid. If the electroplating sludge is dissolved in dilute sulfuric acid, The dissolution reaction is as follows:
Cu(0H)2 + H2SO4 = CuS〇4 + 2H2OCu(0H)2 + H2SO4 = CuS〇4 + 2H2O
Ni(0H)2 + H2SO4 = NiS〇4 + 2H2O Ζη(0Η)2 + H2SO4 = ZnS〇4 + 2He0Ni(0H)2 + H2SO4 = NiS〇4 + 2H2O Ζη(0Η)2 + H2SO4 = ZnS〇4 + 2He0
Fe(0H)2 + 祕=FeS〇4 + 2H2〇 2Cr(0H)3 + 3 H2SO4 = Cr2(S〇4)3 + 6H2OFe(0H)2 + secret = FeS〇4 + 2H2〇 2Cr(0H)3 + 3 H2SO4 = Cr2(S〇4)3 + 6H2O
Ca(0H)2 + H2SO4 = CaS〇4 j + 2H2O 在-些實例中’所使用之酸液為重量百分濃度為2〇%之硫酸，添加量為石灰 污泥體積之4~8倍。 其中’在A步驟1巾’還可進行獅，以強化溶解效果，麟機之轉 速為20〜60轉/分鐘。 以稀硫酸溶出含重金屬污泥，尤其是電艘石灰污泥，可使其中絕大部 分有價重金屬以離子狀態進人溶出液中，稀硫酸溶出桃石灰污泥之氧化 石M·)渣為6〜7% ’猶浸剌元素組絲看，酸浸拉要成分為氧化 矽（Si〇2)與少量不溶的礦石，因此整個溶出的過程，可使電錄石灰污泥減 量化與無害化。本例中的酸液pH值控制在1· 〇~3. 〇。 201245054 以10〜30%的硫酸溶解含重金屬驗性污泥，使之生成硫酸鈣溶解，重金 屬也同時溶解，用5〜30%鹼液氫氧化鈉（Na〇H)調整pH值為i. 〇〜3. 〇時， 硫酸妈元全>儿版’但重金屬不沉澱’ C步驟3中硫酸1弓（CaS〇4)沉澱物與 酸浸渣中的氧化矽（Si〇2)，混合後可作為水泥廠之添加料，或是石膏板之 添加料。 B步驟2 :利用超音波之能量與震盪，作用於含重金屬硫酸詞鹼性污泥 之酸浸液，使重金屬在酸性條件下，容易與硫酸約（CaS〇4)分離。固液分 離出硫酸鈣後的重金屬溶液，先以硫酸亞鐵在酸性條件下將未還原之六價 鉻還原成三價鉻，其沉澱之pH值為5· 6，鋼沉澱之PH值為6. 8，鋅沉澱的 pH值為7. 9 ’鎳沉澱的pH值為9. 0，但當pH達8~9時，鉻、銅、辞、鎳會 發生共同沉澱。加入的硫酸亞鐵量，以硫酸亞鐵(FeS〇4).硫酸辞（7H2〇 ) 計算，為重金屬離子總量的15〜30倍，酸性條件下反應卜即分鐘，然後再 加5〜30%之鹼液控制，當pH值達8〜9時，通入空氣，將亞鐵(Fe2+)部分氧化 成鐵(Fe3+) ’與W、Of、Zrf、Ni2+共同產生結晶反應形成MFe_代表重 金屬）’為一種具有尖結晶石結構之鐵氧晶體，相當穩定，不會再有二次溶 出情形，反應時間為20分鐘〜2小時，反應溫度為50〜90°C ,處理後水的pH 值和重金屬濃度均可低於排放標準。 鐵氧晶體原料可進-步加工’經脫水乾燥後，使含水量達到卜⑽，粉 碎篩分到8(HGG目，加人磁鐵礦粉中’作為磁性材料添加劑和鐵合金添加 料；如加溫到500〜8〇(TC，粉碎篩分至100〜400目，含水率控制在2 5%， 可製成磁性材料添树、Fe㈣雜獅加料，以及電波魏體材料添加 料，如以超細粉碎機粉碎成咖目以上之微麵料和奈米材料，則可製成 201245054 ♦ % 塗料之添加料，降低成本。 重金屬之鐵氧晶體後之分離液含NazSO4的水溶液，經蒸發濃縮至 30〜60%，並冷卻至常溫(2〇°c)後，硫酸納水溶液（似占〇4)結晶析出，與母 液分離，然後以水洗去殘存母液，再以100〜30(rc熱空氣乾燥，冷卻至常溫 (20°C)後’即成含結晶水硫酸納水溶液（NazS〇4)成品。結晶的母液返送回 硫酸亞鐵溶液中，循環使用。 在一些實例中，本發明之固液分離方式可為板框壓濾、帶式壓濾、真 空吸濾或離心分離’如為離心分離，離心機轉速為2〇〇〇〜6000轉/分鐘。 在一些實例中，硫酸亞鐵溶液為濃度10〜30%之硫酸亞鐵水溶液，或硫 酸清洗鋼板除銹之硫酸亞鐵廢液，更能達到廢棄物再利用之目標，且大幅 降低處理成本。 本發明不僅技術通用範圍廣，適合處理各類含重金屬鹼性污泥，包含 垃圾焚化廠產生之含重金屬灰渣，以及電鍍石灰污泥等，而且技術條件容 易控制，設備簡單，極易大規模推廣，可以大幅降低污泥處理成本，是一 種可以將污泥減量化、無害化與資源化之處理技術；本發明不僅在環境生 態與社會效益上有明顯貢獻，由於處理成本低，本發明亦可在經濟上達到 相當之效益。 請參閱「第2圖」所示，圖中見悉，係本發明一種含重金屬鹼性污泥 資源化處裡方法之處理流程示意圖，含重金屬之電鍍石灰污泥丨輸送到硫 酸混合槽22，同時以水槽21〇中的水將添加之硫酸調整成重量百分濃度為 20%，貯存於硫酸貯槽21中，並將電鍍石灰污泥體積4倍量之酸液，輸送 進入硫酸混合槽22，開動攪拌機’轉速每分鐘30轉，混合時間為3〇分鐘， 201245054 * 並維持於常溫(20°C)，使石灰污泥中與硫酸反應生成的硫酸鈣及重金屬溶 解。 然後以每分鐘3000轉之離心機23進行固液分離，酸不溶物之固體部 分進入酸不溶物貯槽24,液體部分以超音波反應器25進行脫重金屬之震璗 反應，超音波之頻率為20KHz，反應溫度為40°C，反應時間為20分鐘，使 重金屬離子與硫酸約分離，再通入沉澱槽251中，加入鹼液貯槽2510中已 調配好之20%之鹼液氫氧化鈉（NaOH)，並以pH控制儀2511調整鹼液添加 量，使pH維持在2. 7;添加鹼液之目的為使硫酸約沉澱，但重金屬不沉澱， 仍溶解於溶液中。 然後輸送進入離心機23以每分鐘3000轉之離心機23進行固液分離， 固體部分進入沉渣槽230，與酸不溶物24槽中的氧化矽（Si〇2) —併進入 混合機240授拌混合，混合機轉速每分鐘2〇轉，然後經包裝後可運至水泥 廠26，作為水泥添加料。 液體部分則進入鐵氧體反應槽231 ’並加入重量百分濃度2〇%之硫酸亞 鐵溶液211，添加量以硫酸亞鐵(FeS〇4).硫酸鋅（7H2〇 )乾基計算，為重 金屬離子總量的15倍’反應賴1Q分鐘，用加無·加熱至赃，接 著再加入重量百分比2〇%之鹼液212氫氧化納（隨），並以邱控制儀213 調整驗液212添加量，反應時間卜〗、時，接著以空壓機，鼓入空氣，氣 液比控制在1:4 ’形成褐黑色具有尖晶石結構之含重金屬鐵氧晶體，利用離 心機232以每分鐘3〇〇〇轉進行固液分離。 液體部分硫酸鈉水溶液（Na孤）232〇濃度約在通左右， 經二效真空 蒸發濃縮㈣21濃紐約5Q%，趣冷卻^您之冷凝水聊冷卻 201245054 至常溫(2(TC)後，由水槽23240間之結晶器2324將NaaSO4結晶析出，與母 液23241分離，然後以水洗液23243去殘存母液23241，再以100~300°C熱 空氣乾燥，冷卻至常溫(20°C)後，即成含結晶水Nai!S〇4成品，可供製革等行 業使用。結晶的母液23241返送回硫酸亞鐵溶液槽23242中，循環使用， 而洗滌結晶的廢液，可以符合放流水標準，逕行排放23244。 固體部分為含水率約為40%之含重金屬鐵氧晶體233，以流化床乾燥機 234進行乾燥脫水鐵氧晶體234〇，溫度為15阢，使含水率降至脒以内。 乾燥後之鐵氧晶體233以粉碎機2341粉碎成1〇〇目粉末，可作為冶煉鐵合 金添加料2342 ;如以高溫加熱爐235將含重金屬鐵氧晶體233加熱至 8〇〇°C ’並將含水率降至3%，可使晶體重新排列，製成磁性材添加料235卜Ca(0H)2 + H2SO4 = CaS〇4 j + 2H2O In some examples, the acid used was a sulfuric acid having a concentration by weight of 2% by weight, which was added in an amount of 4 to 8 times the volume of the lime sludge. In the 'A step 1 towel', a lion can also be carried out to enhance the dissolution effect, and the speed of the machine is 20 to 60 rpm. Dissolving heavy metal sludge with dilute sulfuric acid, especially electric lime sludge, can make most of the valuable heavy metals enter the human leachate in the ion state, and the sulfuric acid M·) slag of the dilute sulfuric acid dissolving the peach lime sludge is 6 ~7% 'The immersed bismuth element group shows that the acid leaching component is cerium oxide (Si〇2) and a small amount of insoluble ore, so the whole dissolution process can reduce and harmless the electroless lime sludge. The pH of the acid solution in this example is controlled at 1·〇~3. 201245054 Dissolve heavy metal-containing test sludge with 10~30% sulfuric acid, dissolve it into calcium sulfate, dissolve heavy metal at the same time, adjust the pH value with 5~30% alkali sodium hydroxide (Na〇H). ~3. 〇,, the sulfate mother Yuan Quan > children's version 'but the heavy metal does not precipitate' C step 3 in the sulfuric acid 1 bow (CaS 〇 4) precipitate and the leaching of cerium oxide (Si 〇 2) in the acid leaching residue, after mixing Can be used as an additive in cement plants or as an additive to gypsum board. Step B 2: Using the energy and oscillation of the ultrasonic wave, it acts on the acid leaching solution containing the heavy metal sulfate alkaline sludge, so that the heavy metal is easily separated from the sulfuric acid (CaS〇4) under acidic conditions. The heavy metal solution after separating the calcium sulfate by solid-liquid separation, firstly reducing the unreduced hexavalent chromium to trivalent chromium under acidic conditions with ferrous sulfate, the pH of the precipitation is 5.6, and the PH value of the steel precipitate is 6 8. The pH of the zinc precipitate is 7.9. The pH of the nickel precipitate is 9.0, but when the pH reaches 8-9, the chromium, copper, rhodium and nickel will co-precipitate. The amount of ferrous sulfate added is calculated by the ferrous sulfate (FeS〇4). sulfuric acid (7H2〇), which is 15~30 times of the total amount of heavy metal ions, and the reaction condition is minute after the acidic condition, and then 5~30 % alkali control, when the pH reaches 8~9, the air is oxidized to iron (Fe3+) by partial oxidation of Fe (Fe2+) with W, Of, Zrf and Ni2+ to form MFe_ representing heavy metal ' is a ferrite crystal with a sharp crystal structure, quite stable, no secondary dissolution, the reaction time is 20 minutes to 2 hours, the reaction temperature is 50~90 ° C, the pH of the treated water And heavy metal concentrations can be lower than the emission standards. The ferrite crystal raw material can be processed in a step-by-step process. After dehydration and drying, the water content is up to (10), and the pulverization is sieved to 8 (HGG mesh, adding magnetite ore powder) as a magnetic material additive and a ferroalloy additive; Warm to 500~8〇(TC, crushed and sieved to 100~400 mesh, moisture content controlled at 25%, can be made into magnetic material, tree, Fe (four) mixed lion feeding, and electric wave Wei body material additive, such as super When the fine pulverizer is pulverized into micro-fabric and nano-materials above the coffee, it can be made into 201245054 ♦ % coating additive to reduce the cost. The separation liquid of heavy metal ferrite crystals contains NazSO4 aqueous solution and is concentrated to 30 by evaporation. ~60%, and after cooling to normal temperature (2 ° ° C), sodium sulphate aqueous solution (like 〇 4) crystallized, separated from the mother liquor, and then washed with water to remove the mother liquor, and then dried at 100 ~ 30 (rc hot air, After cooling to normal temperature (20 ° C), the finished product containing sodium sulphate solution (NazS 4 ) is crystallized. The mother liquor of the crystal is returned to the ferrous sulfate solution for recycling. In some examples, the solid-liquid separation of the present invention The method can be plate frame pressure filtration, belt pressure filtration, true Suction filtration or centrifugation 'If centrifuged, the centrifuge speed is 2 〇〇〇 to 6000 rpm. In some examples, the ferrous sulfate solution is a ferrous sulfate aqueous solution having a concentration of 10 to 30%, or a sulfuric acid cleaning steel plate. The rust-removing ferrous sulfate waste liquid can achieve the goal of recycling waste and greatly reduce the treatment cost. The invention not only has a wide range of technologies, but also is suitable for treating various types of alkaline sludge containing heavy metals, including waste incineration plants. Containing heavy metal ash and slag, electroplating lime sludge, etc., and the technical conditions are easy to control, the equipment is simple, and it is easy to be promoted on a large scale, which can greatly reduce the sludge treatment cost, and is a kind of sludge that can be reduced, harmless and resourced. Processing technology; the present invention not only has significant contributions to environmental ecology and social benefits, but also has economic benefits in terms of low processing costs. Please refer to "Figure 2", which is shown in the figure. The schematic diagram of the treatment process of the method for recycling heavy metal alkaline sludge in the present invention, the electroplated lime sludge containing heavy metal is transported to the sulfuric acid mixture 22. At the same time, the added sulfuric acid is adjusted to a weight percentage of 20% by using water in the water tank 21〇, stored in the sulfuric acid storage tank 21, and the acid liquid of the electroplated lime sludge volume is transferred to the sulfuric acid mixing tank. 22, start the mixer 'rotation speed 30 minutes per minute, mixing time is 3 〇 minutes, 201245054 * and maintained at room temperature (20 ° C), so that the lime sludge formed by the reaction with sulfuric acid in the lime sludge and heavy metals dissolved. Then every minute The 3000-turn centrifuge 23 performs solid-liquid separation, the solid portion of the acid-insoluble matter enters the acid-insoluble storage tank 24, and the liquid portion is subjected to the shock reaction of the de-heavy metal by the ultrasonic reactor 25, and the frequency of the ultrasonic wave is 20 KHz, and the reaction temperature is 40 ° C, the reaction time is 20 minutes, the heavy metal ions and sulfuric acid are separated, and then into the precipitation tank 251, added to the lye storage tank 2510 has been prepared with 20% of the alkali sodium hydroxide (NaOH), and The pH controller 2511 adjusts the amount of the alkali solution to maintain the pH at 2.7; the purpose of adding the lye is to precipitate the sulfuric acid, but the heavy metal does not precipitate and is still dissolved in the solution. Then, it is transported into the centrifuge 23 to perform solid-liquid separation at a centrifuge 23 of 3000 rpm, and the solid portion enters the sediment tank 230, and is oxidized with cerium oxide (Si〇2) in the tank of the acid-insoluble matter 24, and is fed into the mixer 240. Mixing, the speed of the mixer is 2 rpm, and then packaged and transported to the cement plant 26 as a cement additive. The liquid portion enters the ferrite reaction tank 231' and is added with a ferrous sulfate solution 211 having a weight percentage of 2% by weight, and the addition amount is calculated by using a dry basis of ferrous sulfate (FeS〇4) and zinc sulfate (7H2〇). 15 times of the total amount of heavy metal ions' reaction for 1Q minutes, heating with no addition to 赃, followed by addition of 2% by weight of lye 212 NaOH (s), and adjusting the test solution 212 with Qiu controller 213 The amount of addition, the reaction time, and then, by air compressor, air is blown in, and the gas-liquid ratio is controlled at 1:4' to form a brown-black-containing heavy metal ferrite crystal having a spinel structure, using a centrifuge 232 per The solid-liquid separation was carried out in 3 minutes. The liquid part of sodium sulphate aqueous solution (Na alone) 232 〇 concentration is about tongs, concentrated by two-effect vacuum evaporation (four) 21 concentrated New York 5Q%, fun cooling ^ your condensed water chat cooling 201245054 to normal temperature (2 (TC), by the sink The crystallizer 2324 of 23240 precipitates NaaSO4 crystals and separates from the mother liquid 23241, and then the mother liquid 23241 is left by the washing liquid 23243, and then dried at 100 to 300 ° C in hot air, and cooled to normal temperature (20 ° C) to form a The finished product of crystallization water Nai!S〇4 can be used in tanning and other industries. The crystallized mother liquor 23241 is returned to the ferrous sulfate solution tank 23242 for recycling, and the crystallization waste liquid can meet the discharge water standard and discharge 23244. The solid portion is a heavy metal ferrite crystal 233 having a water content of about 40%, and the fluidized bed dryer 234 is used to dry and dehydrate the ferrite crystal 234 〇 at a temperature of 15 Torr to reduce the water content to within 脒. The oxygen crystal 233 is pulverized into a 1 〇〇 powder by a pulverizer 2341, and can be used as a smelting iron alloy additive 2342; for example, the heavy metal ferrite crystal 233 is heated to 8 〇〇 ° C ' in a high temperature heating furnace 235 and the water content is lowered. 3%, can make crystal The body is rearranged to make a magnetic material additive 235
Fe系列催化劑添加料2352，以及電波吸收體材料添加料編，如以超細粉 碎機236 &碎成_目以上之微米材料和奈来材料，則可製成特種塗料之 添加料2360。 顯缺說明書中，本剌以特定具體實施例為參考來描述，然而 改變都不脫離本創作之寬廣的精神與範圍。而該對應之 涵^^^來加以說明而非限制本發明之鱗。因此，表示本發明應 所有出現在本發明之附加的申請專利範圍與其相等項之修正與變化。 201245054 【圖式簡單說明】 第1圖：係本發明含重金屬鹼性污泥資源化處裡方法之步驟流程示意圖。 第2圖：係本發明含重金屬鹼性污泥資源化處裡方法之處理流程示意圖。 【主要元件符號說明】 含重金屬之電鍍石灰污泥1 硫酸混合槽22 水槽210 硫酸亞鐵溶液211 鹼液212 pH控制儀213 硫酸貯槽21 硫酸混合槽22 離心機23 沉渣槽230 鐵氧體反應槽231 空壓機2310 加熱器2311 離心機232 硫酸鈉水溶液2320 二效真空蒸發濃縮器2321 冷卻器2322 冷凝水2323 12 201245054 . · 結晶器2324 水槽23240 母液23241 硫酸亞鐵溶液槽23242 水洗液23243 排放23244 鐵氧晶體233 流化床乾燥機234 乾燥脫水鐵氧晶體2340 粉碎機2341 鐵合金添加料2342 加熱爐235 磁性材添加料2351 催化劑添加料2352 電波吸收體材料添加料2353 粉碎機236 特種塗料之添加料2360 酸不溶物24 混合機240 超音波反應器25 沉澱槽251 鹼液貯槽2510 pH控制儀2511 水泥廠26 13 201245054The Fe series catalyst additive 2352, and the electric wave absorber material additive, such as the ultrafine pulverizer 236 & crushed into a micron material and a nematic material, can be made into a special coating additive 2360. In the description of the present invention, the present invention is described with reference to the specific embodiments, and the changes are not departing from the spirit and scope of the present invention. This correspondence is intended to be illustrative and not to limit the scale of the invention. Therefore, it is intended that the present invention cover all modifications and variations of the scope of the appended claims. 201245054 [Simplified description of the drawings] Fig. 1 is a schematic flow chart showing the steps of the method for recycling heavy metal alkaline sludge in the present invention. Fig. 2 is a schematic view showing the treatment process of the method for recycling heavy metal alkaline sludge in the present invention. [Explanation of main components] Electroplated lime sludge containing heavy metals 1 Sulfuric acid mixing tank 22 Water tank 210 Ferrous sulfate solution 211 Alkaline liquid 212 pH controller 213 Sulfuric acid storage tank 21 Sulfuric acid mixing tank 22 Centrifuge 23 Sediment tank 230 Ferrite reaction tank 231 air compressor 2310 heater 2311 centrifuge 232 sodium sulfate aqueous solution 2320 two-effect vacuum evaporation concentrator 2321 cooler 2322 condensate 2323 12 201245054 . · crystallizer 2324 sink 23240 mother liquor 23241 ferrous sulfate solution tank 23242 water wash 23243 discharge 23244 Ferrite crystal 233 Fluidized bed dryer 234 Dry dehydrated ferrite crystal 2340 Shredder 2341 Iron alloy additive 2342 Heating furnace 235 Magnetic material additive 2351 Catalyst additive 2352 Radio wave absorber material additive 2353 Grinder 236 Additive for special coatings 2360 Acid insolubles 24 Mixer 240 Ultrasonic reactor 25 Precipitation tank 251 Alkaline tank 2510 pH controller 2511 Cement plant 26 13 201245054
步驟1 A 步驟2 B 步驟3 C 步驟4 D 14Step 1 A Step 2 B Step 3 C Step 4 D 14