1322794 九、發明說明： 【發明所屬之技術領域】 本發明係有關於一種鐵系污泥整合性濕式冶金回收及 處理方法’特別係指利用濕式冶金技術分離污泥中的重金 屬’先以酸浸潰將污泥中之重金屬離子溶出’浸潰條件為 pH=〇-2、溫度30°C，浸潰液採用硫酸（H2S04)以適當固 液比（S/L)浸潰，浸潰後殘渣可通過TCLP溶出標準直接掩 埋’惟製備針鐵礦需使溶液中Fe3+濃度在沈殿過程令維持〈 1 OOOppm，故在浸潰廢液添加鐵粉(Fe)進行重金屬離子(Mn+) 置，成為金屬(Μ) ’並將三價鐵離子(Fe3+)轉換成為二價鐵 (Fe2+)，鐵粉置換係藉由[Fe]/[Mn+]莫耳比計算鐵粉添加量， 並在常溫下進行之，次再以針鐵礦法一併去除鐵離子，針鐵 礦法控制條件為pH=l-7 ’反應溫度7〇_1〇〇〇c，並在酸性 條件下利用h2o2作為其氧化劑來源，當pH及氧化還原電 位(ORP)穩定時表示反應完成，形成針鐵礦；本發明結合酸 浸潰、鐵粉置換及針鐵礦化程相進行污泥中鐵及重金屬回 收’利用此-處理技術可將污辭啼齡，達到減廢及資 源永續使用之目的。 【先前技術】 •金屬表面處理業在製造過程巾所使用的顧各不相 同’製程中所產生的廢水—般處理方法為傳統的中和法，卻 會產生大量的重金屬污泥，而污泥中亦含有許多成分 不等的重金屬，此廢棄物根據環鱗「有害事#廢棄物認定 5 1322794 標準」之毒性特性溶出程序(TCLp)超出溶出標準，屬需列管 -的有害事業廢棄物。但重金屬污泥若能經過適當回收處理裝 - 置’不僅可達到資源再利用目的，更可減少廢棄物處理成本。 污泥資源化技術概分濕式冶金技術及乾式技術，其中無 機類污泥以濕式冶金技術為主，有機類污泥則以乾式技術為 主。國内污泥資源化技術一般使用酸浸潰置換技術、酸浸潰· 氧化沈殿技術、酸浸潰結晶技術及高溫冶煉技術。由於污泥 _ 含水分且顆粒具有均質性，因此利用濕式冶金技術回收污泥 中之重金屬較具效益，並且可利用該技術分離鐵及作為生產 資源化材料的應用。 酸浸潰進行污泥中重金屬回收主要包括銅、鎳、銀、鉛、 · 錫為主，採用之浸潰液包括硫酸、鹽酸、石肖酸、王水等化學 ， 溶液，亚辅以微波消化進行，其中最常用的浸潰液為硫酸， 其反應式如下： Μ(ΟΗ)η+ηΗ+->Μη++ηΗ20 、鐵粉置換屬於一種化學置換方法，鐵粉置換係將鐵粉作 為犧牲金屬取代溶液中欲去除或回收之金屬離子，化學置換 可將浴液中重金屬去除並同時進行回收，其成本低廉且易於 控制。鐵粉置換係為異相反應，藉由電子傳送之氧化還原反 應以自發性反應進行，其反應電位為其主要因素，由金屬之 - 氧化還原電位排序，故化學置換反應的驅動力為氧化還原電 / 位反應的電位差，由此可知鐵之置換對象包括卩卜匚心c〇、 价、Sn、Pb、Η、Cu、A卜Pt、Au等。鐵粉反應如下： nFe +2Mn+->nFe2++2M „ 6 1322794 關於針鐵礦的鹼性條件製備，初始反應如下：1322794 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to an integrated wet metallurgy recovery and treatment method for iron-based sludge, particularly to the separation of heavy metals in sludge by wet metallurgy technology. The acid leaching dissolves the heavy metal ions in the sludge. The impregnation conditions are pH=〇-2, temperature 30 °C, and the immersion liquid is immersed in sulfuric acid (H2S04) at an appropriate solid-liquid ratio (S/L). The post-residue can be directly buried by the TCLP dissolution standard. However, the preparation of goethite should be such that the Fe3+ concentration in the solution is maintained at <1 OOOppm during the shovel process. Therefore, the iron powder (Fe) is added to the leaching waste liquid for heavy metal ions (Mn+). Becomes a metal (Μ) and converts ferric ions (Fe3+) into ferrous iron (Fe2+). The iron powder replacement calculates the amount of iron powder added by [Fe]/[Mn+] molar ratio, and at room temperature In this case, the iron ion is removed by the goethite method. The control condition of the goethite method is pH=l-7' reaction temperature 7〇_1〇〇〇c, and h2o2 is used as the oxidant under acidic conditions. Source, when the pH and oxidation-reduction potential (ORP) are stable, the reaction is completed, forming a needle iron ; Dipping the present invention in conjunction with the acid, iron and replacement of the drive phase goethite iron and heavy metals in sludge recovery 'exploit - Sewage speech processing techniques may cry age, achieve sustainable use of resources and reduce waste. [Prior Art] • The metal surface treatment industry uses different wastewater treatment methods in the process of manufacturing process towels. The traditional treatment method is traditional neutralization method, but it produces a large amount of heavy metal sludge, and sludge. It also contains a lot of heavy metals with different contents. According to the toxic characteristic dissolution program (TCLp) of the ring scale "Hazardous Materials #3,22,794,794", it exceeds the dissolution standard and is a hazardous business waste that needs to be listed. However, if the heavy metal sludge can be properly recycled, it can not only achieve the purpose of resource reuse, but also reduce the cost of waste disposal. The sludge recycling technology is divided into wet metallurgy technology and dry technology. Among them, the inorganic sludge is mainly wet metallurgy technology, and the organic sludge is mainly dry technology. Domestic sludge recycling technology generally uses acid leaching replacement technology, acid leaching, oxidation sulphate technology, acid leaching crystallization technology and high temperature smelting technology. Because sludge _ contains moisture and the particles are homogeneous, it is more efficient to use wet metallurgy to recover heavy metals from the sludge, and this technology can be used to separate iron and use it as a resource for production. The recovery of heavy metals in sludge by acid leaching mainly includes copper, nickel, silver, lead, and tin. The immersion liquids include sulphuric acid, hydrochloric acid, sulphuric acid, aqua regia and other chemicals, solutions, and sub-assisted by microwave digestion. The most commonly used impregnation solution is sulfuric acid, and its reaction formula is as follows: Μ(ΟΗ)η+ηΗ+->Μη++ηΗ20, iron powder replacement belongs to a chemical replacement method, and iron powder replacement system uses iron powder as The sacrificial metal replaces the metal ions to be removed or recovered in the solution, and the chemical replacement removes and simultaneously recovers the heavy metals in the bath, which is low in cost and easy to control. The iron powder replacement system is a heterogeneous reaction, and the redox reaction by electron transport is carried out in a spontaneous reaction. The reaction potential is the main factor, and the metal-redox potential is ranked, so the driving force of the chemical displacement reaction is redox The potential difference of the /bit reaction, it can be seen that the object of replacement of iron includes 卩 匚 heart c〇, valence, Sn, Pb, Η, Cu, A, Pt, Au, and the like. The iron powder reaction is as follows: nFe +2Mn+->nFe2++2M „ 6 1322794 For the preparation of the basic conditions of goethite, the initial reaction is as follows:
FeS04+2NaOH-^Fe(OH)2+Na2S04 氫氧化物沈澱在不同的鹼添加量、曝氣逮率及溫度條件 下，將產生之不同反應過程，所生成之沉澱物隨著反應過程可 分別獲得 a -FeOOH、r -FeOOH、心Fe〇〇H、Fe3〇4、7 而 〇 及a-Fe203等產物。 依適當濃度比例的硫酸亞鐵與氫氧化鈉的溶液混合，生成FeS04+2NaOH-^Fe(OH)2+Na2S04 hydroxide precipitation will produce different reaction processes under different alkali addition, aeration rate and temperature conditions. The precipitate formed can be separated with the reaction process. Products such as a-FeOOH, r-FeOOH, core Fe〇〇H, Fe3〇4, 7 and a-Fe203 are obtained. Mixing a solution of ferrous sulfate and sodium hydroxide in an appropriate concentration ratio to generate
Fe(〇H)2的灰白色沉澱物。而Fe(〇H)2在鹼性溶液中，會溶解生 成HFe〇2—其反應式如下所示：An off-white precipitate of Fe(〇H)2. While Fe(〇H)2 is dissolved in an alkaline solution, it produces HFe〇2—the reaction formula is as follows:
Fe(OH)2+〇H-->HFe02 - + h20 在所通入空氣的氣泡周圍液膜受溶氧的氧化，會生成一不 穩定相的[Fe2(QH)3]n，晶核的錯化合物，其反應式如下： HFe02_ + 02->[Fe2 (OH)3]n3n+ 在水溶液中沈析出a-Fe0(0H)，其反應式如下所示： [Fe2(OH)3]n +H20-» [a-FeO(〇H)]n 當繼續曝氣反應液時’溶氧的氧化作用使Fe(〇H)2持續 被令解生成HFe〇2 ’持續沈析出a_Fe〇(〇H)，使晶核數增 加且晶核亦成長。 關=針鐵礦的酸性條件製備，初始反應如下： 2Fe + H2〇2+2H20-> 2 a -Fe00H+4H+ 影響針鐵魅祕件包括pH、溫度及雙氧水添加速度， 型及過遽特性影響最 其中又以雙氧水添加速度對針鐵礦晶 大。 讀鐵m、針賴法和純齡為目前在料冶金中常 用的除鐵方法。飾雖在低pHT存在，因此酸浸潰後之 溶液不須縣加祕提高pH值，但缺闕在操作過程溶液 中須有心6顺4+等離子，故必需再額外添加陽離子， 且產生賴量大、微财，黃鉀聽含大量水， 在堆放中錄金屬容易流失，造成環境污料問題；赤鐵礦 法與針鐵礦法對於紐量以及含轉較黃鉀雖均大大減 少’但赤鐵礦法因需使用高壓釜沈殿鐵，投資較高，並且反 應溫度必須在約操作，耗能高；針輔法在驗性條件 下製備針鐵礦需要添加液驗’其僅需曝氣增加溶氧（D〇) ，操作費用比黃鉀鐵礬大約減少10 %，產生之針鐵礦可作 為多項應用。又，針鋪法不僅可以作為除鐵的有效方法， 而且因針鋪對陰軒具有強吸附雜，氟、氣離子可隨針 鐵礦吸附作用而達去除之功能。 本發明人有鑑於濕式冶金方法中，以酸浸潰重金屬污泥 ，雖具有殘渣量少、所需時間短等優勢，但卻有大量的鐵離 子溶出等缺點，造成後續過濾及處理上的困擾，尤其酸浸潰 液中鐵離子以Fe3及Fe2+同時存在，而大部分以Fe3+型態存 在’僅含有少量Fe2+ ;因此，本發明係利用濕式冶金技術分 離污泥中的金屬成分，並以鐵粉置換技術將酸浸潰液中的金 屬離子(Mn+)置換成為金屬（μ)，且將Fe3+還原為Fe2+，再 將Fe2+緩慢氧化成易於過濾之針鐵礦(G〇ethite)，即可進行針 1322794 鐵礦及金屬之分離與回收；如此，本發明係結合酸浸潰、鐵 粉置換及針鐵礦化程序以進行鐵系污泥之整合性濕式冶金 回收及處理’同時將前述各習知技術之缺點加以改良，遂得 以首先發明本發明。 【發明内容】 本發明所運用濕式冶金技術以分離出污泥中的金屬成 分，其技術手段係先以酸浸潰（硫酸）將污泥中之重金屬離 子溶出’浸潰條件為pH=〇-2、溫度3(TC，浸潰液採用1 〜2NH2S〇4以固液比(s/l) : 1/1〜1/2〇浸潰0.5小時以上， 浸潰後殘渣可通過TCLP溶出標準可直接掩埋，惟製備針鐵 礦需使溶液中Fe3+濃度在沈澱過程中需維持< 1〇〇〇ppm，故 在浸潰廢液添加鐵粉將重金屬離子置換成為金屬，並將三價 鐵離子(Fe3+)轉換成為(Fe2+)二價鐵離子，且在常溫下控制 [Fe]/[M ]莫耳比撥拌以進行鐵粉置換，再以針鐵礦法一併 去除鐵離子’針鐵礦法控制條縣ρΗ=μ7，反應溫度7〇 -i〇〇c，並在酸性條下以Η2〇2作為其氧化劑來源，當ρΗ 及氧化還原電位(ORP)敎時表示反應完成，即可形成針鐵 礦；本發明結合酸浸潰、鐵粉置換及針鐵礦化程序以進行污 泥中鐵及重金屬分離回收。 本技術之標的包括： 1. 以硫酸浸潰含鐵系污泥’使紐減少以達到廢棄物減 量之目的。 2. 本發明適用於以鐵系藥劑處理廢水形成之鐵系重金屬 9 1322794 污泥 料，而置換後之重金屬粉末可成為具經濟價值的原 料而產生的針鐵礦可資源化材料庳' A吸紐Μ # 用，如辦水處理作 為及附材枓、色顏_、觀_ 料、空氣污染防治材料。 材料的主要原 【實施方式】 〜有關本發明為達上述之使用目的與功效，所採用之技 術手段’ 較佳可行之實施例，同時配合圖式所示， 祥述如下： 百先，請參閱第-圖所示，本發明之實施步驟如下： (1) 酸浸鐵系污泥：將鐵系污泥置於硫酸濃度為卜別之 酸液中進行攪拌(ρΗ=〇-2)，浸漬〇.5〜3小時，其t污泥 與硫酸固液比為"卜㈣，溫度最好為3〇°c，浸潰後 進打固液分離，得—含重金屬續浸潰液，而殘渣可 直接掩埋處理； 一 (2) 進灯鐵粉置換技術：由步驟⑴酸浸潰後取得阳為〇 〜2的含重金屬之酸浸潰液，再添加鐵粉控制 莫耳比或使浸漬液中氧化還原電位(〇Rp)<〇，在pH為 〇〜2、溫度約為3〇〇c條件下反應，將重金屬離子(Mn+) 置換成金屬(Μ)，Fe3+還原為Fe2+，並且可使濾液中Fe3+ 濃度<1000 ppm，反應達平衡_及〇Rp值達穩定)後 ，進行固液分離，所得之固相殘渣進行TCLP、X光繞 射光譜儀(XRD)分析’而其中鐵粉可再供作為置換過程 10 之原料’另固液分離後所得之遽液則供續行下一步驟 之針鐵礦化； ⑴針鐵技術··取步驟(2)所得之_進行針鐵礦化， 其操作條件為pH=l-7，反應溫度7〇 _1〇〇t，攪拌速率 200-400rpm ’於酸性條件下以氏〇2作為其氧化劑（溫 度為70〜lOOt： ’最好為85ΐ )，# pH及氧化還原= 位(ORP)穩定時表示反應完成，由步驟⑴反應過程 中長出易於過濾分離之針鐵礦，以利後續過濾及產品 純化； 如此，以硫酸浸潰污泥，可使殘渣減少以達廢棄物減量 之目的，且藉由鐵粉置換技術分離出酸浸潰液中的金屬離子 ’使之形成金屬，_後_纽產品純化，而針鐵礦可供 應用於吸附材料。 八 【說明案例及實施成效：】 根據本發明所運用之技術手段而可達之成效，茲舉出實 施例參數說明如下： 本案實施例採用電路板業經化學混凝處理法所產生之 鐵系污泥，污泥中所含重金屬成分及含量如表一所示： 表一、電路板業鐵系污泥成分分析 元素 Cu Fe Zn Cd Pb Cr Ni mg/kg 136,300 201,100 433 <0.01 16 372 2,431 先取實際電路板業鐵系污泥進行全量分析，瞭解該批污 泥主要重金屬成分。 本發明主要分成三錄序：程序-為酸浸潰，操作條件 為反應溫度為常溫3〇ΐ、獅料释、浸潰液為2N 之邱〇4、固液比(S/ lh/io、视拌浸潰時間約】小時 (pH-0-2) ’固液分離後’固相進行Τ(χρ毒性特性溶出試驗， 液相進行水質分析；程序二為將辩—獲得之含重金屬之酸 改潰液進彳T化學置換，為了使娜子置換成金屬銅並使後續 的針鐵礦化過程順利進行’必須預先降低Fe3+濃度，故在酸 次潰液中加入鐵粉進行置換，操作條件為反應溫度為常溫30 °C、攪拌速率200rpm、[Fe]/ [Cu2+]莫耳比4 〇，將銅離子置 換成金屬銅，Fe3+還原為Fe2+，反應20分鐘PH及氧化還原 電位(ORP)達穩定後，經固液分離進行水質分析，程序三為 針鐵礦化，取置換後濾液加入大量液鹼調整pH，為避免反 應中過量酸鹼添加導致產物中有過量鹽類之產生，針鐵礦操 作條件係為pH=4 ’反應溫度8〇t：，攪拌速率200rpm，h2〇2 添加量1.8 ml/min/1 ’當PH及ORP穩定時表示反應完成（反 應時間約360分鐘）’針鐵礦化完成將混和液1)11調整符合放 流水標準（pH=6〜9)，再進行固液分離；反應中PH、ORP 及溫度的變化如第二圖〜第四圖所示’pH、ORP及溫度的變 化可瞭解各反應之控制條件及各階段反應終止之時間。 本實例採用實際印刷電路板業污泥屬鐵系污泥，該污泥 經過酸浸潰-鐵粉置換-針鐵礦化後液相之水質分析結果 12 1322794 如表二所示 元素 Cu Fe Zn Cd Pb Cr Ni 酸浸潰 9,200 8,070 24.36 N.D. 1.2 12 HO 鐵粉置換 62 21,230 18 N.D. 0.8 9.0 107 針鐵礦化 0.16 1.99 0.06 N.D. 0.52 0.13 0.77 法規標準 3.0 單位：ppm 10 5.0 0.03 1.0 2.0 1.0Fe(OH)2+〇H-->HFe02 - + h20 The liquid film around the air bubble is oxidized by dissolved oxygen, which will form an unstable phase of [Fe2(QH)3]n, crystal nucleus. The wrong compound has the following reaction formula: HFe02_ + 02->[Fe2(OH)3]n3n+ precipitates a-Fe0(0H) in aqueous solution, and its reaction formula is as follows: [Fe2(OH)3]n +H20-» [a-FeO(〇H)]n When the aeration reaction solution is continued, the oxidation of dissolved oxygen causes Fe(〇H)2 to continue to be hydrolyzed to form HFe〇2' to continuously precipitate a_Fe〇 (〇 H), the number of crystal nuclei is increased and the crystal nuclei are also grown. Off=Acid iron ore is prepared by acidic conditions. The initial reaction is as follows: 2Fe + H2〇2+2H20-> 2 a -Fe00H+4H+ affects the needle iron charm including pH, temperature and hydrogen peroxide addition speed, type and over-twist characteristics The most important effect is the addition of hydrogen peroxide to the goethite crystal. The read iron m, the needle-draw method and the pure age are the iron removal methods commonly used in metallurgy. Although the decoration is present at a low pHT, the solution after the acid leaching does not require the county to increase the pH value, but the defect must have a 6 cis 4+ plasma in the operating solution, so additional cations must be added, and the reliance is large. , micro-finance, yellow potassium listens to a large amount of water, the metal is easily lost in the stacking, causing environmental pollution problems; hematite method and goethite method for the amount and the conversion of yellow potassium are greatly reduced 'but red The iron ore method requires the use of an autoclave, which has a high investment, and the reaction temperature must be operated at a high energy consumption. The needle-assisted method requires the addition of a liquid test to prepare goethite under the test conditions. Dissolved oxygen (D〇), the operating cost is reduced by about 10% compared with jarosite, and the produced goethite can be used for many applications. In addition, the needle-sand method can not only be used as an effective method for removing iron, but also because the needle shop has a strong adsorption impurity to the Yinxuan, and the fluorine and gas ions can be removed by the adsorption of the goethite. The present inventors have in view of the wet metallurgy method, the acid-impregnated heavy metal sludge has the advantages of a small amount of residue and a short time required, but has a large number of defects such as iron ion elution, resulting in subsequent filtration and treatment. Trouble, especially in the acid leaching solution, iron ions exist simultaneously with Fe3 and Fe2+, and most of them exist in the Fe3+ form, which contains only a small amount of Fe2+; therefore, the present invention utilizes wet metallurgy technology to separate metal components in the sludge, and The metal ion (Mn+) in the acid leaching solution is replaced with metal (μ) by iron powder replacement technology, and Fe3+ is reduced to Fe2+, and then Fe2+ is slowly oxidized into easy-filtered goethite (G〇ethite), that is, Separation and recovery of iron ore and metal can be carried out on needle 1322794; thus, the present invention combines acid impregnation, iron powder replacement and goethite mineralization procedures for integrated wet metallurgical recovery and treatment of iron-based sludge' The disadvantages of the above-mentioned prior art are improved, and the present invention can be first invented. SUMMARY OF THE INVENTION The wet metallurgy technique of the present invention utilizes the separation of metal components in sludge, and the technical means is to first dissolve the heavy metal ions in the sludge by acid leaching (sulfuric acid). The impregnation condition is pH=〇. -2, temperature 3 (TC, immersion solution using 1 ~ 2 NH2S 〇 4 to solid-liquid ratio (s / l): 1 / 1 ~ 1/2 〇 immersion for more than 0.5 hours, the residue after leaching can pass the TCLP dissolution standard It can be directly buried, but the preparation of goethite needs to maintain the concentration of Fe3+ in the solution during the precipitation process to maintain <1〇〇〇ppm, so the iron powder is added to the waste liquid to replace the heavy metal ions into metal, and the ferric iron The ion (Fe3+) is converted into (Fe2+) ferrous ion, and the [Fe]/[M] molar ratio is controlled at room temperature for iron powder replacement, and the iron ion 'needle is removed by the goethite method. The iron ore method controls the county ρΗ=μ7, the reaction temperature is 7〇-i〇〇c, and Η2〇2 is used as the oxidant source under the acid strip. When ρΗ and redox potential (ORP)敎, the reaction is completed, ie It can form goethite; the invention combines acid leaching, iron powder replacement and goethite mineralization procedure to carry iron and heavy gold in sludge Separation and recovery. The subject of the technology includes: 1. The iron-containing sludge is leached with sulfuric acid to reduce the amount of waste to achieve the purpose of waste reduction. 2. The invention is applicable to iron-based heavy metals formed by treating wastewater with iron-based chemicals 9 1322794 Sludge material, and the replaced heavy metal powder can be a valuable material for the production of goethite resource-recyclable materials 庳' A Μ Μ 用 用 用 用 用 用 用 用 用 用 用 用 用 用 用 用 用 用 用The main raw material of the material is the same as the above-mentioned purpose and effect, and the technical means adopted are better and feasible, and the figure is shown in the figure. As stated in the figure above, the implementation steps of the present invention are as follows: (1) Acid-impregnated iron-based sludge: The iron-based sludge is placed in an acid solution having a sulfuric acid concentration of Stir (ρΗ=〇-2), immersed for 5~3 hours, the ratio of t sludge to sulfuric acid solid-liquid is "Bu (4), the temperature is preferably 3〇°c, after the impregnation, the solid-liquid separation is obtained. - containing heavy metal continuous immersion liquid, and the residue can be directly buried One (2) into the lamp iron powder replacement technology: after the acid (1) acid leaching, obtain the heavy metal acid leaching solution of Yang 〇~2, and then add iron powder to control the molar ratio or make the redox potential in the immersion liquid (〇Rp)<〇, reacting at a pH of 〇2 and a temperature of about 3〇〇c, replacing heavy metal ions (Mn+) with metal (Μ), Fe3+ with Fe2+, and making Fe3+ in the filtrate After the concentration <1000 ppm, the reaction reaches equilibrium _ and the 〇Rp value is stable, the solid-liquid separation is performed, and the obtained solid residue is subjected to TCLP and X-ray diffraction spectrometer (XRD) analysis, and the iron powder can be re-supplied as The raw material of the replacement process 10 is obtained by the separation of the solid and liquid liquids for the next step of goethite mineralization; (1) Needle iron technology·· taking the step (2) obtained for the needle iron mineralization, the operation thereof The conditions are pH=l-7, the reaction temperature is 7〇_1〇〇t, and the stirring rate is 200-400 rpm. Under acidic conditions, 〇2 is used as its oxidant (temperature is 70~100t: 'preferably 85ΐ),# When the pH and redox = position (ORP) are stable, the reaction is completed, and the goethite which is easy to be separated by filtration is obtained during the reaction in the step (1). In order to facilitate subsequent filtration and product purification; thus, the sludge is leached with sulfuric acid, the residue can be reduced to achieve the purpose of waste reduction, and the metal ions in the acid leaching solution are separated by the iron powder replacement technique. The formation of metal, _ post _ new product purification, and goethite can be applied to the adsorption material. VIII [Description of the case and implementation results:] According to the technical means used in the present invention, the parameters of the embodiment are as follows: The embodiment of the present invention adopts the iron stain generated by the chemical coagulation treatment method of the circuit board industry. The composition and content of heavy metals in mud and sludge are shown in Table 1: Table 1. Analysis elements of iron sludge in circuit board industry Cu Fe Zn Cd Pb Cr Ni mg/kg 136,300 201,100 433 <0.01 16 372 2,431 The actual circuit board industry iron sludge was analyzed in full quantity to understand the main heavy metal components of the sludge. The invention is mainly divided into three recording sequences: the program is acid immersion, and the operating conditions are the reaction temperature is 3 常 at room temperature, the schist release, the immersion liquid is 2N, the solid-liquid ratio (S/lh/io,拌 浸 】 】 】 】 】 】 】 pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH pH 固 固In order to replace the metal into copper and to make the subsequent goethite process smoothly, 'the concentration of Fe3+ must be reduced beforehand. Therefore, iron powder is added to the acid solution to replace the operating conditions. The reaction temperature is normal temperature 30 ° C, stirring rate 200 rpm, [Fe] / [Cu 2+ ] molar ratio 4 〇, copper ions are replaced by metal copper, Fe 3 + is reduced to Fe 2+ , reaction 20 minutes PH and oxidation reduction potential (ORP) After stabilization, the water quality analysis is carried out by solid-liquid separation. The third procedure is goethite mineralization. After the replacement, the filtrate is added with a large amount of liquid alkali to adjust the pH. In order to avoid excessive acid and alkali addition in the reaction, excessive salt is produced in the product. The operating conditions of iron ore are pH=4' reaction temperature 8〇t:, stir Rate 200 rpm, h2 〇 2 Addition amount 1.8 ml / min / 1 'When the pH and ORP are stable, the reaction is completed (reaction time is about 360 minutes) 'The completion of the needle iron mineralization is adjusted to meet the discharge water standard (pH) =6~9), and then carry out solid-liquid separation; the changes of pH, ORP and temperature in the reaction are as shown in the second figure to the fourth figure. The changes of pH, ORP and temperature can be used to understand the control conditions of each reaction and the reaction of each stage. The time of termination. This example uses the actual printed circuit board industry sludge is iron-based sludge, the sludge after acid leaching - iron powder replacement - needle iron mineralization liquid phase water quality analysis results 12 1322794 as shown in Table 2 Element Cu Fe Zn Cd Pb Cr Ni Acid leaching 9,200 8,070 24.36 ND 1.2 12 HO Iron powder replacement 62 21,230 18 ND 0.8 9.0 107 Needle iron mineralization 0.16 1.99 0.06 ND 0.52 0.13 0.77 Regulatory standard 3.0 Unit: ppm 10 5.0 0.03 1.0 2.0 1.0
Fe3+與Cu2+置換率如表三所示。 表三鐵粉置換結果 元素 Fen+ Cu2+ Fe3+ 酸浸潰 8,070 9,200 2,380 鐵粉置換 21,230 62 1.99 置換率(〇/〇) · ___ — 99.3 99.9 由水質分析結果發現，經pH調整後可符合放流水標準 ’另由表三可知Fe3+與Cu2+置換率均達到99%以上，溶液中 Fe3+濃度為1.99ppm(<l，000ppm)，可使針鐵礦化順利進行。 為了確定酸浸潰後所產生殘渣是否有重金屬溶出問題 ’因此對酸浸潰殘渣及鐵粉置換後殘渣進行TCLP分析，另 外為了瞭解合成之針鐵礦是否有重金屬溶出之情形，亦對針 鐵礦進行TCLP分析，分析結果如表四所示，由結果可知經 13 1322794 過酸浸潰後所產生之殘渣符合法規標準，合成之針鐵礦亦無 重金屬溶出問題。 元素 Cu Fe Zn Cd Pb Cr Ni 酸浸潰 3.12 0.44 0.03 N.D. 0.09 N.D. 0.29 鐵粉置換 0.05 1168 0.03 N.D. 0.14 0.04 0.38 針鐵礦化 1.74 0.10 0.08 N.D. 0.10 N.D. 8.56 TCLP標準 W Air ： r\r\m 15 — 一 LO 5.0 5.0 — 經由本發明程序酸浸潰、鐵粉置換及針鐵礦化之技術整 合，污泥中的鐵可成為黃色沈澱物，將此黃色沈澱物進行χ 光繞射光瑨儀(XRD)鑑定分析，結果如第五圖所示，由此黃 色’儿澱物之XRD分析圖譜比對確認為針鐵礦(G〇ethite， α-FeOOH)產物。 經由以上說明可知，本發明可具以下各項優點： 。1•依本發明以硫酸浸潰⑽、污泥，可使鐵㈣泥殘渣達 最小化，達到廢棄物減量之目的。 2.本發明崎顯技術分離出酸浸潰巾的鋪，使之形 成易於過濾之針鐵礦達到產品純化之目的。 成本 3工依本發簡術所得胁·「針賴」可湘於陰離子及 ^子吸_，如此可將鐵質加郎收歸源化而降低處理 又以鐵粉置換技The substitution rates of Fe3+ and Cu2+ are shown in Table 3. Table 3 Iron powder replacement result element Fen+ Cu2+ Fe3+ acid impregnation 8,070 9,200 2,380 Iron powder replacement 21,230 62 1.99 Replacement rate (〇/〇) · ___ — 99.3 99.9 It was found by water quality analysis that the pH can be adjusted to meet the discharge water standard' In addition, it can be seen from Table 3 that the substitution rates of Fe3+ and Cu2+ are both above 99%, and the Fe3+ concentration in the solution is 1.99 ppm (<1,000 ppm), which can smoothly carry out goethite mineralization. In order to determine whether the residue produced after acid leaching has a problem of heavy metal dissolution, the TCLP analysis is performed on the acid leaching residue and the residue after iron powder replacement, and in order to understand whether the synthetic goethite has heavy metal dissolution, it is also suitable for needle iron. The TCLP analysis was carried out on the ore. The results of the analysis are shown in Table 4. From the results, it is known that the residue produced after 13 1322794 peracid impregnation meets the regulatory standards, and the synthetic goethite has no problem of heavy metal dissolution. Element Cu Fe Zn Cd Pb Cr Ni acid impregnation 3.12 0.44 0.03 ND 0.09 ND 0.29 Iron powder replacement 0.05 1168 0.03 ND 0.14 0.04 0.38 Needle iron mineralization 1.74 0.10 0.08 ND 0.10 ND 8.56 TCLP standard W Air : r\r\m 15 — a LO 5.0 5.0 — Through the technical integration of the acid leaching, iron powder replacement and goethite mineralization of the present invention, the iron in the sludge can become a yellow precipitate, and the yellow precipitate is subjected to a krypton spectrometer ( XRD) Identification analysis, the results are shown in the fifth figure, and the XRD analysis pattern of the yellow 'yield' is confirmed to be a gostenite (α-FeOOH) product. As can be seen from the above description, the present invention can have the following advantages: 1. According to the invention, the (4) sludge can be minimized by sulfuric acid impregnation (10) and sludge, and the waste reduction can be achieved. 2. The invention of the present invention separates the shop of the acid-impregnated scarf to form a ready-to-filter goethite for the purpose of product purification. Cost 3 workers according to the threat of the hair extension, "needle" can be in the anion and ^ sub-suction _, so that the iron can be reduced to return to the source and reduce the treatment and iron powder replacement technology
Ml㈣利用針鐵礦技術分離出鐵後， 14 術*即可生，成高單價、高純度之銅金屬，㈣放流水可達放 流標準，固相殘渣及產品亦符合法規TCLP之溶出標準。 綜上所述，本發明技術利用一鐵系污泥之整合性濕式冶 金回收及處理方法，不娜廢棄物減量 '廢水放流符合標準 ’同時產生可供刺狀「針_」及高單價、高純度之「 金屬銅」’可將廢棄物予以資源化，不僅具產業可利用性且 具高經濟· ’本發明實_確實已能_所麵之目的及 功效，又未見有相_徵者公财先，故本伽#能符合發 明專利之申請要件，纽法提出申請，懇請早日審結，並核 賜專利，實深感德澤。 【圖式簡單說明】 第一圖所示係為本發明以鐵系 處理流程。 /亏泥整合性濕式冶金回收及 第二圖所示係為本發明反應中之PH變化。（1:酸浸潰， 11 .鐵粉置換，III :針鐵礦化） 第二圖所示係為本發明反應中之氧化還原電位(⑽)變 化。（I:酸浸潰’ II:鐵粉置換，ΙΓη針鐵礦化） 第四圖所示係為本發明反應中之溫錢化。（丨：酸浸潰， 11 ·鐵粉置換，III :針鐵礦化）。 光繞射光譜儀(XRD)晶 第五圖所示係為本發明針鐵礦之X 相判定。 15Ml (4) After separation of iron by goethite technology, 14 can produce raw, high-priced copper metal with high purity, (4) discharge water can reach discharge standard, solid residue and products also meet the dissolution standard of TCLP. In summary, the technology of the present invention utilizes an integrated wet metallurgy recovery and treatment method of an iron-based sludge, and the waste reduction of the waste water 'the discharge of the wastewater meets the standard' simultaneously produces a thorn-like "needle" and a high unit price. The high-purity "metal copper" can be used to recycle waste, which is not only industrially usable but also highly economical. 'The invention has been able to achieve the purpose and effect, and there is no phase. The public finance first, so Benga # can meet the application requirements of the invention patent, New Zealand filed an application, so please conclude as soon as possible, and grant a patent, the deep sense of Deze. [Simple description of the drawings] The first figure shows the iron processing process of the present invention. / Depletion integrated wet metallurgy recovery and the second figure shows the pH change in the reaction of the present invention. (1: acid leaching, 11. iron powder replacement, III: goethite mineralization) The second figure shows the oxidation-reduction potential ((10)) change in the reaction of the present invention. (I: acid leaching 'II: iron powder replacement, ΙΓη needle iron mineralization) The fourth figure shows the warming of the reaction of the present invention. (丨: acid leaching, 11 · iron powder replacement, III: goethite mineralization). Light diffraction spectrometer (XRD) crystal The fifth figure shows the X phase determination of goethite in the present invention. 15