1250214 玖、發明說明： 【發明所屬之技術領域】 本發明是有關於一種金屬錫冶煉的方法，特別是指一 種藉由週波爐提供能源，而將含錫化合物冶煉還原成金屬 錫的方法。 【先前技術】 金屬冶煉技術發展至今已相當成熟，其技術内容可參 考化學、冶礦等書籍，或相關的專利案、論文等文獻資料， 10 15 20 其中與金屬錫冶煉有關的部分可參考中華民國專利公告_泰 號312707及333558,以及美國專利US4236916及 US4283045等專利說明書的内容。 金屬冶煉過程中主要是藉由燃燒含碳化合物，如煤 焦、活性碳、木炭、天然氣、液化石油氣、重油、柴油等 燃料以提供熱源，或再輔以電熱源，然後將燃燒產生的一 氧化碳及未燃燒的碳元素作為還原劑，將金屬化合物（以金 屬氧化物為主）還原成元素態的金屬。而金屬冶煉的爐體型 式則主要可區分為反射爐（reverberat〇]T furnace)及旋轉爐鲁鲁 (rotary furnace)等。另外，在以電力進行金屬熔煉方面， 依回收金屬的種類、形態的不同，可使用電弧爐、電熱爐 或是週波爐進行炫煉。 在印刷電路板製程中，會有一道鍍錫（鉛）的程序以保 護印刷電路板在蝕刻時不被蝕刻液侵蝕。在蝕刻完成後， 就以剝錫（鉛）液將錫（鉛）鍍層剝除，因此會產生剝錫（鉛） 廢液，以及鍍錫錫泥和喷錫錫渣等。另外，電子業進行表 4 1250214 面構裝_τ)時，也會產生許多的錫渣，而電鍵錫業則會 產生電鍍的錫污泥。上述這些含錫的廢料必須進行回收， 其回收的技術可利用化學中和、電解及過濾等方法作初步 的處理，之後再以冶煉技術獲得金屬錫。 雖然冶煉金屬錫的技術已經相當成熟，但含錫的廢料 中錫的回收率仍然偏低，約僅5…7〇%，且在冶煉過程;， 因錫瘵氣及其他廢氣的產生相當嚴重，因此空氣污染防户 設備投資相當大，且具有高爐渣產生的缺點。 週波爐經常使用於金屬的溶煉鑄造，例如中溫鋁、銅 (800-140GC)的溶煉及向溫鑄鐵、鐵合金細。〇的_ 熔煉上。其原理是利用在週波爐的坩鍋中加入導體，例如 金屬或石墨等’而具有導磁性’然後在高週波磁場不斷循 環變換下，金屬或石墨等導體材料内部產生涡電流（eddy current) ’此渦電流進而轉換成熱能，使坩鍋内的溫度快速 提升而可進行金屬的熔煉。 發明人在進行含錫廢料處理研究過程中’將週波爐應 用於處理剝錫⑹廢液或是其他含錫廢料所產生的含錫化籲鲁 口物的/口煉’發現可以大巾s提升錫回率，並能降低冶煉廢 氣及爐渣的產生量，因而有本發明的提出。 【發明内容】 因此’本發明的目的’在於提供—種可提高錫回收 率’並能降低冶練廢氣及爐渣的產生量的自含錫化合物中 冶煉金屬錫的方法。 因此’本發明之自含錫化合物中冶煉金屬錫的方法， 1250214 二有下列步驟。將—導體加人—週波爐中，使該週波爐具 磁性’再將一含錫化合物、一含碳選原劑及一冶煉助劑 加入该週波爐中而與該導體形成一冶煉混合物。該週波爐加 5熱朗達—冶煉溫度，而在該冶煉溫度下，該冶煉混合物發 生氧化還原反應，並經一反應時間，而獲得一金屬錫。 【實施方式】 有關本i明之則述及其他技術内容、特點與功效，在 以下配合參考圖式之數個較佳實施例的詳細說明中，將可 清楚的理解。 ) 纟發明自含錫化合财冶煉金屬錫的方法，為利用週 波爐提供能源的方式，將剝錫⑹廢液或其他含錫廢料處 理過私中所產生的含錫化合物，添加適量含碳化合物及冶 煉助劑，於強還原狀態下冶煉製得金屬錫。 如圖1所示，本發明即為利用週波爐的特性，首先在 1 週波爐的義中加入導體，例如金屬敍/或石墨，使週波 爐中具有導磁性（步驟υ。然後將剝錫⑻廢液或其他含錫 廢料在處理過程中所產生的含錫化合物如㈣或錫泥等 加入週波爐中，並添加適量的含碳化合物及冶煉助劑（步驟 2)，再與上述導體摻拌而形成冶煉混合物，其中添加含碳 > 化合物係作為還原劑，而冶煉助劑係用以降低爐渣 避免冶煉過程中錫蒸氣過度逸出。接著啟動週波爐升溫進 行冶煉（步驟3)，其中週波爐的頻率設定為__5_Hz。 當週波爐提昇冶煉混合物的溫度至6〇〇-15〇〇。〇時，冶煉混 合物即會自動發生氧化還原反應（步驟4)，使得含錫化合物 1250214 被還原成液態金屬錫並產生有爐渣，然後將產生的爐渣撈 除（步驟5)，最後可獲得液態金屬錫（步驟❸，此一金屬錫 - 例如疋南純度的金屬錫或是錫鉛合金，而整個氧化還原反 應時間約需1-6小時。 在此須加以說明的是，上述含錫化合物、含碳還原劑 及〜煉助劑所構成的冶煉錫原料，除了可在週波爐升溫進 仃冶煉（步驟3)之前便與導體摻拌（步驟2實線部分），也可 以在週波爐升溫而將導體熔融之後，再行加入該冶煉錫原 料（如圖1步驟2虛線部分），另外，可以將一部分的冶煉籲 1〇 7原料先與導體摻拌，等到週波爐升溫之後，再將剩餘的 口煉錫原料全部或是再分批加入週波爐之中（步驟2實線 及虛線部分）。 利用本發明的方法進行金屬錫的冶煉，其中含錫化合 15 物的來源並不限定於處理剝錫（鉛）廢液所產生的錫泥，亦 15 可為富锡礦、各種錫化合物、電子業表面構裝（SMT)所產 生的錫渣、印刷電路板之鍍錫錫泥與噴錫錫渣，及電鍍錫 業之錫尼或其混合物，而含錫原料中若含有銅、鐵、錯籲_ ^重金屬或其混合物，並不會影響利用本發明的方法進行 j煉。作為還原劑的含碳化合物可以為焦碳、木炭、活性 2〇 <、無煙煤、石墨、黑煙、紙及歸等或其混合物，而冶· 煉助劑則可以為氟化約、氧化約、石朋酸納、氧化銘、氧化 夕玻璃畚、生石灰、氧化鐵、氧化鎂等或其混合物。 •以下將以數個實施例對於本發明的方法加以詳細說 7 1250214 <貫施例一 > 取i623g因處理剝錫廢液所產生的乾錫泥，内含有 60%的錫’添加4〇〇g碳酸納作為冶煉助劑及活性碳 作為還原劑，並予以摻拌形成冶煉錫原料。首先，添加370g 5 纟屯度為92%的金屬錫，於週波爐㈣锅中使爐内具有導磁 性，然後提升冶煉溫度至可產生氧化還原反應 的溫度，接 著再將前述配製的冶煉錫原料分三批投料，每批間隔丨小 日守，總反應時間4小時，總共冶煉製得n59g純度為92% 的金屬錫，該金屬錫塊的立體圖如圖2所示，其中錫回收參 1〇 率為74.5%。本較佳實施例中所使用的週波爐容積為 10L(升）’隶大輸出功率為5〇 kW(瓧），週波爐頻率設定為 3000Hz(赫茲），冶煉溫度為ΐ2〇(μΐ3〇〇°0。 <實施例二> 15 取1623g因處理剝錫廢液所產生的乾錫泥，内含有 60%的錫，添加950g純度為92%的金屬錫，添加i〇〇g碳 酸鈉作為冶煉助劑，並以l〇〇g焦碳粉、5〇g木炭及5〇g活籲 性碳作為還原劑，並予以掺拌，之後全部加料至週波爐的 坩鍋中，然後提升冶煉溫度至可產生氧化還原反應的溫 20 度，經2小時的反應時間後，總共冶煉製得I900g純度為 92%的金屬錫，該金屬錫塊的立體圖如圖3所示，其中錫 回收率為89.8%。本較佳實施例中所使用的週波爐容積為 10L，最大輸出功率為50 kW，週波爐頻率設定為3000Hz， 冶煉溫度為1200-1300°C。 1250214 <實施例三> ίο 15 20BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of metal tin smelting, and more particularly to a method for smelting and reducing tin-containing compounds into metal tin by providing energy by a centrifugal furnace. [Prior Art] The development of metal smelting technology has been quite mature so far. The technical content can refer to books such as chemistry and metallurgy, or related patents, papers and other literature materials. 10 15 20 Among them, the parts related to metal tin smelting can refer to China. The contents of the patent specifications of the Republic of China Patent No. 312707 and 333558, and the patent specifications of US Pat. No. 4,236,916 and US Pat. Metal smelting process mainly by burning carbon-containing compounds, such as coal char, activated carbon, charcoal, natural gas, liquefied petroleum gas, heavy oil, diesel and other fuels to provide heat source, or supplemented by electric heat source, and then the carbon monoxide produced by combustion And the unburned carbon element is used as a reducing agent to reduce a metal compound (mainly a metal oxide) to an elemental metal. The furnace type of metal smelting can be mainly divided into a reverberatory furnace (reverberat〇) T furnace) and a rotary furnace, a rotary furnace. In addition, in the case of metal melting by electric power, depending on the type and form of the recovered metal, it is possible to use an electric arc furnace, an electric furnace or a centrifugal furnace for smelting. In the printed circuit board process, there is a tin-plated (lead) process to protect the printed circuit board from etching by the etchant during etching. After the etching is completed, the tin (lead) plating layer is stripped with a tin (lead) liquid, so that a tin (lead) waste liquid, a tin-plated tin mud, and a tin-tin solder residue are generated. In addition, when the electronics industry performs the surface mount _τ), it also produces a lot of tin slag, while the key tin industry produces electroplated tin sludge. These tin-containing wastes must be recovered, and the recovery technology can be initially treated by chemical neutralization, electrolysis, and filtration, and then metal tin can be obtained by smelting techniques. Although the technology for smelting metal tin is quite mature, the recovery rate of tin in tin-containing scrap is still low, only about 5...7%, and during the smelting process; the production of tin and other exhaust gases is quite serious. Therefore, the air pollution prevention household equipment investment is quite large, and has the disadvantage of blast furnace slag generation. The pulsating furnace is often used for metallurgical casting, such as medium temperature aluminum, copper (800-140GC), and fine iron and iron alloy. 〇 _ smelting. The principle is to use a conductor, such as metal or graphite, in the crucible of a centrifugal furnace to have magnetic permeability. Then, under the cyclical transformation of a high-frequency magnetic field, an eddy current is generated inside a conductor material such as metal or graphite. This eddy current is further converted into heat energy, so that the temperature in the crucible is rapidly increased and the metal can be smelted. During the research process of tin-containing waste treatment, the inventor used the Zhoubo furnace to treat the tin-containing (6) waste liquid or other tin-containing wastes. The tin recovery rate and the amount of smelting exhaust gas and slag generated can be reduced, and thus the present invention has been proposed. SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide a method for smelting metallic tin from a tin-containing compound which can improve the tin recovery rate and can reduce the amount of smelting exhaust gas and slag. Therefore, the method for smelting metallic tin from the tin-containing compound of the present invention, 1250214, has the following steps. The conductor is added to the winding furnace to magnetically reciprocate the centrifugal furnace. A tin-containing compound, a carbon-containing sizing agent and a smelting aid are added to the centrifugal furnace to form a smelting mixture with the conductor. The cycle furnace is charged with a 5 hot Randa-smelting temperature, and at the smelting temperature, the smelting mixture undergoes a redox reaction, and a metal tin is obtained after a reaction time. [Embodiment] The detailed description of several preferred embodiments, which are described below with reference to the drawings, will be clearly understood.纟Inventing a method for smelting metal tin from a tin-containing compound, in order to provide energy by means of a centrifugal furnace, the tin-containing compound produced by treating the tin (6) waste liquid or other tin-containing waste is treated with a proper amount of carbon-containing compound. And smelting auxiliaries, smelting in a strong reducing state to obtain metal tin. As shown in Fig. 1, the present invention utilizes the characteristics of a centrifugal furnace. First, a conductor, such as metal or graphite, is added to the meaning of a 1 cycle furnace to make the magnetic furnace have magnetic permeability (step υ. Then the stripping is performed (8) The tin-containing compound (such as (4) or tin mud generated during the treatment of waste liquid or other tin-containing waste is added to the centrifugal furnace, and an appropriate amount of carbon-containing compound and smelting aid (step 2) is added, and then mixed with the above conductor. And forming a smelting mixture, wherein a carbon-containing compound is added as a reducing agent, and the smelting aid is used to reduce slag to avoid excessive escape of tin vapor during the smelting process. Then, the temperature of the centrifugal furnace is started to be smelted (step 3), wherein the cycle The frequency of the furnace is set to __5_Hz. When the temperature of the smelting mixture is increased to 6〇〇-15〇〇., the smelting mixture will automatically undergo a redox reaction (step 4), so that the tin-containing compound 1250214 is reduced to Liquid metal tin and produce slag, and then the resulting slag is removed (step 5), and finally liquid metal tin can be obtained (step ❸, this metal tin - such as the purity of 疋Metal tin or tin-lead alloy, and the entire redox reaction time takes about 1-6 hours. It should be noted that the tin-containing compound, the carbon-containing reducing agent and the refining aid constitute a tin-smelting raw material. In addition to mixing with the conductor before the tempering of the pulverizing furnace (step 3) (step 2, the solid line part), it is also possible to add the smelting tin raw material after the temperature of the centrifugal furnace is heated to melt the conductor (Fig. 1) Step 2: the dotted line part). In addition, a part of the smelting and smelting materials may be first mixed with the conductor, and after the temperature of the pulverizing furnace is raised, the remaining smelting tin raw materials may be added to the pulverizing furnace in whole or in batches ( Step 2: solid line and broken line). The metal tin is smelted by the method of the present invention, wherein the source of the tin-containing compound 15 is not limited to the tin mud produced by the treatment of the tin (lead) waste liquid, and 15 Tin-rich tin, various tin compounds, tin slag from surface mount (SMT), tin-plated tin and tin-plated slag for printed circuit boards, tin-tin or other mixtures of tin-plated tin, and tin-containing If the raw material contains , iron, wrong metal, or a mixture thereof, does not affect the use of the method of the present invention. The carbon-containing compound as a reducing agent may be coke, charcoal, active 2 〇 <, anthracite, graphite, black Tobacco, paper and categorization or mixtures thereof, and smelting and refining auxiliaries may be fluorinated, oxidized, saponin, oxidized, oxidized glass, quicklime, iron oxide, magnesium oxide, etc. or mixtures thereof In the following, the method of the present invention will be described in detail in several embodiments. 7 1250214 <Example 1> Take i623g dry tin mud produced by treating the stripping waste liquid, containing 60% tin 'added 4〇〇g sodium carbonate is used as a reducing agent for smelting auxiliaries and activated carbon, and is mixed to form smelting tin raw materials. First, add 370g of metal tin with a degree of 92%, and make it in the furnace of the Zhoubo furnace. It has magnetic permeability, then raises the smelting temperature to a temperature at which a redox reaction can be generated, and then the above-mentioned prepared smelting tin raw materials are fed in three batches, each batch is kept at a small interval, the total reaction time is 4 hours, and a total of smelting is obtained to obtain n59g. Purity is 92 % of metal tin, the metal tin block is shown in Figure 2, where the tin recovery rate is 74.5%. The volume of the centrifugal furnace used in the preferred embodiment is 10 L (liter), the output power of the large-scale furnace is 5 〇 kW (瓧), the frequency of the centrifugal furnace is set to 3000 Hz (hertz), and the smelting temperature is ΐ2 〇 (μΐ3〇〇°). 0. <Example 2> 15 Take 1623 g of dry tin mud produced by treating the stripping waste liquid, containing 60% tin, adding 950 g of tin metal having a purity of 92%, and adding i〇〇g sodium carbonate as Smelting auxiliaries, and using l〇〇g coke powder, 5〇g charcoal and 5〇g of living carbon as reducing agent, and mixing, then all are added to the crucible of the coke oven, and then the smelting temperature is raised. To the temperature of 20 ° which can produce redox reaction, after 2 hours of reaction time, a total of I900g of tin metal with a purity of 92% is obtained by smelting. The perspective view of the metal tin block is shown in FIG. 3, wherein the tin recovery rate is 89.8. The volume of the centrifugal furnace used in the preferred embodiment is 10 L, the maximum output power is 50 kW, the frequency of the surge furnace is set to 3000 Hz, and the smelting temperature is 1200-1300 ° C. 1250214 <Example 3> ίο 15 20
取2350g因電子業表面構裝（SMT)所產生的錫渣，該 錫渣含59%錫與31%鉛，添加3〇〇g純度為92%的金屬錫， 5〇g奴酸鈉、40g氧化鎂、3〇g氧化鐵作為冶煉助劑，並以 i〇〇g焦碳粉及20g焦碳粉作為還原劑，並予以摻拌，之後 全部加料至週波爐的坩鍋中，然後提升冶煉溫度至可產生 氧化還原反應的溫度，經2小時的反應時間後，總共冶煉 製得2612g錫鉛合金，該錫鉛合金含62%錫與％%鉛，錫 與鉛的回收率分別為97.4%與93·2%。冶煉程序後段的撈 渣過程與除渣後的金屬湯液如圖4與圖5所示。本較佳實 施例中所使用的週波爐容積為1〇L，最大輸出功率為5〇 kW，週波爐頻率設定為3〇〇〇Hz，冶煉溫度為η⑼—η⑼ °C。 歸納上述，本發明之自含錫化合物中冶煉金屬錫的方 法利用週波爐提供能源，將含錫化合物與含碳化合物及 冶煉助劑摻拌混合，而在高溫下冶煉還原得金屬錫，利用 本發明所提供的方法，在整個冶煉的過程中，提高了錫回 收率，並能降低冶煉廢氣及爐渣的產生量，故確實能達到 本下明的目的。 9 1250214 【圖式簡單說明】 圖1是本發明自含錫化合物中冶煉金屬锡的方法的流 粒圖， 圖2是本發明 之弟一較佳實施例所冶煉製得的金屬錫 塊的立體圖； 圖疋本發明之第二較佳實施例所冶煉製得的金屬錫 塊的立體圖； 圖4是本發明之第三較佳實施例冶煉程序後段的撈渣 過程；以及 圖5疋本發明之第三較佳實施例冶煉程序除清後所獲 得的金屬湯液。 15【圓式之主要元件代表符號說明】 步驟 10Take 2350g of tin slag produced by surface mount (SMT) of the electronic industry. The tin slag contains 59% tin and 31% lead, and 3 〇〇g of 92% pure metal tin, 5 〇g sodium sulphate, 40g Magnesium oxide and 3〇g iron oxide are used as smelting auxiliaries, and i〇〇g coke powder and 20g coke powder are used as reducing agents, and are mixed, and then all are added to the crucible of the coke oven, and then the smelting is improved. The temperature reached a temperature at which a redox reaction could be produced. After a reaction time of 2 hours, a total of 2612 g of tin-lead alloy was obtained, which contained 62% tin and %% lead, and the recovery rates of tin and lead were 97.4%, respectively. With 93.2%. The slag-removing process in the latter stage of the smelting process and the metal broth after slag removal are shown in Figs. 4 and 5. The volume of the centrifugal furnace used in the preferred embodiment is 1 〇L, the maximum output power is 5 〇 kW, the frequency of the surge furnace is set to 3 〇〇〇 Hz, and the smelting temperature is η (9) - η (9) ° C. In summary, the method for smelting metal tin from the tin-containing compound of the present invention uses a centrifugal furnace to provide energy, and the tin-containing compound is mixed with the carbon-containing compound and the smelting aid, and the metal tin is smelted and reduced at a high temperature. The method provided by the invention improves the tin recovery rate and reduces the amount of smelting waste gas and slag generated during the whole smelting process, so that the purpose of the present invention can be achieved. 9 1250214 BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart of a method for smelting metallic tin from a tin-containing compound of the present invention, and FIG. 2 is a perspective view of a metal tin block obtained by smelting a preferred embodiment of the present invention. Figure 3 is a perspective view of a metal tin block obtained by smelting a second preferred embodiment of the present invention; Figure 4 is a slag removing process in a subsequent stage of the smelting process of the third preferred embodiment of the present invention; and Figure 5 The third preferred embodiment is a smelting process in addition to the metal soup obtained after the clarification. 15 [Description of the main components of the circle] Step 10