經濟部中央榡準局員工消費合作社印製 312707 A7 B7 五、發明説明（1 ) 本發明是有關將電子產品製程中經由電鍍過程而衍生 的焊錫廢液内的焊錫金屬予以回收之方法。由於對焊錫廢液 内焊錫金屬的回收技術尚未有所成就，因此焊錫廢液通常在 未經處理之下就由工廠排放而出，對環境造成重大污染。而 本發明在經由簡易的各步驟製程後即可有效地回收焊錫金 屬，並減低廢液對環境的污染程度。 在現今電子產品的生產製程中，尤其是在電子構裝製程 的步驟中，都會大量使用焊錫（鉛-錫合金），除了因應導電 性、機械強度以及疲勞壽命的考量外，主要是爲了因應在電 子元件製程中，溫度不能太高的要求，以焊錫之共晶組成（63 錫-37鉛）爲例，其熔點爲183 °C，即使是含有高濃度鉛的組 成（95鉛-5錫），其液相點亦小於320 °C (見 M.Hansen,K.Anderko,"Constitution of Binary Alloys" ,Me Graw-ffill,New York, 1989,P.1106.)。共晶焊錫最常鍍於 接腳，印刷電路板線路或打線接點等處，而就製程而言，可 利用波焊、蒸鍍或電鍍方式所進行，其中屬電鍍方式的應用 最爲久遠並且已臻成熟，因此被大量應用在印刷電路板的生 產製程中。 雖然，電鍍技術已被廣泛利用，但在電鍍的製程中最大 的問題就是電鍍廢液的處理或是在製造電路板的蝕刻過程 所產生的廢液與沈澱物的處理。在廢液處理的習知技術中， 是將焊錫廢液或其它含焊錫成份的廢液，例如：蝕刻液等， 給予適當的沈澱，使排放液内的重金屬含量合乎預定的排放 標準，但沈澱後的沈澱物卻仍缺乏適當的處理方法，根據目 3 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐〉 (請先閱讀背面之注意事項再填寫本頁) 丨裝------訂----('·線 經濟部中央標準局員工消費合作社印製 3J2707 A7 B7 五、發明説明（2 ) 前的方法是將沈澱物予以掩埋，可是掩埋沈澱物將會造成環 境的污染。因此本發明即針對含焊錫成份的廢液予以沈澱， 並將沈澱物適當處理而回收高價値的焊錫金屬，並藉以避免 廢液及沈澱物對環境的污染。 由於電鍍製程及蝕刻製程所產生的含烊錫廢液都大多 以沈澱方式處理，但運用此方式後所得的沈澱物都是屬於化 合物的狀態，而且多爲穩定的化合物，例如：水合氧化物或 氫氧化物等，此類化合物將不易以電子還原方式予以還原回 收。因此，本發明係利用高溫熔煉還原方式將焊錫沈澱物予 以還原回收，本方式不但克服習知技術的缺點，並且在製程 中亦無空氣煙塵的產生，所以將毫無空氣污染之虞。 在電鍍焊錫或純錫的製程中，清洗鍍件後會產生含有 鉛、錫成份的廢液，電鍍液在使用一段時間後，若不能保持 穩定則會產生高金屬濃度的濃厚酸性廢液，以及例如在印刷 電路板等物件時，蝕刻後也會生成濃厚的酸性廢液甚或沈澱 物，諸如此類的酸性廢液大抵以沈澱方式處理而使排放液符 合法定的放流標準，但是，最終仍會剩餘下有害的沈滅;物。 在這些沈澱物中，主要是以鉛、錫的水合氧化物或氫氧 化物爲主成份，此些成份其實當屬於具有高利用價値的礦 源，因此不論從環保角度亦或資源回收的角度觀之，都値得 並且也應當予以回收處理。以焊錫的主成份：鉛、錫而言， 天然的鉛礦以閃鉛礦（Galena，PbS)爲主，而錫礦 (Cssiterite,SnO)則是金屬錫之主要來源，在提煉過程中，閃 奶療經锻燒（Roasting)後，再經高爐還原而成敍金屬，而錫 4 ---------1 I裝---- (請先閱讀背面之注意事項再填寫本頁)Printed by the Employee Consumer Cooperative of the Central Bureau of Economics of the Ministry of Economic Affairs 312707 A7 B7 V. Description of the invention (1) The present invention relates to a method for recovering solder metal in solder waste liquid derived from the electroplating process in the manufacturing process of electronic products. Since the recovery technology of solder metal in the solder waste liquid has not yet been achieved, the solder waste liquid is usually discharged from the factory without treatment, causing great pollution to the environment. However, the present invention can effectively recover the solder metal after a simple step process and reduce the degree of environmental pollution caused by the waste liquid. In the production process of today's electronic products, especially in the steps of the electronic assembly process, a large amount of solder (lead-tin alloy) is used. In addition to the consideration of conductivity, mechanical strength and fatigue life, it is mainly to respond to In the manufacturing process of electronic components, the temperature should not be too high. Take the eutectic composition of solder (63 tin-37 lead) as an example, its melting point is 183 ° C, even if it contains a high concentration of lead (95 lead-5 tin) , Its liquidus point is also less than 320 ° C (see M. Hansen, K. Anderko, " Constitution of Binary Alloys ", Me Graw-ffill, New York, 1989, P.1106.). Eutectic solder is most often plated on pins, printed circuit board circuits or wire bonding contacts, etc., and as far as the manufacturing process is concerned, wave soldering, evaporation or electroplating can be used. Among them, the application of electroplating is the longest and It has matured, so it has been widely used in the production process of printed circuit boards. Although the electroplating technology has been widely used, the biggest problem in the electroplating process is the treatment of electroplating waste liquid or the treatment of waste liquid and sediment produced during the etching process of manufacturing circuit boards. In the conventional technology of waste liquid treatment, solder waste liquid or other waste liquid containing solder components, such as etching liquid, is given an appropriate precipitation to make the heavy metal content in the discharge liquid meet the predetermined discharge standard, but the precipitation After the sediment is still lack of proper treatment method, according to the third paper size, the Chinese national standard (CNS) A4 specification (210X297 mm) is applicable (please read the precautions on the back and fill in this page) 丨 Installation --- --- book ---- ('· Printed 3J2707 A7 B7 by the Employees ’Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Description of the Invention (2) The previous method was to bury the sediment, but burying the sediment will cause the environment Therefore, the present invention aims at precipitating the waste liquid containing solder components, and appropriately treating the precipitate to recover high-value solder metal, and thereby avoiding the pollution of the waste liquid and the sediment to the environment. Due to the electroplating process and the etching process Most of the tin-containing waste liquid produced is treated by precipitation, but the precipitates obtained after using this method are all in the state of compounds, and they are mostly stable compounds. Such as: hydrated oxides or hydroxides, etc., such compounds will not be easily recovered by electron reduction. Therefore, the present invention utilizes high-temperature smelting reduction to restore and recover solder deposits, which not only overcomes the conventional techniques Disadvantages, and there is no air smoke in the process, so there is no risk of air pollution. In the process of electroplating solder or pure tin, waste liquid containing lead and tin components will be generated after cleaning the plated parts. After being used for a period of time, if it is not stable, it will produce thick acidic waste liquid with high metal concentration, and for example, in printed circuit boards, etc., thick acidic waste liquid or even precipitates will be generated after etching, etc. It is probably treated by precipitation to make the discharge meet the legal discharge standards, but in the end, harmful sediments will still remain. In these precipitates, mainly hydrated oxides or hydroxides of lead and tin are used as The main ingredients, these ingredients actually belong to the ore source with high utilization value, so no matter from the perspective of environmental protection or resource recovery From the angle of view, both are worthwhile and should also be recycled. In terms of the main components of solder: lead and tin, natural lead ore is mainly Galena (PbS), while tin ore (Cssiterite, SnO) It is the main source of metal tin. During the refining process, after flash milk therapy is roasted, it is reduced by blast furnace to form metal, and tin 4 --------- 1 I equipment- -(Please read the notes on the back before filling this page)
、1T in 線 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 經濟部中央標準局員工消費合作社印製 312707 A7 B7 五、發明説明（） 3 礦經由焦碳大約在1100 °c下還原成錫金屬。但由於含鉛、 錫成份的廢液經處理後所得的錫、鉛沈澱物化學組成與夭 然錫、鉛礦源的化學組成不同。因此使用於錫、鉛天然礦 源的提煉過程並不適用於處理沈澱物中的錫、鉛金屬。本 發明的目的即是採用一回收製程用以將濃厚酸性廢液予以 適當沈澱，並將此沈澱物與電鍍烊錫蝕刻所產生的沈澱物 中的焊錫成份一併還原成純金屬焊錫而給予回收。 本發明的特徵主要是：（1)中和沈澱處理步驟可以處理 含高濃度鉛、錫金屬離子的廢液（lOOOppm以上乃至 lOOOOppm以上）；（2)轉化處理是將沈澱物中的焊錫金屬轉 化成氧化態而能緊接著進行還原處理；（3)還原處理步驟不 會產生任何的有害煙塵；以及（4)還原處理步驟的操作溫度 低於傳統自錫礦提煉錫的操作溫度。 本發明利用酸鹼中和法將廢液中所含的鉛、錫金屬沈 殿，此廢液可爲強酸性的廢液，其酸驗値(pH値）小於一般 酸驗儀（pH meter)所能偵測的範圍，此廢液中所含的错、錫 金屬離子濃度分別高達數萬個ppm，在經過中和沈澱後， 可使百分之99以上的金屬離子一次沈澱下來，利用過濾收 集後，將沈澱物給予適當之水洗再予以烘乾以使沈澱物能 緊接進行轉化及還原處理等步驟。 已烘乾之沈澱物必須接受適當的高溫轉化處理，此步 驟是絕對必須的，否則後續的還原處理就不易成功。在轉 化之後，將沈澱物與含碳的還原料共置於容器内（例如坩鍋 等）以進行還原處理，在一段時間之後就可獲得焊錫金屬。 5 (請先閱讀背面之注意事項再填寫本頁) 線 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 經濟部中央標準局貝工消費合作社印製 312707 1}餘正 年月 α ， a? __. Β7__ 五、發明説明（4 ) 在轉化處理時，其轉化溫度可在600〜750 °C之間，而轉化 時間介於2〜10小時，另外在還原處理時，還原溫度為 800〜950 °C之間，還原時間介於1.5~3小時；還原處理用的 還原料可為含碳的物質，例如各類碳粉。 以下將以圖示配合實施例，做本發明之詳細說明： 圖示之簡單說明： 根據本發明的製程，其流程如第1圖所示。 第2圖是本發明實施例一之滴定圖。 第3圖是本發明實施例二之滴定圖。 第4圖是本發明實施例三所獲得之沈澱物的外觀圖； 第5圖是依本發明實施例四所得之銲錫金屬與一沈澱 凝塊的外觀比較圖。 在本發明的流程圖中，各步驟的說明如下： 步驟1是含有鉛、錫金屬之廢水（或稱廢液），例如電鍍 廢水；步驟3則是含有鉛、錫金屬的廢水中亦夾雜有鉛、 錫金屬的沈澱物（例如：在印刷電路板製作線路的生產過程 中使用適當之錫、鉛蝕刻液所蝕刻之錫、鉛可能因濃度高 於飽和濃度而生成的沈澱物），經過濾（步驟4)以將沈澱物 (步驟8)與廢水（步驟5)分離，如此所得之廢水以及步驟1 之廢水皆可以利用本發明所述之沈澱方式加以沈澱（步驟 2)，在中和沈殿處理中為添加4~6N的氫氧化納溶液 (NaOH)，例如5N之氫氧化鈉溶液或1-3M的碳酸鈉溶液 (Na2C03)，例如利用2M之碳酸鈉溶液以進行本處理的中和 沈澱。在中和沈澱處理中，若鹼液濃度低於上述之下限， 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 裝. 訂 A7 B7 五、發明説明（5 ) " 則製程需要耗費大量的水，不甚經濟，而若濃度大於上限， ，會因濃度變化太快而不易控制最終所需的酸鹼値於— 定範圍之内。當廢液的酸鹼値調整至pH1〇〜u時，則烊锡 金屬離子幾乎可以完全沈澱下來。本沈澱處理的反應式如 下：、 1T in linear paper scale is applicable to China National Standard (CNS) A4 specification (210X297mm). Printed by the Employees ’Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 312707 A7 B7 V. Description of invention () 3 The mine is about 1100 ° C via coke Reduced to tin metal. However, the chemical composition of the tin and lead precipitates obtained after the treatment of the waste liquid containing lead and tin components is different from that of the raw tin and lead mines. Therefore, the extraction process used in tin and lead natural ore sources is not suitable for the treatment of tin and lead metals in the precipitate. The purpose of the present invention is to use a recycling process to properly precipitate the thick acidic waste liquid, and to restore this precipitate together with the solder component in the precipitate produced by the electroplating tin etching to pure metal solder and give it back . The features of the present invention are as follows: (1) The neutralization and sedimentation treatment step can process waste liquid containing high concentrations of lead and tin metal ions (more than 1000 ppm or even more than 1000 ppm); (2) The conversion treatment is to convert the solder metal in the precipitate In the oxidation state, the reduction treatment can be carried out immediately; (3) The reduction treatment step does not produce any harmful fumes; and (4) The operation temperature of the reduction treatment step is lower than that of the traditional tin extraction from tin ore. The invention utilizes the acid-base neutralization method to sink the lead and tin metal contained in the waste liquid. This waste liquid can be a strong acid waste liquid, and its acid test value (pH value) is less than that of a general acid test instrument (pH meter). The range of detection, the concentration of chromium and tin metal ions contained in this waste liquid is as high as tens of thousands of ppm respectively. After neutralizing Shendian, more than 99% of metal ions can be precipitated at one time and collected by filtration After that, the precipitate is washed with appropriate water and then dried so that the precipitate can be immediately followed by steps such as conversion and reduction treatment. The dried precipitate must undergo proper high-temperature conversion treatment. This step is absolutely necessary, otherwise the subsequent reduction treatment will not be successful. After the conversion, the precipitate and the carbon-containing raw material are placed together in a container (such as a crucible, etc.) for reduction treatment, and the solder metal can be obtained after a period of time. 5 (Please read the precautions on the back before filling in this page) The size of the line paper is in accordance with the Chinese National Standard (CNS) A4 (210X297mm) Printed by Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 312707 1} α ， a? __. Β7__ V. Description of the invention (4) During the conversion process, the conversion temperature can be between 600 ~ 750 ° C, and the conversion time is between 2 ~ 10 hours, and in the reduction process, the reduction temperature It is between 800 and 950 ° C, and the reduction time is between 1.5 and 3 hours; the raw materials for reduction treatment can be carbonaceous substances, such as various types of carbon powder. The following is a detailed description of the present invention with the help of examples in conjunction with the drawings: A brief description of the drawings: According to the manufacturing process of the present invention, the flow is shown in FIG. Figure 2 is a titration chart of the first embodiment of the present invention. Figure 3 is a titration chart of Example 2 of the present invention. Fig. 4 is an external view of the precipitate obtained in Example 3 of the present invention; Fig. 5 is a comparative view of the appearance of the solder metal obtained in Example 4 of the present invention and a precipitated clot. In the flow chart of the present invention, the description of each step is as follows: Step 1 is the wastewater (or waste liquid) containing lead and tin metal, such as electroplating wastewater; Step 3 is the wastewater containing lead and tin metal is also mixed Precipitations of lead and tin metals (for example: the use of appropriate tin in the production process of printed circuit board fabrication, the etching of tin and lead that may be generated due to the concentration higher than the saturation concentration) (Step 4) In order to separate the sediment (Step 8) from the wastewater (Step 5), both the wastewater thus obtained and the wastewater of Step 1 can be precipitated by the precipitation method described in the present invention (Step 2), in which The treatment is to add 4 ~ 6N sodium hydroxide solution (NaOH), such as 5N sodium hydroxide solution or 1-3M sodium carbonate solution (Na2C03), for example, use 2M sodium carbonate solution for the neutralization of Shendian . In the process of neutralizing Shendian, if the lye concentration is lower than the above lower limit, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) (please read the precautions on the back before filling this page). A7 B7 V. Description of the invention (5) " The process requires a lot of water consumption, which is not economical, and if the concentration is greater than the upper limit, it will be difficult to control the final required acid-base value due to the concentration change in a fixed range within. When the acid-base value of the waste liquid is adjusted to pH 10 to u, the tin metal ions can almost completely precipitate. The reaction formula of this precipitation treatment is as follows:
Sn2++ 20H- — Sn(OH)2 (沈澱） pb2++20H_ — Pb(OH)2 (沈藏） 經步驟2沈澱處理後之溶液再經過濾（步驟後，其排 放液所含的金屬量已低於250Ppm，此棑放液（步驟7)應送 至廢水處理廠處理之；過濾後所得的沈澱物（步驟8)經水清 洗（步驟9)以去除所含有的驗液，再經過遽後（步騄1〇)，將 清洗排放液（步驟11)排放，此時沈殿物（步驟12)在7〇〜8〇 C下乾燥（步驟13)以去除水份後，需利用600〜750 °C之間 的溫度以進行熱轉化處理（步驟14)2〜10小時，例如3小 時，若轉化之溫度或時間低於上述之下限，則將造成沈澱 物内焊錫金屬轉化的不完全，使後續的金屬還原率甚低抑 或失敗，而若轉化之温度或時間高於上述之上限，則徒然 造成能源的浪費。本轉化處理的反應式爲：Sn2 ++ 20H- — Sn (OH) 2 (precipitation) pb2 ++ 20H_ — Pb (OH) 2 (sedimentation) The solution after the precipitation treatment in step 2 is then filtered (after the step, the amount of metal contained in the discharge liquid has been Below 250Ppm, this discharge liquid (step 7) should be sent to the wastewater treatment plant for treatment; the precipitate obtained after filtration (step 8) is washed with water (step 9) to remove the contained test liquid, and then passed through (Step 10), discharge the cleaning discharge liquid (Step 11), at this time Shen Dianwu (Step 12) is dried at 70 to 8 ° C (Step 13) to remove moisture, and 600 to 750 ° The temperature between C and 2 to 10 hours for the thermal conversion treatment (step 14), for example 3 hours, if the conversion temperature or time is lower than the above lower limit, it will cause the incomplete conversion of the solder metal in the precipitate, making the subsequent The metal reduction rate is very low or fails, and if the conversion temperature or time is higher than the above upper limit, it will waste energy in vain. The reaction reaction of this conversion treatment is:
Sn(OH)2—加熱轉化Sn0 + H20 Pb(OH)2-> 加熱轉化Pb0 + H20 經步驟14轉化後之氧化物，再經步驟15之還原處理 後即可獲得焊錫金屬；在還原處理中使用的還原劑爲含碳 的物質，例如各種碳粉，碳粉覆蓋於氧化物上，防止已還 原的金屬再與空氣接觸而氧化，並且由於破粉本身在氧化 7 本紙張尺度適用中國國家梂準（CNS ) A4规格（210X297公釐） — — — — 裝 ~~ ^ {請先閲讀背面之注意事項再填寫本頁) 打 經濟部中央標準局員工消費合作社印策 A7 S127Q7 B7 五、發明説明（6 ) 時會放熱，加上在此還原過程中的沈澱物已先經過步驟14 之轉化處理，因此這個過程中不會有其它雜質產生，並不 須如一般痛物炫煉時添加造渔劑（Slagging agent)，造成爐 渣而消耗部分能源，所以本發明的還原處理所需溫度只須 介於800〜950 °C之間，還原處理時間爲1.5〜3小時，若溫 度低於此下限，則還原無法進行，若時間低於此下限，則 還原率會降低，當溫度或時間高於上述上限時，一方面會 浪費能源，另一方面會使已還原的鉛、錫金屬揮發甚或在 碳粉消耗殆盡後，原先已還原的錫、鉛金屬會再度被氧化， 因此還原溫度與還原時間的控制極爲重要。本還原處理的 反應式爲：Sn (OH) 2—heating to convert Sn0 + H20 Pb (OH) 2-> heating to convert Pb0 + H20 to oxide after conversion in step 14 and then after reduction treatment in step 15 to obtain solder metal; in reduction treatment The reducing agent used in the carbon-containing substances, such as various carbon powders, which are covered with oxides, prevent the reduced metal from being oxidized by contact with the air, and the broken powder itself is oxidized. 7 This paper size is suitable for China Standard (CNS) A4 specification (210X297mm) — — — — Installed ~~ ^ {Please read the precautions on the back before filling out this page) Call the A7 S127Q7 B7 printed by the Consumer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Invention Note (6) will release heat, plus the precipitate in the reduction process has been converted by step 14, so no other impurities will be generated in this process, and it does not need to be added as a general pain object. Slagging agent causes slag and consumes part of the energy, so the temperature required for the reduction treatment of the present invention only needs to be between 800 ~ 950 ° C, and the reduction treatment time is 1.5 ~ 3 hours, if the temperature is lower than this lower limit The reduction cannot be carried out. If the time is lower than this lower limit, the reduction rate will be reduced. When the temperature or time is higher than the above upper limit, on the one hand, energy will be wasted, on the other hand, the reduced lead and tin metals will evaporate or even carbon After the powder is exhausted, the tin and lead metals that have been reduced will be oxidized again. Therefore, it is extremely important to control the reduction temperature and reduction time. The reaction formula of this reduction treatment is:
SnO + C Sn + CO 或 C02SnO + C Sn + CO or C02
PbO + C — Pb + CO 或 C02 以下爲本發明部份之實施例： 實施例一 取用高達39560ppm錫離子濃度以及28100ppm鉛離子 濃度的廢液，利用5N的氫氧化鈉溶液中和沈澱處理（步驟 2)，如第2圖所示，其原始酸鹼値(pH値）幾乎爲零，實際 上爲酸驗儀（pH meter)不易偵測之範圍，利用氬氧化納溶液 中和廢液至酸鹼値達pHIO〜11左右，即可將溶液中的錫含 量降低至250ppm，亦即百分之99以上的踢已經沈殿而聚 集於沈澱物中。 實施例二 取用與實施例一相同的廢液，其鉛含量高達 8 本紙張尺度適用中國國家標準（CNS > Α4規格（210X297公嫠） (請先閱讀背面之注意事項再填寫本頁) 裝-PbO + C — Pb + CO or C02 The following are some examples of the present invention: Example 1 uses waste liquid with a concentration of up to 39,560 ppm of tin ions and a concentration of 28,100 ppm of lead ions, using 5N sodium hydroxide solution to neutralize Shendian treatment ( Step 2) As shown in Figure 2, the original pH value is almost zero, which is actually a range that is difficult to be detected by a pH meter. The sodium hydroxide solution is used to neutralize the waste liquid to When the acid-base value reaches about pHIO ~ 11, the tin content in the solution can be reduced to 250ppm, that is, more than 99% of the kick has been deposited in the precipitated hall. Example 2 The same waste liquid as Example 1 is used, and its lead content is as high as 8. The paper standard is applicable to the Chinese national standard (CNS > Α4 specification (210X297 public daughter) (please read the precautions on the back before filling this page) Outfit-
、1T 經濟部中央標準局員工消費合作社印製, Printed by 1T Employee Consumer Cooperative of Central Bureau of Standards, Ministry of Economic Affairs
經濟部中央標準局貞工消費合作社印製 28100ppm ’利用2M的碳酸鈉溶液進行中和沈殿處理（步驟 2)，如第3圖所示（僅繪製經中和沈澱處理而使鉛離子濃度 降至450ppm以下範圍的溶液成份圖）’此廢液之原始酸驗 值亦超出酸驗儀所能彳貞測之強酸，在添加一定量的2M碳酸 鈉溶液後，調整廢液的酸鹼值至ρΗ1〇〜11 ’則廢液中的鉛 含量可降至10〇PPm ’亦即百分之99以上的船均可經沈殿 而聚集至沈澱物中。 實施例三 與前實施例相同的廢液，經中和沈澱處理（步驟2)，其 沈澱物（步驟8)在乾燥（步驟13)後的外觀如第4圖所示，沈 澱物乾燥後會凝聚成碎塊。 實施例四 如實施例三所獲得之沈澱物，在適當溫度，例如 600〜750 °C之間，經轉化（步驟14)2〜10小時之後，加入含 碳的還原料，例如各種碳粉，於還原溫度800〜950。〇之間 及還原時間1.5~3小時内進行還原處理（步驟15)，即可獲致 如第5圖所示之焊錫金屬（步驟16)，其外觀與沈澱凝塊作一 比較，如第5圖所示。 實施例五 電鍍63錫-37鉛（63Sn-37Pb)焊錫的蝕刻製程所產生之 沈澱（步驟3、4、8)，經過本發明之製程，在還原處理（步 驟15)之後’所得之焊錫成份為61錫_39鉛（61Sn 39pb)(步 驟 16)。 雖然本發明已以較佳實施例揭露如上，然其並非用以 限定本發明，任何熟習此項技藝者’在不脫離本發明之精 9 本紙張歧適用獻嫌Γ). --- (請先閲讀背面之注意事項再填寫本頁) 袈. ^12707 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（8 ) 神和範圍内，當可作些許之更動與潤飾，因此本發明之保 護範圍當祝後附之申請專利範圍所界定者爲準。 (請先閱讀背面之注意事項再填寫本頁) 裝· 訂 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）Printed 28100ppm by Zhengong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs' Use 2M sodium carbonate solution to neutralize Shen Dian (step 2), as shown in Figure 3 (only the neutralized Shen Dian is processed to reduce the concentration of lead ions Solution composition diagram below 450ppm) 'The original acid test value of this waste liquid also exceeds the strong acid measured by the acid tester. After adding a certain amount of 2M sodium carbonate solution, adjust the pH value of the waste liquid to pH 1 〇 ~ 11 ', the lead content in the waste liquid can be reduced to 10〇PPm', that is, more than 99% of the ships can accumulate in the sediment through Shen Dian. Example 3 The same waste liquid as the previous example, after neutralizing Shendian treatment (step 2), the appearance of the precipitate (step 8) after drying (step 13) is shown in Figure 4, after the precipitate is dried Condensed into pieces. Example 4 The precipitate obtained in Example 3 is added at a suitable temperature, for example between 600 and 750 ° C, after conversion (step 14) for 2 to 10 hours, a carbon-containing raw material, such as various carbon powders, is added. At a reduction temperature of 800 ~ 950. Between 〇 and the reduction time of 1.5 ~ 3 hours (step 15), you can get the solder metal as shown in Figure 5 (Step 16), and its appearance is compared with Shendian clot, as shown in Figure 5 As shown. Embodiment 5 The precipitation (steps 3, 4, and 8) produced by the plating process of 63 tin-37 lead (63Sn-37Pb) solder, after the reduction process (step 15) through the process of the present invention, the resulting solder composition It is 61 tin_39 lead (61Sn 39pb) (step 16). Although the present invention has been disclosed as above with preferred embodiments, it is not intended to limit the present invention. Anyone who is familiar with this skill can apply Γ to this paper without departing from the essence of the present invention.) --- (Please Read the precautions on the back before filling in this page) 袈. ^ 12707 Printed by the Ministry of Economic Affairs Central Standards Bureau Employee Consumer Cooperatives A7 B7 V. Invention description (8) Within the scope of God and God, some changes and retouching can be done, so this The protection scope of the invention shall be as defined in the appended patent application scope. (Please read the precautions on the back before filling out this page) Binding · Order This paper size is applicable to China National Standard (CNS) A4 specifications (210X297mm)