TWI290181B - Electrolytic tank for treatment of wastewater with high-concentration cyanide - Google Patents
Electrolytic tank for treatment of wastewater with high-concentration cyanide Download PDFInfo
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- TWI290181B TWI290181B TW92126815A TW92126815A TWI290181B TW I290181 B TWI290181 B TW I290181B TW 92126815 A TW92126815 A TW 92126815A TW 92126815 A TW92126815 A TW 92126815A TW I290181 B TWI290181 B TW I290181B
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- electrolytic cell
- waste liquid
- cyanide
- treating
- high concentration
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- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000002351 wastewater Substances 0.000 title abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000010439 graphite Substances 0.000 claims abstract description 29
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 29
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 15
- 239000012212 insulator Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims description 46
- 239000002699 waste material Substances 0.000 claims description 46
- 239000004033 plastic Substances 0.000 claims description 18
- 229920003023 plastic Polymers 0.000 claims description 18
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 239000010931 gold Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000010117 shenhua Substances 0.000 claims 4
- 239000011810 insulating material Substances 0.000 claims 1
- 229910000510 noble metal Inorganic materials 0.000 abstract 1
- 239000010970 precious metal Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 208000028659 discharge Diseases 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101001026573 Homo sapiens cAMP-dependent protein kinase type I-alpha regulatory subunit Proteins 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000037118 bone strength Effects 0.000 description 1
- 102100037490 cAMP-dependent protein kinase type I-alpha regulatory subunit Human genes 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000010792 electronic scrap Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- Water Treatment By Electricity Or Magnetism (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
Description
1290181 五、發明說明（1) 【發明所屬之技術領域】 本發明有關一種含高濃度氰化物廢液的處理裝置，詳 言之’是有關一種用於處理含高濃度氰化物廢液之電解 槽。能夠同時達成處理含高濃度氰化物廢液及回收貴重金 屬粉末之雙重目的。 【先前技術】 電鍍業與金屬製品加工業產生含氰化物（氰系）廢水， 其特徵是廢水量大、氰化物含量低，濃度範圍1 〇〜1290181 V. INSTRUCTION DESCRIPTION OF THE INVENTION (1) Technical Field of the Invention The present invention relates to a treatment apparatus containing a high concentration of cyanide waste liquid, and in particular relates to an electrolysis tank for treating a waste liquid containing a high concentration of cyanide . It can achieve the dual purpose of treating high-concentration cyanide waste liquid and recovering precious metal powder at the same time. [Prior Art] The electroplating industry and the metal products processing industry produce cyanide-containing (cyanide) wastewater, which is characterized by large amount of wastewater and low cyanide content, and the concentration range is 1 〇~
15 0mg/i。使用習用方法二階段式鹼性加氣化法可有效處 理該種類之廢水，但是在處理階段中，易產生具有揮發性 且骨性為CN之1/3強之CNC1 ’屬於危險物質，稍有不慎易 危害操作人員。 目前電子產業興盛’電子廢料回收業因應而生，例如 錄金之印刷電路板、金手指、軟性基板、導線架、及变組 件等廢料回收，需配製高濃度氰化鈉溶液並添加剝金& \ 將錢金層剝離溶解後剩下底材，再從含金之剝離液進行 析與精煉回收純金。作業流程所產生之含氰化物廢液，复 特徵是廢水量少、氰化物含量高，濃度範圍3, 〇〇〇〜 、15 0mg/i. The two-stage alkaline gasification method can effectively treat the wastewater of this kind, but in the treatment stage, it is easy to produce CNC1 which is volatile and has a bone strength of 1/3 of CN. It is a dangerous substance, slightly Inadvertently jeopardizing the operator. At present, the electronics industry is booming. The electronic scrap recycling industry has been born. For example, the printing of printed circuit boards, gold fingers, flexible substrates, lead frames, and variable components for gold recording requires the preparation of high-concentration sodium cyanide solution and the addition of gold stripping &; \ After the gold layer is stripped and dissolved, the substrate is left, and then the gold-containing stripping solution is used for precipitation and refining to recover pure gold. The cyanide-containing waste liquid produced in the operation process is characterized by a small amount of waste water and a high cyanide content, and a concentration range of 3, 〇〇〇~,
6,00〇mg/l，且含有微量貴重金屬。若以習用’二階段式 性加氣化法處理，廢液必須先稀釋約5 〇 〇倍才能處理，二 加用水量及成本，$時所含微量貴重金屬將混成污泥曰 法问收。 7瘵 有利用平板式電析槽方法進行貴金屬回收，其陰極工 〇6,00 〇mg / l, and contains a trace of precious metals. If it is treated by the conventional two-stage gasification method, the waste liquid must be diluted by about 5 〇 〇 to be treated first. When the water consumption and cost are added, the trace amount of precious metals contained in the mixture will be mixed into the sludge. 7瘵 There is a plate type electrolysis cell method for precious metal recovery, and its cathode work
12901811290181
造成電流效率無法提 。因此，亦不適用於此 作面積較小，操作電流密度較高， 南，此現象在低濃度範圍更趨明顯 類廢水。 ” 〇有使用振盪式流體化電析槽（中華民國專利第1 45477 號’其專利權人與發明人亦為本案之申請人及發明人）於 回收氰系電鍍廢液中貴金屬及破壞其氰離子的電析裝置及 其^法，涉及一種陰極進行貴金屬回收，陽極進行氰離子 破壞分解的一振盪式流體化電析槽及其方法。但進行規模 放大廠型化時遇到了瓶頸，例如大型的振盪器須特別設計 =作，費時及成本高，且長時間負載高重量而振動，機件 容易損壞；陰極析出之責重金屬粉末無法排出，必須折卸 整槽石墨條清洗，操作繁複；多孔性塑膠管的孔隙會自發 還原結藏金屬垢，降低電解效率，甚至使陽極與陰極發^ 接觸而短路，因此尚需要改善。 【發明内容】 鑑於上述，本發明之目的是提供一種用於處理含高濃 度氰化物廢液之電解槽，可避免上述習知技術所遇到之$ 種問題’有效率的處理含氰化物廢水及回收貴重金屬。 本發明之用於處理含高濃度氰化物廢液之電解槽，包 括電解槽容器；至少一個陽極，位於該電解槽容器中，由 至少一支匯電石墨棒與複數個石墨粒所組成；至少—個降 極，位於該電解槽容器中，由至少一支金屬棒組成；至^ 一個多孔絕緣物，是用以防止該陽極與該陰極接觸；及_The current efficiency cannot be raised. Therefore, it is not suitable for this area, the operating current density is relatively high, and the phenomenon is more obvious in the low concentration range. 〇The use of an oscillating fluidized electrolysis cell (the Republic of China Patent No. 1 45477 'the patentee and the inventor is also the applicant and inventor of this case) recovers the precious metal and destroys the cyanide in the cyanide electroplating waste liquid. The ion electrolysis device and the method thereof relate to an oscillating fluidized electrolysis cell and a method thereof for recovering precious metal from the cathode and performing cyanide destruction and decomposition of the anode, but encountering a bottleneck when performing scale-up planting, for example, large-scale The oscillator must be specially designed to be time-consuming and costly, and it will vibrate for a long time with high weight and vibration, and the parts will be easily damaged. The metal powder of the cathode can not be discharged, and the graphite strip must be removed and cleaned, and the operation is complicated; The pores of the plastic tube spontaneously reduce the accumulated metal scale, reduce the electrolysis efficiency, and even short-circuit the anode and the cathode, and therefore need to be improved. SUMMARY OF THE INVENTION In view of the above, it is an object of the present invention to provide a treatment for An electrolytic cell containing a high concentration of cyanide waste liquid can avoid the problem of the above-mentioned prior art, and the efficient treatment of cyanide-containing Waste water and recovery of precious metals. The invention relates to an electrolytic cell for treating a high concentration cyanide waste liquid, comprising an electrolytic cell container; at least one anode, located in the electrolytic cell container, by at least one collecting graphite rod and a plurality of Graphite particles; at least one descending pole, located in the cell container, consisting of at least one metal rod; to a porous insulator to prevent the anode from contacting the cathode;
1290181 五、發明說明（3) 排放管，其 用以排放該 使用本 以電解方式 可進行氰離 原析出，底 達成處理含 放流水標準 具有低污染 大，具有極 具有至少一 電解槽中電 發明之用於 處理含高濃 子之氧化分 部排放管可 高濃度氰化 及回收貴重 、低成本、 高產業價值 個支管 解析出 處理含 度氰化 解，陰 間隔性 物廢液 金屬粉 高回收 連通於電解槽容器底部，是 之貴重金屬粉末。 南濃度氛化物廢液之電解槽 物廢液時，於電解槽之陽極 極可進行貴重金屬離子之還 排出貴重金屬粉末，而同時 至環境保護署（EPA)製訂之 末之雙重目的。故本發明極 率、操作容易，工業用途廣 【實施 為 顯易懂 本 一電解 而十腐I虫 一支以 時的陽 堆積中 佳為20 佳具有 棒（1 3 ) 電位適 方式】 明之上述和其他目的、特徵、和優點能更明 ，參考第1及2圖作詳細說明如下： 之用於處理含局濃度氰化物廢液之 槽容器（1 0 )，形妝另戸斗叮分 ^ &狀及尺寸可依所需而定，較佳選用 的材料，例如PVC塑膠等等。電解槽容器中有至少 ^的匯電石墨棒（11)及複數個石墨粒（12)組成電解 Ό各匯電石墨棒分開插置在複數個石墨粒形成的 ^石墨粒接觸而可電相連。棒匯電石墨棒的直徑較 mm及石墨粒的含碳量較佳為g 8至丨〇 〇重量％及較 边徑0· 2至10· 〇mm。電解槽容器中有至少一個金屬 做為陰極，金屬棒氧 ^ ^ 知了為例如選用耐腐蝕及氧化還原 且電解物之電解的材質，例如不鏽鋼管、鍍銥鈦管1290181 V. INSTRUCTIONS (3) Discharge pipe, which is used for discharging the use of the present invention, can be cyanide-precipitated by electrolysis, and has a low pollution level with the bottom discharge treatment standard, and has at least one electrolytic cell in the invention. It can be used to treat high-concentration oxidizing fraction discharge pipe, which can be used for high-concentration cyanidation and recovery of valuable, low-cost, high-industry value. The branch is treated with cyanide solution, and the high-recovery of waste metal powder At the bottom of the cell container is a precious metal powder. In the case of the electrolysis tank waste liquid of the concentration liquid in the south, the precious metal ions can be discharged from the anode of the electrolysis tank to discharge the precious metal powder, and at the same time, to the double purpose of the end of the Environmental Protection Agency (EPA). Therefore, the invention has the advantages of extreme rate, easy operation, and wide industrial use. [The implementation is easy to understand. The electrolysis of the ten rots and the worms of the worms are good. The best is 20 good with a good (1 3) potential mode] And other purposes, features, and advantages can be more clearly described with reference to Figures 1 and 2 as follows: The tank container (10) for treating the cyanide waste liquid containing the local concentration, the shape of the makeup and the other buckets are divided into ^ The shape and size can be determined as desired, and the preferred materials are, for example, PVC plastic. At least one of the electroconductive graphite rods (11) and the plurality of graphite particles (12) constitute electrolysis. Each of the converging graphite rods is inserted into the graphite particles formed by a plurality of graphite particles to be electrically connected. The diameter of the rod-shaped graphite rod is smaller than that of mm and the carbon content of the graphite particles is preferably g 8 to 丨〇 〇 by weight and the side diameter is from 0.2 to 10 · 〇 mm. The electrolytic cell container has at least one metal as a cathode, and the metal bar oxygen is known as, for example, a material which is resistant to corrosion and redox and electrolytic electrolysis, such as a stainless steel tube or a rhodium-plated titanium tube.
12901811290181
ί等。選用不鑛鋼管時，外徑可為例如2G至6Gmm。各金屬ί et al. When a non-mineral steel pipe is selected, the outer diameter may be, for example, 2G to 6Gmm. Various metals
0 ?而而疋，但須互相隔離，本發明中使用多孔 絕緣物（14)防止陽極與陰極的接觸，例如使用管狀多孔絕 緣物將金屬棒環繞在管中達成與石墨棒及石墨粒隔離之目 的。但是電解液（廢液）仍可經由絕緣物上的孔洞自由流動 在陰極與陽極之間，達到電解之目的。此多孔絕緣物可選 用夕孔性塑膠管，例如具有外徑3 〇至丨2 〇mm及孔徑2 〇至2 5 〇 之多孔性塑膠管，材質可為pE、pp、或pvDF塑膠等 等三電解時，金屬（尤其是貴重金屬）會在陰極（例如不鏽 ，官上）析出，但因陰極形狀、沉積的厚度及水流的沖擊 專因素’使彳于/儿積的金屬脫離不鏽鋼管以粉末狀往下沉 降’因此如圖所示，本發明尚包括一排放管（丨7 )以排放該 電解槽中電解析出之貴重金屬粉末。排放管可具有至少一 個支管（16)連通於該電解槽容器底部，較佳直接連通金屬 棒（13)(陰極）所在之管狀多孔絕緣物（14)，因此不會收集 到石墨殘渣，而便利於收集析出之貴重金屬粉末。排放管 可為外徑為5 0至1 5 0 mm，傾斜度5至6 0度，材質可為例如壓 克力、PP、或PVC等等。0, but 疋, but must be isolated from each other, the present invention uses a porous insulator (14) to prevent the anode from contacting the cathode, for example, using a tubular porous insulator to surround the metal rod in the tube to separate from the graphite rod and the graphite particles. purpose. However, the electrolyte (waste liquid) can still flow freely through the holes in the insulator between the cathode and the anode for the purpose of electrolysis. The porous insulator can be selected from a sinusoidal plastic tube, for example, a porous plastic tube having an outer diameter of 3 〇 to 2 〇 mm and a pore diameter of 2 〇 to 25 〇, and the material can be pE, pp, or pvDF plastic, etc. During electrolysis, metals (especially precious metals) are precipitated at the cathode (for example, stainless, officially), but due to the shape of the cathode, the thickness of the deposit, and the impact of the water flow, the metal is removed from the stainless steel tube. The powder settles down. Thus, as shown, the present invention also includes a discharge pipe (丨7) for discharging the precious metal powder which is electrically resolved in the electrolytic cell. The discharge pipe may have at least one branch pipe (16) communicating with the bottom of the electrolytic vessel vessel, preferably directly connected to the tubular porous insulation (14) where the metal rod (13) (cathode) is located, so that graphite residue is not collected, and the convenience is facilitated. The precipitated precious metal powder is collected. The discharge pipe can have an outer diameter of 50 to 150 mm and a slope of 5 to 60 degrees, and the material can be, for example, acrylic, PP, or PVC.
本發明之用於處理含高濃度氰化物廢液之電解槽更可 包括一進流口（ 2 0 )，較佳位於電解槽容器（1 〇 )的底部，做 為電解液（即，廢液）之入口，入口處可設置過濾裝置，例 如球形過濾網（2 1 )，防止石墨渣及其他殘渣流出孔外。在 電解槽容器（1 0 )的頂部可設置至少一個溢流裝置，在溢流The electrolytic cell for treating a high concentration cyanide waste liquid of the present invention may further comprise an inlet port (20), preferably located at the bottom of the cell tank (1 〇), as an electrolyte (ie, waste liquid) At the entrance of the inlet, a filtering device, such as a spherical filter (2 1 ), may be provided at the inlet to prevent graphite slag and other residues from flowing out of the hole. At least one overflow device may be provided at the top of the electrolytic cell vessel (10), in the overflow
1290181 五、發明說明（5) 處可設置過濾、裝置，例如球形過濾、網（2 4 )，而溢流槽（2 5 ) 貯存溢流的電解液（廢液），再由溢流孔（26)排放，較佳是 設置迴流裝置，使溢流液經由溢流管（27 )、再經由電解槽 底部的進流口（ 2 0 )迴流至電解槽容器（1 0 )中。 排放管的支管（1 6 )與管狀多孔絕緣物（1 4 )之銜接連 通，可使用例如塑膠由任（union)(15a)達成。 排放管（1 7 )的上端管口進一步可利用例如一端封閉的 由任（15b)蓋住，下端可裝置一排液閥（22)，可將廢液排 放，以及裝置一閥（2 3 )(例如蝶閥）以供貴重金屬粉末的排 放收集。1290181 V. INSTRUCTIONS (5) Filters and devices such as spherical filters and nets (2 4 ) can be installed, while overflow tanks (25) store the overflowing electrolyte (waste liquid) and then overflow holes ( 26) Discharge, preferably by providing a reflux device, such that the overflow liquid is returned to the electrolytic cell vessel (10) via the overflow pipe (27) and through the inlet (20) at the bottom of the electrolytic cell. The branch pipe (16) of the discharge pipe is in communication with the tubular porous insulation (14) and can be achieved, for example, by a plastic (15a). The upper end of the discharge pipe (17) can be further covered by, for example, one end (15b), the lower end can be equipped with a drain valve (22), the waste liquid can be discharged, and the device is a valve (2 3 ) (eg butterfly valves) for the collection of precious metal powder emissions.
利用本發明之用於處理含高濃度氰化物廢液之電解槽 進行廢液電解時之流程如下述：The flow of the waste liquid electrolysis using the electrolytic cell of the present invention for treating a liquid mixture containing a high concentration of cyanide waste liquid is as follows:
含高濃度氰化物廢液自循環貯槽以泵浦抽送，經廢液 經由進流口（ 2 0 )及球型過濾網（2 1 )進入電解槽（丨〇 )，於電 解槽（1 0 )的陽極（匯電石墨棒（1 1 )及石墨粒（丨2 ))將廢液所 含氰離子（CN-)進行氧化分解成N2與C〇2，於電解槽（1{J)的陰 極（不鏽鋼管（13))將廢液所含微量貴重金屬離子例如，农 金、鈀、銀、銅等，還原析出成貴重金屬粉末，掉落到貴 重金屬粉末排放管（丨7 )。每隔一段時間，先開啟底部排液 閥（22)( 口徑例如為3/4 ")，將電解槽（1〇)内廢液排空， 再開啟蝶閥（23)(例如口徑4 〃），將貴重金屬粉末排出收 ^廢液彳火電解槽（1 〇)的底部進入，由下往上擴散，經電 解槽（10)頂部的球型過濾網（24)流到溢流槽（2 經 流孔（2㈧及溢流管（27)流回循環貯槽，如此形成循^電凰The high-concentration cyanide waste liquid is pumped from the circulating storage tank, and the waste liquid enters the electrolytic tank (丨〇) through the inlet port (20) and the spherical filter (2 1 ) in the electrolytic cell (10) The anode (conducting graphite rod (1 1 ) and graphite particles (丨2)) oxidatively decomposes the cyanide ion (CN-) contained in the waste liquid into N2 and C〇2 at the cathode of the electrolytic cell (1{J) (Stainless steel tube (13)) reduces the amount of precious metal ions contained in the waste liquid, such as agricultural gold, palladium, silver, copper, etc., into a precious metal powder, and drops it to the precious metal powder discharge pipe (丨7). At regular intervals, first open the bottom drain valve (22) (for example, 3/4 "), empty the waste liquid in the electrolytic cell (1〇), and then open the butterfly valve (23) (for example, caliber 4 〃) The precious metal powder is discharged into the bottom of the waste smoldering electrolysis cell (1 〇), diffused from bottom to top, and flows through the spherical filter (24) at the top of the electrolytic cell (10) to the overflow tank (2 The flow hole (2 (eight) and the overflow pipe (27) flow back to the circulating storage tank, thus forming a loop
12901811290181
可-tn處理之含高濃度氰化物廢液’其氰化物濃度 叮间達約8,〇〇〇mg/L ，較佳之氰化物濃度範圍為 3’ OOOmg/L至6, 000mg/L 。氰化物去除效率可達99 %。 以下列實施例更進_步說明本發明。 實施例 請參閱第1及2圖所示，本發明之用於處理含高濃度氰 化物廢液之電解槽，該電解槽容器（1〇)的是厚度8mm的pvc 塑膠圓桶，直徑78cm、高90 cm。容器内部包含三支匯電石 墨棒（11)置入複數個石墨粒（1 2 )合併作為電解槽的工作陽 極，導電石墨棒（11)的直徑05〇_、長度84cm，複數個石 墨粒的含碳成份99·7%、粒度〜3 〇_、數量2〇〇 kg。谷為又包含六支不鏽鋼管（13)作為電解槽的工作陰 極，不鏽鋼管（13)的材質為SUS3〇4、外徑042· 7mm、厚度 2.0 mm、長度86cm。每支不鏽鋼管（13)的外圍各套有多孔 性塑膠管（14)，藉以將陽極（石墨粒12)與陰極（不鏽鋼管 1 3 )隔開’多孔性塑膠管（1 4 )的材質為pe塑膠、外徑0 7 0 · 4mm、厚度6. 5mm、長度84cm、孔徑Θ0微米。於電解槽容器 (10)的底部，每支多孔性塑膠管（14)的正下方出口，各焊 接有2 · 5 塑膠由任（1 5 )及一小段塑膠短管（1 6 )，再將各 小段塑膠短管（1 6 )'焊接匯集成一支傾斜1 &度的貴重金屬粉 末排放管（1 7 )，完成本發明之用於處理含高濃度氰化物廢 液之電解槽。 使用本發明處理含高濃度氰化物之廢液，電解時間、The high concentration cyanide waste liquid which can be treated with -tn has a cyanide concentration of about 8, 〇〇〇mg/L, and preferably has a cyanide concentration ranging from 3' OOOmg/L to 6,000mg/L. Cyanide removal efficiency can reach 99%. The invention is further illustrated by the following examples. For the embodiment, please refer to the electrolyzers for treating high-concentration cyanide waste liquid according to the first and second figures. The electrolytic cell container (1〇) is a pvc plastic drum with a thickness of 8 mm and a diameter of 78 cm. 90 cm high. The inside of the container contains three sets of graphite rods (11) and a plurality of graphite particles (1 2 ) are combined to serve as the working anode of the electrolytic cell. The diameter of the conductive graphite rod (11) is 05〇_, the length is 84cm, and the plurality of graphite particles are The carbon content is 99.7%, the particle size is ~3 〇_, and the quantity is 2〇〇kg. The valley contains six stainless steel tubes (13) as the working cathode of the electrolytic cell. The stainless steel tube (13) is made of SUS3〇4, outer diameter of 042·7 mm, thickness of 2.0 mm, and length of 86 cm. Each of the stainless steel tubes (13) is provided with a porous plastic tube (14), thereby separating the anode (graphite particles 12) from the cathode (stainless steel tube 13). The material of the porous plastic tube (1 4 ) is Pe plastic, outer diameter 0 7 0 · 4mm, thickness 6. 5mm, length 84cm, aperture Θ 0 microns. At the bottom of the electrolytic cell container (10), the outlet directly below each porous plastic tube (14) is welded with 2 · 5 plastics (1 5 ) and a short plastic short tube (16), and then Each of the small sections of plastic short tubes (16) is welded to form a tilted 1 & precious metal powder discharge pipe (17) to complete the electrolytic cell of the present invention for treating a high concentration cyanide waste liquid. Using the present invention to treat a waste liquid containing a high concentration of cyanide, electrolysis time,
1290181 ___ 五、發明說明（7) 電壓、電流、溫度、廢液迴流速率等操作條件及氰化物濃 度如表1所示。結果顯示，氰化物濃度高達3, 82Omg/1的廢 液1,200公升，經電解2天後，氰化物濃度降至0.25mg/l， 可達到EPA的放流水標準（氰化物1. 0 mg/1 )。 表1 天數 第1天 第2天 第3天 第4天 取樣時間 09 ： 00 16 : 00 09 : 00 16 ： 00 09 ： 00 16 ： 00 09 ： 00 16 ： 00 樣品編號 AD9 A16 BQ9 Β16 009 C16 D09 D16 電壓(V) 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 電流(A) 390 440 460 450 440 440 440 420 溫度(°C) 22 28 35 34 29 31 29 30 迴流速率 (Unin) 30 30 30 30 30 30 30 30 氣錄雜 (CN^mg^) 3,820 1β80 112 1.64 0.25 0.24 0.24 0.23 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。任何熟習此技藝者，在不脫離本發明之精神1290181 ___ V. INSTRUCTIONS (7) Operating conditions such as voltage, current, temperature, and waste liquid recirculation rate and cyanide concentration are shown in Table 1. The results showed that the cyanide concentration was up to 3, 82Omg / 1 of waste liquid 1,200 liters, after 2 days of electrolysis, the cyanide concentration was reduced to 0.25mg / l, can reach the EPA discharge water standard (cyanide 1. 0 mg / 1 ). Table 1 Day 1 Day 2 Day 3 Day 4 Sampling Time 09 : 00 16 : 00 09 : 00 16 : 00 09 : 00 16 : 00 09 : 00 16 : 00 Sample No. AD9 A16 BQ9 Β16 009 C16 D09 D16 Voltage (V) 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 Current (A) 390 440 460 450 440 440 440 420 Temperature (°C) 22 28 35 34 29 31 29 30 Reflow rate (Unin) 30 30 30 30 30 30 30 30 gas recording (CN^mg^) 3,820 1β80 112 1.64 0.25 0.24 0.24 0.23 Although the invention has been disclosed above in the preferred embodiments, it is not intended to limit the invention. Anyone skilled in the art without departing from the spirit of the invention
07iS-：04301TFiNI),PI09200r；particia.ptd 第12頁 129018107iS-: 04301TFiNI), PI09200r; particia.ptd Page 12 1290181
0718-10430TWF(Nl);P10920017;part:c：2.ptd 第13頁 1290181 __ 圖式簡單說明 第1圖為本發明之用於處理含高濃度氰化物廢液之電 解槽一實施例之示意圖。 第2圖為第1圖之本發明之用於處理含高濃度氰化物廢 液之電解槽一實施例之頂視圖。 圖式符號說明： 1 0〜電解槽容器 1 1〜匯電石墨棒 1 2〜石墨粒 1 3〜金屬棒（例如，不鏽鋼管） 1 4〜多孔絕緣物（例如，多孔性塑膠管） 15a〜由任(union ) 1 5 b〜一端封閉之由任（u n i ο η ) 16〜支管 1 7〜排放管 2 0〜進流口 2卜球型過濾網 2 2〜排液閥 23〜閥（例如，蝶閥） 2 4〜球型過濾網 2 5〜溢流槽 2 6〜溢流孔 2 7〜溢流管0718-10430TWF(Nl);P10920017;part:c:2.ptd Page 131290181 __ BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of an embodiment of an electrolytic cell for treating a waste liquid containing a high concentration of cyanide according to the present invention. . Fig. 2 is a top plan view of an embodiment of the present invention for treating an electrolytic cell containing a high concentration of cyanide waste liquid of Fig. 1. Schematic diagram description: 1 0 ~ electrolytic cell container 1 1 ~ sinking graphite rod 1 2 ~ graphite particles 1 3 ~ metal rod (for example, stainless steel tube) 1 4 ~ porous insulation (for example, porous plastic tube) 15a~ By any (union) 1 5 b~ one end closed by any (uni ο η ) 16 ~ branch pipe 1 7 ~ discharge pipe 2 0 ~ inlet port 2 ball type filter 2 2 ~ drain valve 23 ~ valve (for example , butterfly valve) 2 4 ~ ball filter 2 5 ~ overflow tank 2 6 ~ overflow hole 2 7 ~ overflow tube
0718-KK30TWF(N：).F：〇9200!7;particia.ptd 第14頁0718-KK30TWF(N:).F:〇9200!7;particia.ptd第14页
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| TWI475133B (en) * | 2009-10-13 | 2015-03-01 | Sangyoup Suk | Electrolyzer for withdrawing valuable metal which having more contact specific surface area |
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| TWI475133B (en) * | 2009-10-13 | 2015-03-01 | Sangyoup Suk | Electrolyzer for withdrawing valuable metal which having more contact specific surface area |
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