TWI281955B - Treatment method of waste tin lead stripping solution - Google Patents

Abstract

This invention relates to a treatment method of waste tin lead stripping solution, which can be applied on recycling a waste tin stripping or tin lead stripping solution from, for example, a lead frame or a printed circuit board in the electronic industry. The method comprises an oxidation step for oxidizing stannic ions and lead ions into oxide and hydroxide precipitates of tin and lead at high temperature; a solid/liquid separation step for solid/liquid separating oxide and hydroxide precipitates of tin and lead obtained in the oxidation step; a reduction step for reducing the solid oxide and hydroxide precipitates of tin and lead obtained in the solid/liquid separation step into metal tin and tin-lead alloy; and a recycling step for neutralizing the filtrate obtained in the solid/liquid separation step with a base, which is followed by processes such as filtration, evaporation/crystallization, dissolution by adding acid, extraction, electrolysis/reduction, displacement reaction, etc. to produce valuable resources such as metal copper, copper sulfate, ferrous sulfate, ferric sulfate, ammonia, sodium nitrate or potassium nitrate so that the purpose of waste solution treatment and total resource recycling can be achieved.

Description

1281955 玖, invention description [Technical field of invention] ^本明 is a kind of treatment method for stripping lead waste liquid, which is applied in the electronic industry Lu Wang, due to stripping of electric ore tin or electric money tin staggered layer Waste liquid, in addition, the present invention is also related to a method for recovering metallic tin, metallic copper, copper sulfate, ferrous sulfate or ferric sulfate from a waste liquid order capable of self-peeling electroplating tin or electrocalyx. [Prior Art] In the manufacturing process of a general printed circuit board, it is often necessary to plate a tin layer or a tin-lead layer on the copper layer to protect the copper layer during the alkaline etching process. After removing the copper layer of the non-line portion after etching, it is usually dissolved by a strong acid of nitric acid = stripping the electroplated tin layer or the electroplated tin-lead layer, so that the line portion of the copper layer can see a strong acid solution using a nitric acid system. For the method of stripping the tin plating layer or plating the tin-lead layer, reference can be made to U.S. Patent Publication Nos. 5, 9, 9, 7, 5, 928, 529, 5, 989, 449, 6, 258, 294 B1 and 2 In the case of 〇1/_73ΠΑ, etc., the main component of the strong acid solution of the towel is nitric acid &L iron. During the stripping of the tin plating layer or the tin-bonding layer, the concentration of free nitrate anion in the solution is low. At 4 Ν, or when the tin content is higher than l〇〇g/L, it is necessary to re-form the new nitric acid solution, thus causing the waste liquid to peel off the tin plating layer or the tin-lead layer. In the waste liquid of the electroplated tin layer or the tin-plated lead layer, it contains 2 to 15 g/L of copper ions, iron ions or ferrous ions of 4 〇g/L, and tin of 1 to 12 〇g/L. Ionic or stannous ions (since the waste liquid is stored or transported, tin ions are oxidized to form tin oxide or tin hydroxide precipitates, so sometimes they are present in the waste liquid 1281955

The tin ion and stannous ion content will be less than 1〇g/L. ), the lead ion of Hg/L and the free nitric acid solution of 2.0 to 6. ON, so it is necessary to properly dispose the waste liquid of the stripped tin plating or the tin-lead layer to avoid the strict environment. The current treatment method of the wood can firstly use the sodium nitrate to neutralize the free nitric acid in the stripping solution, and adjust the pH between 8 and 13 曰 to make most of the damage: heavy metal cations form oxides or hydrogen. a precipitate of oxide, which is obtained by smelting the oxide or hydroxide solid, and then refining the metal tin by a smelting method, or dissolving the solid substance in a high concentration alkali solution, and then reducing it by electrolysis The metal tin is obtained, and the liquid is evaporated to crystallize to form a sodium silicate crystal. However, the main disadvantage of the f-use technique is that the oxide or hydroxide solids contain a lot of heavy metals such as copper, iron and iron, especially the purity of the metal tin obtained by copper smelting or electrolysis. /曰All ===Republic of China Patent Law Notice No. 1 7791 No. 1 "Recovering from 1 (four) waste liquid, ~3 and not 竿1 replacing the tin ion or stannous ion in the waste liquid with μ, it is recycled. "The treatment described in the patent content; gold = the original agent and the sinking agent, and the process is complicated, so it is uneconomical to become H. During the treatment, tin or stannous ions are easily formed into telluride or Precipitation of hydroxide precipitates, and the reduction of metal tin by sheet replacement is also a disadvantage of this. It is not easy to find a suitable time to disclose the use of ion exchange resin in the case of the "mineral regeneration method and apparatus" of the Republic of China Patent No. 258758. In the case of the method, in the case of B, it is revealed that the method of adding reducing agent, killing agent and neutralization can make the discharged water after treatment reach the replacement and still add to your yin. _ ^ + IW i Lv 1281955 A method for recovering tin-plating auxiliaries and metallic tin from iron, chromium and tin in electroplating bath. However, this method also has the disadvantage of being quite complicated in the process, and therefore is not suitable for treating the waste liquid after stripping the electroplated tin layer and the tin-lead layer. In addition, in the case of the Republic of China Patent Bulletin No. 472〇3, “Methods for Stripping Lead Waste Waste Liquid”, it was revealed that the addition of a sedative agent and a neutralizing agent (inspective drug 剤) to the waste liquid was carried out, and filtration was carried out. Heating a deamination, precipitation and dissolution, etc., a series of separate private orders to achieve the recovery of valuable components in the waste liquid and the environmental protection of the waste liquid. The method can produce 95% pure sodium stannate, 80% sodium fluoride or sodium nitrate and 93% copper sulfate crystals from the components recovered by the stripping lead waste liquid. Sodium stannate can be electrolytically scoured to obtain 99 9% of metallic tin; sodium or succinic acid and copper sulphate can be recrystallized to increase their purity. Although this method can achieve the environmental protection work of the recovery of valuable components in the waste liquid and the treatment of waste liquid, it has the same disadvantages as the above-mentioned conventional technology, that is, the oxide or hydroxide solid content produced after the neutralization contains a lot of Heavy metals such as copper, iron and ^, especially when the copper content is too high, make the subsequent process of refining tin too complicated. ·· As for the pre-existing patents of the Republic of China Patent Announcement No. 4 Tiger, US Patent No. 576, 6UG349 and 62_5, mention „ . The process of tin mud in the tin bath or the process of stripping the wrong waste liquid Sinking in the middle!: Tin mud,: After the strong dissolution, the method of reducing the metal tin by electrolysis:, ” can be used as a reference for the treatment of tin mud. In addition, the present invention - Patent Publication No. 4981 12 "A method for removing copper and tin ions in the waste liquid of the tin or the residual tin-lead", the content of the treatment of the detoxification waste liquid may also be And 1281955 into the tea test. SUMMARY OF THE INVENTION In view of the above, there is a need for an economical and efficient method for recovering metal ions contained in waste liquid. Therefore, the object of the present invention is to provide a method for treating a stripping or stripping lead waste liquid to recover metal 35, metallic copper or copper sulfate and ferrous sulfate into iron sulfate, comprising: an oxidation step: at a high temperature Tin oxide and lead oxide and hydroxide sinker; ion oxidation to tin bismuth lead oxide and oxidation of tin and lead

Solid-liquid separation step: solid-liquid separation of tin and hydroxide precipitate obtained in the oxidation step; reduction step: reducing solid matter and hydroxide obtained by the solid-liquid separation step into metal tin or tin-lead alloy; After the neutralization, electrolytic reduction, replacement of ferrous sulfate, iron sulfate recovery step: the solid-liquid separation step is generated, through filtration, evaporation crystallization, acid dissolution, extraction reaction and other procedures to recover metal copper, copper sulfate, Valuable resources such as ammonia, sodium nitrate or potassium silicate. According to the method of the present invention, the purpose of the waste liquid treatment can be surely achieved, and the effect of complete recovery of resources can be achieved. [Embodiment] The process of stripping, neutralizing, evaporating and reducing the tin-lead waste liquid, and referring to the first figure, the method for treating the stripping or the method of the present invention is mainly carried out by using the method of temperature oxidation, smelting, electrolytic reduction and crystallization. Oxidation step, solid-liquid separation step 11 1281955 Recovery step. - The oxidation step of the alum method is carried out at a high temperature under the step of oxidizing tin and lead milk * wind oxide sulphide in a circle of 45 fiJ i2 〇〇 c, preferably at 6 〇 to 1 (^c Within the temperature range = = When the hunger is oxidized, the rate of formation of the stagnation is too slow to carry out the oxidation, and there will be a lot of money to be evaporated out, and the risk of volatiles such as the rat emulsion (10)x). Therefore, in the temperature range of 45 to 12 = preferably in the temperature range of 60 to mt; the emulsification step will have a rapid separation of tin from the waste liquid to form tin and oxides and hydrogen (IV) The effect. ^ In the oxidation step, aeration oxidation method, chemical oxygen =, or electrolytic oxidation method may be used alone, or may be used in combination to increase the oxidation effect. The method of μ is to facilitate the direct oxidation of the oxidation reaction body into the waste liquid by ozone, oxygen or air; the chemical oxidation method is to increase the concentration of nitric acid in the waste liquid of the waste liquid or directly add the thick stone. The acid is in the liquid state; and the electrolytic deuteration t, the soil β & potential difference causes the anode region to oxidize to perform the aeration oxidation method described above, the L. ^ ^ T port is a helium molecule which can be rapidly at a high temperature Tin oxide ions and lead ions cause the formation of tin and lead oxides and hydroxides. Therefore, the concentration of lanthanum, tin and lead ions in the solution is rapidly lower than that of yak. For example, at a temperature of 80 ° C, the concentration of tin ions in the waste liquid can be reduced to less than 5 g / L per person for 1 hour. In the aforementioned chemical oxidation method, ^ _ because the concentration of nitric acid in the waste liquid will be abrupt, and the nitric acid can quickly smelt the tin ion and the lead ion at a high temperature, so that the *emulsification method is carried in the electrolytic cell, Add·< Φ 乂TV 辇/士17曰e.,, 12 12 1955, the formation of tin and wrong oxide knives _,, the field of n material and oxygen ritual deposits. For example, at 8〇. The concentration of nitric acid in the waste liquid of the crucible is up to 7 Ν. The concentration of tin ions is reduced to less than 5 g/L, so that r _ T can be obtained in the waste liquid. The chemical oxidation method can be carried out in a concentrated nitric acid which can be directly added to the waste liquid at a concentration of 3 Torr, and commercially available nitric acid having a enthalpy of 5 〇 to 1%. In the above electrolytic oxidation method, ^ 6V . p, # ^ θ anion % potential difference is maintained between 2, hunting by the electrolytic oxidation of the % pole region, causing oxidation of the wrong ions in the wide liquid w and And hydrogen-oxygen heart: "4 g C%% potential difference 4 shoulders under the conditions of electrolytic oxidation 4#| small temple, the concentration of tin ions in the waste liquid can be reduced to below 5g / L. : It needs to be 'in the oxidation step'. If the lead in the high-temperature oxidation waste liquid is too low in efficiency from the 7-Ming emulsion and hydroxide precipitate, it can be added to the waste liquid during or after high-temperature oxidation. The wrong ion equivalent sulfate ion precipitates in order to promote the formation of a sulfuric acid miscrystal. The compound of the sulfate ion includes the sulfuric acid and the sulfuric acid, and is not limited to sulfuric acid or sulfuric acid. In the solid-liquid separation step of the method of the present invention, any conventional solid solution can be used to separate from the waste liquid. The tin and the wrong oxides and hydroxides are produced, and, depending on the situation, the sulfuric acid is staggered. Compared with the conventional technology or the Chinese, the national patent publication No. 3Q, the tin and the wrong oxide and hydroxide in the method of the present invention contain only a trace amount of copper ions and iron (ferrous) ions, so follow-up The reduction step makes it easier to produce high-purity metal tin or tin-a-gold. ° In the reduction step, the 13 1281955 solid tin and the wrong oxide and hydroxide will be separated in the solid-liquid separation step, and the furnace may be produced as a 'precipitate, first washed and dried with water. After that, it is mixed with and grinded with carbon-containing carbon, coke or graphite and sodium carbonate. It is preferably smelted at a high temperature of 6 to 12 Torr to obtain metallic tin or tin-lead. alloy. Or, after washing with water, dissolve the Shen Temple in the strong test. The strong tests that can be used include, but are not limited to, gas oxidation, chlorine oxidation or a mixture thereof. Preferably, the equivalent concentration is between 2. Q and 7 shoulder gas oxides. The potassium hydroxide or a mixed solution thereof is preferably used at a temperature of 8 Torr in the chamber. . When it is between 16 (between rc and the time required for dissolution (4) is two hours, preferably more than 5 hours, so that the tin content in the solution can be set to 3 〇g/L or more, usually up to 5 Between 15 。. After filtering out the undissolved solids, the tin-and-error-containing test solution is subjected to an electrolytic reduction step at a temperature of 5 〇 to the gallbladder, and the metal tin or tin-lead can be recovered. The alloy' and the anode-anode potential difference are preferably between 15 and 7. 〇v. The metal tin or tin mismatched by the smelting method or the electrolytic reduction method can be used in the stannous sulfate solution. Further, it is electrolytically refined to obtain high-purity tin, and the method is the same as that of conventionally electrolytically refining crude copper to become refined copper. a __ After oxidation by high temperature oxidation, most of the tin ions and lead ions in the stripping waste liquid are Has been oxidized to form tin and ritual and phlegm precipitates, and then, solid solution separation step solid-liquid separation;;;::; ' ion or ferrous ion and 2. 〇 to 6. (10) free Nitric acid. - The liquid produced by the solid-liquid separation step is neutralized in the recovery step - sodium or chlorine oxidation and The pH value is adjusted to 8~13, so that the sputum; = 14 1281955 and copper 4 heavy metal ions form oxides and hydroxide precipitates, and after solid-liquid separation, the filtrate containing sodium nitrate or potassium nitrate can be obtained. A filter cake of oxides and hydroxide precipitates such as iron and copper. The obtained filtrate is heated to remove ammonia, and then sodium nitrate or potassium nitrate crystals can be obtained by using the Luofa crystallization method, and the filter cake is dissolved by adding a dilute sulfuric acid solution. Obtaining copper sulfate and iron sulfate or ferrous sulfate by extraction method, or obtaining copper metal powder and ferrous sulfate by replacement method, or preparing copper metal powder and ferrous sulfate by electrolytic reduction method, or by electrolytic reduction method Metallic copper and ferrous sulfate. For the aforementioned extraction method, reference is made to U.S. Patent No. 4,252,621, Chinese Patent Publication No. 1 1 54723A and No. 1297978A, etc., using the trade name ux_54 The copper ion of the solution towel is metallized powder, the money (4) dissolves to form ferrous iron 2' passes; t, the metal copper powder is obtained by drying, and the ferrous sulfate f liquid produced by (4) is evaporated to obtain ferrous sulfate. Crystal, or oxygen , air, etc.::: into iron sulfate solution; the above electrolytic reduction method is to place the dilute sulfuric acid solution in the electrolytic cell, and reduce the copper ions of the solution to metal after the anode and cathode of φ ή6 ^ ^ 1 main enthalpy曰Residual & ferrous solution is evaporated to form ferrous ferrous crystals, or oxygen solution. The hole is specially formed to form iron sulphate organic extractant to extract copper ions in dilute sulfuric acid solution, and then concentrated The sulfuric acid solution is extracted and dissolved in the organic extractant LIX-54, and then used to extract the copper ions in the dilute sulfur solution, and the copper sulfate solution is obtained by cooling crystallization or evaporating, filtering and drying. Crystals, the mother liquor produced by filtration is also refluxed and used to back-extract the copper extract of the organic extractant lix — 54^, and the replacement method is to use iron powder in dilute sulfuric acid solution to set Φ4 15 1281955. EXAMPLES Example 1: A 5 L stripping lead waste liquid containing about 1 〇g/] L Cu 2+ , 3 〇 g / L Fe 2 V Fe 3 + , 30 g / L Sn 2 VS n 4 + and 1 〇 2+ was taken. The waste liquid was heated to 80 C, stirred and oxygen was introduced for 2 hours, and a large amount of tin oxide and hydroxide precipitate were formed in the waste liquid. The tin oxide and hydroxide precipitate were separated by filtration. The obtained solid tin oxide and hydroxide were combined in 2 L of a 3N sodium hydroxide solution at 80 ° C for 6 hours. Then, the temperature of the tin-containing alkali solution is raised to 95r, and the high-temperature electrolytic reduction step is carried out under the condition of a cathode-anode potential difference of 3. OV, and the tin content in the solution is about 3 g/L, and about 12 is recovered. 〇§ Metal tin. Example 2: The same operation as in Example 1, after separating and separating the oxide of tin and the oxychloride from the sulphate, it was washed with water and dried, and lg dry precipitate was taken, and 20 g of active slave and 80. 〇 3 g of carbonic acid were added. Sodium, after mixing and grinding, was smelted at a high temperature of ° C for 4 hours to obtain 512 g of metallic tin having a purity of 98 5%. Example 3:

Take lm containing about 5g/L Cu2+, 30g/L Fe2 + /Fe3+, 3〇g/L

Sn/Sn and 10 ppm Pb2+ ion stripping lead waste liquid, the waste liquid is heated to 90 C (four) and passed through oxygen for 2 hours, a large amount of tin oxide and hydroxide hydroxide are formed in the waste liquid. When the temperature of the waste liquid is reduced to 5 (rc or less; t-knife is separated from the oxide of tin and the oxychloride oxide. The working solid (10). C, the obtained solid tin oxide and hydroxide are dissolved in the ancestors. The concentration was 16 hours in 16 1281955 f potassium oxide solution for 10 hours. Then, the solid solution which was still cold-decomposed in the solution was removed. After the slave, the condition of the temperature of the tin-containing alkali solution i ° and the anode-anode potential difference was 3, The high temperature electrolytic reduction step is carried out = about ^, after, at this time, the tin content in the solution is less than 5 g / L, and 23 kg of metal tin can be obtained. The service example 4 is the same as the operation of the embodiment 3 After the tin oxide and hydroxide precipitate, 254 g of precipitate was taken, 63 6 g of activated carbon and 253.3 g of sodium carbonate were added, mixed and ground, and smelted at a high temperature of 95 〇t for 4 hours to obtain 58. 5 g of metal tin having a purity of 99·5%. Example 5: Similar to the operation of Examples 1 to 4, after separation of tin oxide and hydrogen·oxide precipitate by filtration, the precipitate is reduced by wet electrolysis or by fire. The metal smelting process produces metal tin, and the filtrate is neutralized with a concentration of about 3N sodium hydroxide solution and the pH is adjusted. About 11. The brown filter cake of brown iron, copper, tin, lead and other oxides and hydroxides and the light green filtrate containing sodium nitrate are formed in the filtrate, and 3 〇〇m 1 pale green filtrate is obtained, which can be prepared by evaporation crystallization. Approximately 2Gg of light green or yellowish oleic acid was obtained. The atomic absorption spectrum (A, A) was used to analyze the heavy metal content. The result was ^___ 5 tiger color Cu (ppm) Fe (ppm) Sn (ppm) Pb(ppm) - 1 light green 25. 84 22. 61 ND ND 2 light green ND 14. 89 ND ND 3 light yellow ND 3. 67 ND ND__ Example 6 ·· 17 1281955 Same as Example 5' in transition separation After obtaining a brown cake containing iron, copper, tin and hydroxide, the brown cake is dissolved in a dilute sulfuric acid solution having a concentration of about 1: to form a micro-brown green solution, and the cathode-anode potential difference yv and temperature 15t Under the condition of electrolysis 2 Xiaori Temple, the copper ions in the solution are almost completely electrolytically reduced to metallic copper, and the solution becomes a green solution containing ferrous sulfate. The above embodiment is only an exemplary example of the present technology, and it is not used. The invention is defined in a specific form, and those skilled in the art are aware of the invention. Any modifications or changes shall be made in accordance with this, and such modifications or changes shall be included in the scope of the patent application scope of the present application. [Simplified description of the drawings] (1) The first part of the drawing is a schematic diagram of the process of the present invention. .

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Claims (1)

1281955 Picking up, applying for a patent scope 1. A method for treating a tin-lead waste liquid, comprising: an oxidation step: oxidizing tin ions and a stray ion into a tin, a lead oxide, and a hydroxide precipitate at a high temperature; Separation step: solid-liquid separation of tin, lead oxide and hydroxide precipitate obtained by the oxidation step emulsification step; reduction step: taking the solid-liquid separation boat 5 from the solid-state tin and lead obtained by the knife-off step The vapor and hydroxide are reduced to metal tin or tin-lead alloy; _ recovery step: the filtrate produced by the solid-liquid separation step is neutralized, filtered, crystallized, acid-dissolved, extracted, and electrolyzed. When the program is completed, copper, sulfur, ammonia, sodium sulphate or potassium nitrate is obtained. The treatment method of the ferrous iron and the ferric sulphate in the stripping waste liquid according to the first application of the patent scope 1 wherein the oxidizing step is carried out in the temperature range of 45 to 1 (10); ^ 3, as in the patent application range 1 or ^- Gans t. The treatment method of tin-making oblique waste liquid, "the oxidation step is carried out at 80 to 105. 匕 / / 皿 进行 进行 氧 氧 氧 氧 氧 、 、 、 、 、 , , , , The method of treating the private waste liquid in the straight ϋ 丰 挪 挪 吻 , , , , , , 乃 乃 乃 乃 忐 忐 忐 忐 忐 忐 忐 忐 忐 忐 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 The process of treating the tail liquid, the table, and the middle gasification step are carried out by a chemical oxidation method. Method 6, such as the treatment method of the IW dry waste liquid of the scope of the patent item 19 1281955, wherein the oxidation step is utilized Electrolytic oxidation No. 7, as in the scope of the patent application: [The oxidation step is carried out by a combination of aeration oxidation and waste liquid treatment methods. 'Chemical oxidation method and electricity 8, as claimed in the scope of the fourth or seventh Method, its The aeration oxidation method includes the treatment of introducing oxygen and wrong waste liquid, as in the fourth or second application of the patent scope: into the waste liquid. The method of 'ventilation oxidation includes air treatment: treatment of tin wrong waste liquid 1 如Apply for the scope of patent No. 5 or /I. In the chemical method, the chemical oxidation method in the sputum includes the right point of the bismuth, and the tin sulphur waste liquid, as in the patent scope 5 or: / item =: concentrating. The chemical oxidation method includes direct two:: wrong waste liquid. Money is added with concentrated nitric acid to the waste liquid 1 2. As in the patent application method, the concentration can be used in 5 〇 liquid. The treatment of the stripping tin waste liquid to 100% concentrated nitric acid is added to the waste treatment method, between 6.0 V, as in the patent application range 6 or in the electrolytic oxidation method, the yin and yang lead stripping lead waste liquid The extreme potential difference is maintained at 2.0 to % of the dog's calendar. In the oxidation step, during the oxidation step, it is necessary to add the sulfate ion-containing chemical to the ship ion to form the sulfuric acid miscrystal. 1 5, if the scope of application for patents] &立丨^ 囷乐1 4 stripping lead waste liquid 3 method, wherein the sulfate ion-containing compound is sulfuric acid. 20 1281955 16. The stripping waste liquid of claim 14 The treatment method, wherein the sulfate ion-containing compound is sodium sulfate. 17. The method for treating a stripping waste liquid according to claim 14 wherein the sulfate ion-containing compound is potassium sulfate. The treatment of the stripping waste liquid in the range of the work item, wherein in the reduction step, the activated carbon containing the carbon powder is added. 19. As claimed in the patent scope! The stripping of the item is the treatment of the waste. In the reduction step, the coke of the carbonaceous powder is added. 2 0, such as the scope of patent application! Treatment of the stripping waste liquid in the item In the reduction step, the stone black containing the carbon powder is added. 2 1. The treatment of the stripping waste liquid according to the scope of the patent application. In the reduction step, a mixture of activated carbon, coke and graphite containing carbon powder is added. A « 2 2 : The method of treating the stripping waste liquid of the first application of the patent scope, wherein sodium carbonate is added in the reduction step for high temperature smelting. 2 3. The treatment method for stripping the wrong waste liquid according to the scope of the patent application s' wherein the reduction step is at 6 〇 "H2G (rC temperature range _ smelting. 2 4, as claimed in the scope of the first or second The three methods of stripping the wrong waste liquid. Treatment method 'The reduction step is to carry out the smelting within the temperature range of the temperature. · 2 5. The treatment of the stripping lead waste liquid according to the scope of the patent application The method of 'reduction step is to use the method of electrolysis to reduce the 'first use of strong alkali (four)-' and the oxides and hydroxides dissolved in the dissolved matter, then the electrolytic reduction method 21 2 1281955 Treatment Method 2 7 Treatment Method 2 8 Treatment Method 2 9 If you apply for the patented U25 item, you can find the sodium hydroxide solution. For example, in the case of claim 25, the stripping of the wrong waste liquid | wherein the strong test is potassium hydroxide. Such as the scope of patent application! Or 25 of the tin-making waste liquids, wherein the strong base is a mixture of sodium hydroxide and potassium hydroxide. ‘Shikou applied for the treatment of stripping the wrong waste liquid port of item 25 of the patent scope, wherein the strong base is a solution having a base equivalent concentration of 2〇 to 7·(10). For example, the processing method of the stripping waste liquid of claim 1 or 25, wherein the dissolving is the temperature at the room temperature to the temperature of the boot, and the patent range is 1 or 25 or 3剥 的 # # # # # # # # # # # # # # # # # # # # # # # # # 』u, the degree of the container 3 2, such as the application of the patent treatment method, i in, or 25 of the stripping lead waste liquid" in the original step is electrolytic reduction within 50 n. d The dryness of the dish - 3 3, such as the patent scope of the second mt ^ 丄 丄 2 2 2 2 2 、 、 、 、 、 、 、 、 、 、 、 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原7. Between 〇V. Left · 3 4. For example, the 4 ... method of claim 1 of the patent scope, in which the 逖 步骤 step is recovered, and the 隹 丰 丰 产 六 六 孟 孟 或 或 或 , , , , , , y, in the 丨1 I stannous solution electrolysis in January, the agricultural purity of the tin. 22 1281955 3 5, as claimed in the scope of claim 1 of the stripping lead waste liquid treatment, the method, in the recovery step, The alkali neutralization procedure is to use a base to neutralize the filtrate produced by the solid-liquid separation step and adjust the pH to 8 to 13. 3 6. Treatment of the stripping lead waste liquid according to claim 1 or 3 a method, wherein the recovery step comprises neutralizing the filtrate produced by the solid-liquid separation step, and separating the nitrate-containing filtrate and the copper by filtration a filter cake of iron oxides and hydroxide precipitates. 3 7. For the stripping lead waste liquid of the first or third paragraph of the patent application, the treatment method, the filtrate containing sodium nitrate and potassium nitrate is evaporated Crystallization to obtain crystals of sodium nitrate and potassium nitrate. 3 8. A method for treating a stripping lead waste liquid according to the third or sixth aspect of the patent application, the filter cake containing oxides and hydroxide precipitates such as steel and iron - After dissolving in dilute sulfuric acid solution, copper sulfate, ferrous sulfate and ferric sulfate are obtained by extraction method. - 39. Treatment method for stripping lead waste liquid according to the first or third δ of the patent application scope, the copper-containing and After the filter cake of iron oxide and hydroxide precipitate is dissolved in dilute sulfuric acid solution, the metal copper powder and the sulfuric acid powder are prepared by the replacement method, and the dry spear _L or jb The treatment method of lead waste liquid ' 5 Xuan copper and bell ^ installed t iron temple sulphate and hydroxide precipitate filter cake with dilute sulfuric acid solution> trough solution 'utilizes Lei Nian 2 ^ ~ using electrolytic 逖 original method Metallic copper and ferrous sulfate 0 23