TW201036718A - Method for recovering gold, silver, copper and iron from valuable metal-containing plasma-caused slag - Google Patents

Abstract

There is disclosed an environmentally friendly method for recovering gold, silver, copper and iron from valuable metal-containing plasma-molten slag. At first, plasma is used to burn the used printed circuit boards, thus producing the slag. Then, the slag is grinded. Then, leaching, crystallization, precipitation, replacement and electric winning are conducted to recover gold, silver, copper and iron.

Description

201036718 VI. Description of the invention: [Technical field to which the invention pertains] The present invention rapidly decomposes the resin in the waste printed circuit board by means of plasma burning, and then uses grinding, magnetic separation, screening, etc. to make the valuable metal effective. Separation, to achieve the separation of gold, silver, copper, iron valuable metals in waste printed circuit boards, and then use gold, silver, copper and valuable metals by methods such as impregnation, crystallization, precipitation, displacement, and electrolysis. Resource recycling. The invention belongs to the technical field of environmental protection and waste resource regeneration. 〇 · [Prior Art] Valuable metals such as gold, silver, and copper contained in waste printed circuit boards cannot be recycled if they are discarded, which is not only harmful to the environment, but also a pity. At present, the recycling technology of waste printed circuit boards is mainly the pulverization recovery method and the combustion recovery method. Since the resin component contained in the waste printed circuit board is elastic and non-green, if the direct pulverization method is used, it will consume a large amount of energy, and it will also be generated. Dust, noise and loss of implements. Another example is the use of conventional combustion methods. Due to poor combustion efficiency and long time consuming, the energy loss is also less economical. Therefore, the invention will rapidly decompose and embrittle the resin component in the waste printed circuit board by the plasma roasting method with high combustion efficiency, so as to reduce the energy consumption and the tool loss required for the grinding, so as to facilitate the subsequent waste printed circuit board. Separation and recovery of valuable metals. Patent for the recovery of domestic waste printed circuit board resources, such as the Republic of China Bulletin No. 247281 "Method for Separating and Recovering Valuable Substances from Printed Circuit Boards" and Republic of China Announcement No. 36904 "Re-resources of Waste Printed Circuit Boards" The treatment method 』's content mainly involves the direct pulverization of the waste printed circuit board and the recovery of valuable metals. In addition, the Republic of China Announcement No. 1268184 "Recycling Waste 201036718 Circuit Board Method" is mainly to heat the waste printed circuit board to 200. (4) When the solder is melted, the surface electronic components are removed, and then the cold bribes are used. A valuable substance in a printed circuit board. Based on the above results, it has not been found that any related patents and technologies have been used to rapidly separate and recover valuable metals in waste printed circuit boards by means of plasma burning, grinding, magnetic separation and screening. SUMMARY OF THE INVENTION The gold, silver and copper metal contained in the decadent printed circuit board have a recovery value. If it cannot be recycled and reused, the overall metal resource will be wasted. Therefore, the present invention is subjected to plasma burning, grinding, and magnetic separation. And screening and other means to quickly and reliably carry out the separation and recovery of valuable metals in the waste printed circuit board, in order to achieve effective recovery and reuse of valuable metals. For the purpose of the above, the present invention is a plasma slag obtained by plasma baking and grinding a waste printed circuit board by sieving and magnetic separation, impregnation, crystallization, precipitation, displacement, electrolysis The method of recovering the valence metal in the waste printed circuit board by the method of 'first re-pulping the slag with 0.149mm sieve, and then selecting the iron material by magnetic separation, the iron metal can be sent to the refining The steel plant carries out the refining and smelting of iron metal; while the non-magnetic metal and glass fiber particles after magnetic separation have a high content of copper-containing metal on the sieve material larger than 0.149mm, which can be sent to the copper smelting plant to recover the copper metal 'the sieve smaller than 0.149mm The next substance is firstly immersed in 18N sulfuric acid with a single sulfuric acid, and the solid-liquid ratio is immersed at 10 ° C for 50 hours at 70 ° C for 1 hour, and the copper leaching recovery rate of 90.56% can be achieved. After standing at room temperature for 48 hours, the optimum crystallization effect of 58.28% of copper crystallized into copper sulfate crystals in the impregnation solution can be achieved. After the crystallization, the residual copper metal in the filtrate, 6 201036718 is treated with iron powder as a displacer. When the iron powder is added to the theoretical value 1 〇〇 times, the copper in the filtrate after crystallization can be replaced by copper powder. Recycling. In another case, the copper of the residue was leached with sulfuric acid at a solid-liquid ratio of 5 g/5 〇m to 7 以. (; under the dipping for 2 hours, T will be the residue / check the copper to be impregnated and dissolved, the second copper-containing impregnation solution, and then iron powder as a replacement agent, the amount of 150 times the iron powder theoretical value, can 100% of the copper in the secondary sulfuric acid leaching solution is replaced by copper powder. The silver slag in the secondary sulfuric acid immersion residue is immersed in 8N nitric acid at a solid-liquid ratio of lg/50ml 'at 7 ° C. In the hour, 1% of the silver in the residue can be immersed and dissolved. The best silver-containing impregnation solution is first adjusted with ammonia to adjust the pH value to _ 10 to obtain the silver-containing solution, followed by hydrochloric acid (12N). As a precipitant, 100% precipitation of silver metal can be recovered into silver chloride under the conditions of hydrochloric acid (〇11)/silver solution (ml)=4. The gold contained in the nitrate impregnation residue is 100%. As the impregnating agent, the king water can be impregnated with 100% of the gold in the residue under the condition of solid-liquid ratio of 0.5g (residue)/5〇ml (Aqua regia) at 7〇〇c for 4 hours. Corrosion, the best gold-containing impregnation solution, with zinc powder as a displacer, can replace and recover the gold 99 43% in the best gold-containing immersion liquid. The waste printed circuit board is subjected to plasma roasting and grinding by the invention. Electric pulping The method of sieving, magnetic separation, impregnation, crystallization, precipitation, displacement, electrolysis, etc. can achieve the purpose of waste printed circuit board reduction and resource recovery. [Embodiment] The preferred method of the present invention As shown in the first figure, the collected plasma is firstly smelted, and sieved by a 149149mm sieve 2, and a substance 21 larger than 0.149 mm is selected by magnetic separation 3, and the iron metal 31 can be sent to The steelmaking plant carries out the refinery smelting of iron gold 201036718, and the non-ferrous metal 32 after magnetic separation has a high amount of copper metal, which can be sent to the copper processing plant to recover copper metal, and the less than 149. The iron metal 41 obtained after magnetic separation 4 can also be sent directly to the steelmaking plant for regenerative smelting of iron metal, and the non-ferrous substance 42 after magnetic separation (the appearance of which is shown in Annex 1) is first impregnated with primary sulfuric acid by 5 to 18N sulfuric acid. Under the conditions of solid-liquid ratio i〇g/5〇ml and 7〇°c for 1 hour, 90.56% copper impregnation recovery rate can be achieved. This copper-containing impregnation solution 51 is directly crystallized at room temperature. After standing for 48 hours), 58.28% of the copper crystals in the impregnation solution can be crystallized into copper sulfate crystals 61 (external The best crystallization results shown in annex twenty) of. After the crystallization, the residual copper metal in the optimum crystallization filtrate 62 is replaced by iron powder as the displacer 7. When the iron powder is added to the theoretical value of 1 〇〇, the copper in the filtrate after crystallization can be replaced by 100%. Copper powder 71 is recovered. The copper of another sulfuric acid impregnated residue 52 is impregnated with 18N sulfuric acid at a solid-liquid ratio of 5g/5〇m at 70〇C for 2 hours, and 100% of the copper in the residue can be impregnated and dissolved. The secondary copper-containing immersion liquid 81 is further treated with iron powder as a displacer 9, and the added amount is 15 〇 iron powder theoretical value, and 100% of the copper in the secondary sulfuric acid immersion liquid can be replaced and recovered into copper powder 91. . The silver slag in the secondary sulfuric acid leaching residue 82 is immersed in 8N nitric acid at a solid-liquid ratio of lg/50 nU at 70 ° C for 4 hours, and the silver in the residue is immersed and etched by 10%. The best silver-containing impregnation solution 101, the silver-containing solution 11' obtained by adjusting the pH value with ammonia water, and then hydrochloric acid (12N) as a precipitant 12, in hydrochloric acid (ml) / silver-containing solution (ml) = 4 Under the conditions, 1%% of the silver metal precipitate can be recovered into the vaporized silver 121. The gold 1〇2 contained in the nitric acid impregnation residue is treated with 1% by weight of aqua regia as an impregnating agent, under the conditions of solid-liquid ratio 〇5g (residue)/5〇mi (Aqua regia). At 7〇.匸 匸 4 4 4 4 4 ' 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 99.43% of the 201036718 gold in the liquid is replaced by hi. The advantages of the present invention for making the present invention more progressive and practical are as follows: 1. The invention can quickly and easily recover gold, silver, copper and iron valuable metals in waste printed circuit boards for use as Raw materials for metal smelters to reduce metal waste. 2. The invention can reduce the waste quantity of the circuit board and reduce the harm of harmful substances in the printed circuit board to the environment and the human body. 3. The invention is safe and progressive.

4. The invention has the use value of the business community and the industry. In summary, the invention conforms to the application requirements of the invention patent and submits an application according to law, and invites the bureau to examine the member Wei and resign the patent right of the invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic diagram of the recycling process of the present invention. Q [Description of main component symbols] 1 · · Plasma slag 2 · · Screening 21 · · 0.149mm substance 22 · .-0.149mm substance 3 · Magnetic separation (+〇.i49mm) 31 · · Iron ( +0.149mm) 32··Non-ferrous substances (+〇.i49mm) 4··Magnetic selection (-〇.i49mm) 9 201036718 41 . ·Iron (-0.149mm) 42 ··Non-ferrous substances (-0.149mm) 5· · - Sub-sulfuric acid impregnation 51 ·. - Secondary copper-containing impregnation liquid 52 · · - Secondary sulfuric acid impregnation residue 6 ·. Crystallization 61 · · Copper sulfate crystal 62 · · Best crystallized filtrate 7 · Iron powder Replacement (primary copper-containing impregnation solution) 71· · Copper powder (optimal crystallization filtrate) 8··Secondary sulfuric acid impregnation 81 ··Second copper-containing impregnation liquid 82 ··Secondary sulfuric acid impregnation residue 9 · ·Iron powder replacement (secondary copper-containing impregnation solution) 91 ··Copper powder (secondary copper-containing impregnation solution) 10 ·.Nitrate impregnation 101 ·.Optimum silver-containing impregnation solution 102 ··Nitrate leachate Residue 11 ··Ammonia water adjustment pH 12 · · Hydrochloric acid precipitation 121 · · Silver chloride 13 ·. Aqueous water impregnation 131 · · Best gold-containing impregnation liquid 14 · · Zinc powder replacement 141 ·· Replacement gold

Claims (1)

201036718 VII. Scope of application for patents: 1 · A method for providing valuable metals in recycled printed circuit boards. The ship is made up of plasma slag (4) obtained by plasma pulverization and grinding, and magnetically leached and dissolved. The method of analysing, precipitating, replacing, electrolyzing, etc. to recover valuable metals in waste printed circuit boards, firstly sieving the electro-gray slag with a 0149 mm sieve, and then separately selecting the iron materials by magnetic separation. The iron metal can be sent to the steel mill for the refining and smelting of the iron metal; after the magnetic separation, the non-magnetic metal and the glass fiber particles, the content of the copper-containing metal containing more than 0.149 mm can be sent to the copper smelting plant for recycling. Copper metal, another less than 0.149mm under the sieve material 'first with sulfuric acid immersed in 18N sulfuric acid, solid-liquid ratio 1〇g/5〇n^, 7crc under the conditions of 1 hour, can achieve 90.56% copper The recovery rate of the impregnation, the copper-containing impregnation solution was allowed to stand at room temperature for 48 hours, and the best crystallization effect of 58.28% copper crystallization into copper sulfate crystals in the impregnation solution was achieved. After the crystallization, the residual copper metal in the filtrate is subjected to iron powder as a displacer, and when iron powder is added as a theoretical value of 100 times, 1% by mole of copper in the filtrate after crystallization can be replaced with copper powder for recovery. Another copper sulphide impregnated residue is impregnated with 18N sulfuric acid at a solid-liquid ratio of 5g/5〇ml and 〇 at 70 C for 2 hours, and 100% of the copper in the residue can be immersed and dissolved. The steel immersion liquid is contained, and the iron powder is used as a displacer, and the added amount is 15 times the theoretical value of the iron powder, and the copper ΙΟΟ ο / in the secondary sulfuric acid immersion liquid can be used. It is replaced and recycled into steel powder. The silver in the secondary sulfuric acid impregnation residue is immersed in 8N nitric acid at a solid-liquid ratio of lg/50m at 70 ° C for 4 hours, and the silver in the residue can be impregnated and dissolved. Silver immersion liquid, first adjust the pH value of the silver solution with ammonia water to 1 ,, and then use hydrochloric acid (12N) as a precipitant, and the condition of hydrochloric acid (ml) / silver solution (ml) = 4 The silver metal 100% precipitate was recovered into gasified silver. 201036718 The gold contained in the residue of nitric acid leaching is treated with 100% aqua regia as an impregnating agent. Under the condition of solid-liquid ratio 0.3⁄4 (residual fishing), 11 (aqua regia), at 7 (TC dip) After 4 hours of collapse, 1% of the gold in the residue can be impregnated and dissolved. The best gold-containing impregnation solution can be used to replace the gold in the best gold-containing impregnation solution with zinc powder as a displacer. 9943% will be replaced and recycled. · ❹ 12