KR20140100603A - Refining method of Tin sludge - Google Patents
Refining method of Tin sludge Download PDFInfo
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- KR20140100603A KR20140100603A KR1020130012896A KR20130012896A KR20140100603A KR 20140100603 A KR20140100603 A KR 20140100603A KR 1020130012896 A KR1020130012896 A KR 1020130012896A KR 20130012896 A KR20130012896 A KR 20130012896A KR 20140100603 A KR20140100603 A KR 20140100603A
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- tin
- sludge
- precipitate
- refining
- reducing agent
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- 229910052718 tin Inorganic materials 0.000 title claims abstract description 77
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000010802 sludge Substances 0.000 title claims abstract description 35
- 238000007670 refining Methods 0.000 title claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000003472 neutralizing Effects 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N Tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 37
- 229910001887 tin oxide Inorganic materials 0.000 claims description 35
- 239000002244 precipitate Substances 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000003638 reducing agent Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000008188 pellet Substances 0.000 claims description 8
- 238000006722 reduction reaction Methods 0.000 claims description 8
- 230000005591 charge neutralization Effects 0.000 claims description 7
- 230000001264 neutralization Effects 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 235000013312 flour Nutrition 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- 235000021307 wheat Nutrition 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L Calcium hydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 240000003183 Manihot esculenta Species 0.000 claims description 3
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 3
- 229940080314 Sodium Bentonite Drugs 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N Sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 3
- 239000000571 coke Substances 0.000 claims description 3
- 235000005822 corn Nutrition 0.000 claims description 3
- 235000005824 corn Nutrition 0.000 claims description 3
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 235000013379 molasses Nutrition 0.000 claims description 3
- 229910000280 sodium bentonite Inorganic materials 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 235000019794 sodium silicate Nutrition 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 2
- 235000015450 Tilia cordata Nutrition 0.000 claims description 2
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 2
- 239000004571 lime Substances 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N silicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 240000008529 Triticum aestivum Species 0.000 claims 1
- 240000008042 Zea mays Species 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 6
- 238000004140 cleaning Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract 1
- 239000011135 tin Substances 0.000 description 60
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 8
- 239000000428 dust Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 4
- 241000209140 Triticum Species 0.000 description 3
- 239000010793 electronic waste Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 241000209149 Zea Species 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium monoxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000004484 Briquette Substances 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N Calcium silicate Chemical group [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 229920002456 HOTAIR Polymers 0.000 description 1
- 206010061289 Metastatic neoplasm Diseases 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001186 cumulative Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- AUYOHNUMSAGWQZ-UHFFFAOYSA-L dihydroxy(oxo)tin Chemical compound O[Sn](O)=O AUYOHNUMSAGWQZ-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000001394 metastastic Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/04—Obtaining tin by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
Description
본 발명은 주석오니의 정련방법에 관한 것으로, 더욱 상세하게는 주석의 제련과정, 주석의 정련과정 및 주석의 도금공정 등에서 발생하는 주석오니의 정련방법에 관한 것이다.
The present invention relates to a refining method of tin sludge, and more particularly to a refining method of tin sludge which occurs in a tin smelting process, a tin refining process, and a tin plating process.
최근 전자산업의 비약적인 발전과 함께 전기전제 제품의 디자인 및 제품의 기술혁신 등에 의해서 교체 주기가 점점 짧아지고 있다. 그러나 이러한 사업발전의 결과로서 전자 폐기물의 발생량은 급격히 증가하였다. 이들 전자 폐기물에는 금, 은과 같은 고가의 귀금속 이외에도 구리, 아연, 주석 등의 유가금속이 함유되어 있어 전자 폐기물은 발생과 동시에 처리과정 없이 폐기되거나 소각되는 경우, 환경적인 악영향을 물론 폐기물 내의 유가금속 및 귀금속의 경제적인 손실을 야기하는 문제점이 있었다. In recent years, with the rapid development of the electronics industry, the replacement cycle has become shorter due to the design of the electric premise product and the technical innovation of the product. However, as a result of these business developments, the amount of electronic waste generated has increased sharply. These electronic wastes contain precious metals such as gold and silver as well as valuable metals such as copper, zinc and tin. When electronic wastes are discarded or incinerated without being processed at the same time as they are generated, And economical loss of precious metals.
이에 이들 공정 중 발생하는 폐기물로부터 금속을 회수하는 기술이 개발되고 있다. 그 중에서 특히 주석을 회수하는 방법에는 습식정제법, 건식정제법 등이 있다.Accordingly, techniques for recovering metals from wastes generated during these processes have been developed. Particularly, there are a wet refining method, a dry refining method and the like as a method for recovering tin.
그러나, 습식정제법은 전해액에 음극, 양극판을 설치하여 전기분해시킴으로써 음극판에 주석이 모이도록 하여 주석을 회수하는 방법으로, 가장 많이 사용되고 있지만 처리비용이 고가이고, 정제시간 길며, 사용되는 시약의 양이 많을 뿐만 아니라, 에너지 소모량이 높고, 양극전물(Anode Slime)로 인한 주석과 불순물의 누적증가, 폐액처리 비용의 증가, 시설투자비의 증가 및 처리인력비의 증가 등의 문제점이 있었다.However, the wet refining method is a method of recovering tin by collecting tin by collecting tin on the negative electrode plate by electrolytically dissolving the negative electrode and the positive electrode plate in the electrolytic solution. This tin is most widely used but requires high processing cost, long purification time, There are problems such as high energy consumption, cumulative increase of tin and impurities due to anode slime, increase of waste liquid treatment cost, increase of facility investment cost and increase of processing manpower ratio.
또한, 건식정제법은 고온에서 주석오니를 가열하여 용련과정을 거쳐 주석을 회수하는 방법이다. 그러나 이러한 건식처리법은 초기 설비 투자비가 많이 들 뿐만 아니라, 처리하는 과정에서는 분말상의 주석오니를 처리하게 되면 용해로에서 분진이 발생하여 주석의 회수율을 급격하게 저하시키는 문제점이 있었다.
The dry refining method is a method in which tin is recovered by heating a tin sludge at a high temperature and undergoing a refining process. However, such a dry treatment method has a problem in that not only the initial facility investment cost is high but also, when the tin sludge powder is treated in the process, dust is generated in the melting furnace and the recovery rate of tin is drastically lowered.
따라서, 본 발명은 상기한 문제점을 해결하면서 처리비용이 저렴하며, 정제시간이 짧고, 사용되는 시약의 양이 적은 주석오니의 정련방법을 제공하는 것이다.SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a method for refining tin sludge which is low in processing cost, has a short purification time, and has a small amount of reagent to be used while solving the above problems.
또한, 본 발명의 다른 목적은 에너지 소모량이 낮고, 양극전물(Anode Slime)로 인한 주석과 불순물이 증가 되지 않으며, 폐액처리 비용, 시설투자비 및 처리인력 비용이 저렴한 주석오니의 정련방법을 제공하는 것이다.Another object of the present invention is to provide a refining method of tin sludge which is low in energy consumption, does not increase tin and impurities due to anode slime, and is low in waste solution treatment cost, facility investment cost, and processing labor cost .
본 발명의 또 다른 목적은 주석오니에 함유된 주석을 추출하여 산업자원으로 재활용할 수 있도록 하는 정련방법에 적합한 금속조석을 제공하는 주석오니의 정련방법을 제공하는 것이다.
It is still another object of the present invention to provide a refining method of tin sludge that provides a metal tide suitable for a refining method that enables tin contained in tin sludge to be extracted and recycled as industrial resources.
본 발명의 목적은 주석오니를 금속조석으로 제조하는 금속조석제조단계(S100), 상기 금속조석제조단계(S100)를 통해 제조된 금속조석을 질산용액에 투입하여 침전물과 질산용액을 분리하는 침전물분리단계(S200), 상기 침전물분리단계(S200)를 통해 분리된 침전물을 염기성 중화제를 이용하여 중화 및 세척하는 단계(S300), 상기 중화 및 세척단계(S300)를 통해 얻은 침전물을 여과, 건조하여 고체 주석을 얻는 가공단계(S400)로 이루어지는 것을 특징으로 하는 주석오니의 정련방법에 관한 것이다.The object of the present invention is to provide a method of manufacturing a tungsten sludge, comprising the steps of: preparing tungsten sludge as a metal tongue (S100); depositing a metal tongue prepared through the metal tongue preparation step (S100) (S200), neutralizing and washing the precipitate separated through the precipitate separation step (S200) using a basic neutralizing agent (S300), filtering and drying the precipitate obtained through the neutralization and washing step (S300) And a processing step of obtaining tin (S400).
본 발명의 바람직한 특징에 따르면, 상기 금속조석제조단계(S100)는 주석오니에 바인더 및 제1환원제를 혼합하여 펠렛이나 단광과 같은 형태의 주석산화물로 제조하는 성형단계(S110), 상기 성형단계(S110)를 거쳐 제조된 주석산화물을 용해로에 투입하고 가열하는 가열단계(S120), 및 상기 가열단계(S120)를 통해 용융된 주석산화물에 제2환원제를 투입하여 금속조석으로 제조하는 환원반응단계(S130)로 이루어지는 것으로 한다.According to a preferred feature of the present invention, the metal tongue manufacturing step (S100) comprises: a forming step (S110) of mixing tin sludge with a binder and a first reducing agent to form tin oxide in the form of pellets or single- A heating step (S120) of adding a tin oxide produced through a heating step (S110) to a melting furnace and heating the melted tin oxide to a melting furnace, and a reducing reaction step S130).
본 발명의 더 바람직한 특징에 따르면, 상기 성형단계(S110)는 분말상태의 주석오니 100 중량부에 바인더 1 내지 3 중량부 및 환원제 0.5 내지 1.5 중량부를 혼합하여 이루어지는 것으로 한다.According to a more preferred feature of the present invention, the forming step (S110) comprises mixing 1 to 3 parts by weight of a binder and 0.5 to 1.5 parts by weight of a reducing agent in 100 parts by weight of tin sludge in powder form.
본 발명의 더욱 바람직한 특징에 따르면, 상기 바인더는 타피오카, 당밀, 밀, 옥수수, 규산소다, 벤토나이트 및 소석회로 이루어진 그룹으로부터 선택된 하나 이상으로 이루어지는 것으로 한다.According to a further preferred feature of the present invention, the binder is made of at least one selected from the group consisting of tapioca, molasses, wheat, corn, sodium silicate, bentonite and slaked lime.
본 발명의 더욱 더 바람직한 특징에 따르면, 상기 제1환원제는 코크스분말, 밀가루, 전분 및 목분으로 이루어진 그룹으로부터 선택된 하나 이상으로 이루어지는 것으로 한다.According to a further preferred feature of the present invention, the first reducing agent is at least one selected from the group consisting of coke powder, flour, starch and wood flour.
본 발명의 더욱 더 바람직한 특징에 따르면, 상기 가열단계(S120)는 1230 내지 1300℃의 온도로 이루어지는 것으로 한다.According to an even more preferred feature of the present invention, the heating step (S120) is performed at a temperature of 1230 to 1300 ° C.
본 발명의 더욱 더 바람직한 특징에 따르면, 상기 환원반응단계(S130)는 상기 가열단계를 통해 용융된 주석산화물 100 중량부에 제2환원제 0.4 내지 1.5 중량부를 투입하여 이루어지는 것으로 한다.According to still another more preferred characteristic of the present invention, the reduction reaction step (S130) is carried out by adding 0.4 to 1.5 parts by weight of the second reducing agent to 100 parts by weight of the molten tin oxide through the heating step.
본 발명의 더욱 더 바람직한 특징에 따르면, 상기 제2환원제는 규산석회인 것으로 한다.According to a further preferred feature of the present invention, the second reducing agent is silicate lime.
본 발명의 더욱 더 바람직한 특징에 따르면, 상기 질산의 농도는 20 내지 70%이며, 바람직하게는 30 내지 60%인 것으로 한다.According to a further preferred feature of the present invention, the concentration of the nitric acid is 20 to 70%, preferably 30 to 60%.
본 발명의 더욱 더 바람직한 특징에 따르면, 상기 침전물분리단계(S200)는 20 내지 40℃, 바람직하게는 25 내지 30℃의 온도로 이루어지는 것으로 한다.According to a further preferred feature of the present invention, the precipitate separation step (S200) is performed at a temperature of 20 to 40 ° C, preferably 25 to 30 ° C.
본 발명의 더욱 더 바람직한 특징에 따르면, 상기 침전물분리단계(S200)로부터 형성된 침전물은 염기성 중화제를 이용하여 pH 4 내지 8로 중화시키는 것으로 이루어진다.According to a further preferred feature of the present invention, the precipitate formed from the precipitate separation step (S200) is neutralized to pH 4 to 8 using a basic neutralizing agent.
상기 염기성 중화제는 가성소다 또는 과산화수소인 것으로 한다.The basic neutralizing agent is caustic soda or hydrogen peroxide.
본 발명의 더욱 더 바람직한 특징에 따르면, 상기 여과는 여과지 또는 유리필터를 이용하여 이루어지는 것으로 한다.According to a further preferred feature of the present invention, the filtration is performed using a filter paper or a glass filter.
본 발명의 더욱 더 바람직한 특징에 따르면, 상기 건조는 180 내지 200℃ 온도에서 2 내지 4시간 동안 이루어지는 것으로 한다.
According to an even more preferred feature of the present invention, the drying is performed at a temperature of 180 to 200 ° C for 2 to 4 hours.
본 발명에 따른 주석오니의 정련방법은 처리비용이 저렴하며, 정제시간이 짧고, 사용되는 시약의 양이 적은 탁월한 효과를 나타낸다. 또한, 에너지 소모량이 낮고, 양극전물(Anode Slime)로 인한 주석과 불순물이 증가 되지 않으며, 폐액처리 비용, 시설투자비 및 처리인력 비용이 저렴하며, 주석오니에 함유된 주석을 추출하여 산업자원으로 재활용할 수 있도록 하는 정련방법에 적합한 금속조석을 제공하는 탁월한 효과를 나타낸다.
The refining method of the tin sludge according to the present invention exhibits an excellent effect that the processing cost is low, the refining time is short, and the amount of the reagent to be used is small. In addition, the energy consumption is low, the tin and the impurities due to the anode slime are not increased, the waste solution processing cost, the facility investment cost and the manpower cost are low, and the tin contained in the tin sludge is extracted and recycled as industrial resources The present invention provides an excellent effect of providing a metal trowel suitable for a refining method capable of making a metal trowel.
도 1은 본 발명에 따른 주석오니의 정련방법을 나타낸 순서도이다.1 is a flowchart showing a refining method of tin sludge according to the present invention.
이하에는, 본 발명의 바람직한 실시예와 각 성분의 물성을 상세하게 설명하되, 이는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 발명을 용이하게 실시할 수 있을 정도로 상세하게 설명하기 위한 것이지, 이로 인해 본 발명의 기술적인 사상 및 범주가 한정되는 것을 의미하지는 않는다.
Hereinafter, preferred embodiments of the present invention and physical properties of the respective components will be described in detail with reference to the accompanying drawings. However, the present invention is not limited thereto, And this does not mean that the technical idea and scope of the present invention are limited.
본 발명에 따른 주석오니의 정련방법은 주석오니를 금속조석으로 제조하는 금속조석제조단계(S100), 상기 금속조석제조단계(S100)를 통해 제조된 금속조석을 질산용액에 투입하여 침전물과 질산용액을 분리하는 침전물분리단계(S200), 상기 침전물분리단계(S200)를 통해 분리된 침전물에 염기성 중화제를 이용하여 중화 및 세척 하는 단계(S300), 및 상기 중화 및 세척단계(S300)를 통해 얻은 침전물을 여과, 건조하여 고체 주석을 얻는 가공단계(S400)로 이루어진다.
The method for refining tin sludge according to the present invention comprises the steps of preparing a tin (S100) for manufacturing a tin sludge as a metal tin, a step for adding the metal tin produced through the step (S100) (S300) of neutralizing and washing the precipitate separated through the precipitate separation step (S200) using a basic neutralizing agent, and a step (S300) of removing the precipitate obtained through the neutralization and washing step (S300) (S400) for obtaining solid tin by filtration and drying.
상기 금속조석제조단계(S100)는 주석오니를 금속조석으로 제조하는 단계로, 주석오니에 바인더 및 제1환원제를 혼합하여 펠렛(Pallets)이나 단광(briquette)과 같은 형태의 주석산화물로 제조하는 성형단계(S110), 상기 성형단계(S110)를 거쳐 제조된 주석산화물을 용해로에 투입하고, 가열하는 가열단계(S120), 및 상기 가열단계(S120)를 통해 용융된 주석산화물에 제2환원제를 투입하여 금속조석(粗錫)으로 제조하는 환원반응단계(S130)로 이루어진다.The metal tongue manufacturing step (S100) is a step of producing tin sludge as a metal tin. The tin sludge is mixed with a binder and a first reducing agent to form a tin oxide such as pellets or briquette A step S120 of heating the tin oxide produced through the forming step S110 and a heating step S120 of heating the molten tin oxide into the melting furnace, And a reduction reaction step (S130) of making metallic tungsten (crude tin).
상기 성형단계(S110)는 주석오니에 바인더 및 제1환원제를 혼합하여 펠렛이나 단광과 같은 형태의 주석산화물로 제조하는 단계로, 분말상태의 주석오니 100 중량부에 바인더 1 내지 3 중량부 및 환원제 0.5 내지 1.5 중량부를 혼합하여 이루어진다.The forming step S110 is a step of mixing the tin sludge with the binder and the first reducing agent to prepare tin oxide in the form of pellets or monochromatic light. In 100 parts by weight of the tin sludge in powder form, 1 to 3 parts by weight of a binder, 0.5 to 1.5 parts by weight.
주석오니는 성상이 가루(입자상물질) 또는 미분(微粉)과 같은 주석산화물로 존재할 수 있는데, 이를 직접 용해로에서 처리시에는 분진이 발생할 수 있으며, 이러한 분진발생은 계속적으로 증가될 수 있고, 계속되는 분진의 발생은 주석의 회수율(Recovery)을 급격히 떨어뜨린다.The tin sludge may be present as a tin oxide such as powder (particulate matter) or fine powder (dust) when treated directly in a melting furnace, and the generation of such dust can be continuously increased, The recovery of tin abruptly decreases.
따라서, 건조된 미분 상태의 드로스(Dross)나 더스트(Dust)를 처리할 경우에도 주석산화물을 펠렛이나 단광으로 성형하기 위하여 바인더가 혼합되는데, 상기 바인더는 주석산화물의 화학적 성상 등을 고려하여 사용해야 하며, 사용량은 바인더가 혼합되어 펠렛이나 단광으로 성형된 주석산화물을 손으로 쥐었을 때 뭉침현상이 발생할 정도가 바람직하며, 수분의 함량이 10 내지 12%인 것이 더욱 바람직하다.Therefore, when treating the dried Dross or Dust of the pulverized state, the binder is mixed to form the tin oxide into pellets or a single light. The binder should be used in consideration of the chemical properties of the tin oxide And the amount of use is preferably such that when the binder is mixed and tin oxide formed by pellet or single light is grasped by hand, aggregation occurs, and it is more preferable that the content of moisture is 10 to 12%.
또한, 상기의 가루 또는 미분상태인 주석산화물은 입자가 매우 미세하기 때문에 습도의 조절을 위해 곤죽상태의 주석산화물에 건조된 미분상태의 산화물 더스트(Dust)와 건조된 미분 상태의 드로스(Dross) 및 바인더를 혼합하여 수분 및 점결도 등을 맞출 수도 있다.In order to control the humidity, the tin oxide, which is the powder or the fine powder state, is very fine. Therefore, in order to control the humidity, the oxide dust and the dried fine powder state dross, And the binder may be mixed to adjust the moisture and the degree of hardness.
상기 주석오니가 주석 도금공정에서 발생되는 주석산화물인 경우에는 주석산화물에 함유되어 있는 폐산에 의한 영향이 없도록 세척하거나, 중화시켜 사용하는 것이 바람직한데, 주석산화물을 중화시키는 방법은 주석산화물에 함유된 액량을 고려하여, 중화제인 가성소다 또는 과산화수소로 처리하는 것이 바람직하며, 이때, 가성소다 또는 과산화수소의 사용량은 주석산화물의 pH가 6.5에 도달할 때까지 처리하는 것이 바람직하다.When the tin sludge is tin oxide generated in the tin plating process, it is preferable to clean or neutralize the tin oxide so that there is no influence of the waste acid contained in the tin oxide. It is preferable to treat with caustic soda or hydrogen peroxide which is a neutralizing agent in consideration of the liquid amount. It is preferable that the caustic soda or the hydrogen peroxide is used until the pH of the tin oxide reaches 6.5.
상기의 성형단계(S110)에서 주석산화물의 양이 많은 경우에는 성구기(成球機)(Palletaizer) 또는 단광기(成球機)(Briquetter)를 이용하여 성형단계를 진행하는 것이 바람직하며, 상기 성형단계(S110)를 통해 성형된 주석산화물은 일정한 강도가 유지될 수 있도록 건조시켜야 하는데. 주석산화물이 용해로에서 적합한 성형강도를 나타낼 수 있도록 온풍으로 가열하거나, 자연상태에서 3 내지 5일 정도 자연통풍하여 건조한다.If the amount of tin oxide is large in the forming step S110, it is preferable to perform the molding step using a ball peener or a briquetter, The tin oxide formed through the molding step (S110) must be dried to maintain a constant strength. The tin oxide is heated by hot air so as to exhibit a suitable molding strength in the melting furnace, or dried by natural ventilation for about 3 to 5 days in a natural state.
이러한 건조의 과정을 거치면 용해로에서 처리시에 분진을 발생시키지 않는 주석산화물이 제조된다. Through such a drying process, tin oxide is produced which does not generate dust upon treatment in the melting furnace.
이때, 상기 바인더는 타피오카, 당밀, 밀, 옥수수, 규산소다, 벤토나이트 및 소석회로 이루어진 그룹으로부터 선택된 하나 이상으로 이루어지는 것이 바람직하며, 상기 제1환원제는 연소시에 탄화하여 탄소를 발생하거나, 일산화탄소를 발생시킬수 있는 것이면 특별히 한정되지 않지만, 코크스분말, 밀가루, 전분 및 목분으로 이루어진 그룹으로부터 선택된 하나 이상으로 이루어지는 것이 바람직하다.The binder may be at least one selected from the group consisting of tapioca, molasses, wheat, corn, sodium silicate, bentonite, and slaked lime. The first reducing agent may be carbonized during combustion to generate carbon, But is preferably made of at least one selected from the group consisting of coke powder, wheat flour, starch and wood flour.
상기 가열단계(S120)는 상기 성형단계(S110)를 거쳐 제조된 주석산화물을 용해로에 투입하고, 가열하는 단계로, 상기 성형단계(S110)에서 펠렛이나 단광의 형태로 성형된 주석산화물을 용해로에 투입하고 1230 내지 1300℃의 온도로 가열하여 용융하는 단계다.The heating step S120 is a step of injecting and heating the tin oxide produced through the forming step S110 into the melting furnace and heating the tin oxide formed in the form of pellets or a single light in the forming step S110 to the melting furnace And is heated and melted at a temperature of 1230 to 1300 ° C.
이때, 상기 주석산화물을 용융하는 과정에서는 펠렛이나 단광의 형태로 성형된 주석산화물을 사용하기 때문에, 분진이 발생하지 않는다.At this time, in the process of melting the tin oxide, since tin oxide formed in the form of pellets or a single light is used, dust is not generated.
상기 환원반응단계(S130)는 상기 가열단계(S120)를 통해 용융된 주석산화물에 제2환원제를 투입하여 금속조석으로 제조하는 단계로, 상기 가열단계(S120)를 통해 용융된 주석산화물 100 중량부에 제2환원제 0.4 내지 1.5 중량부를 투입하여 이루어진다.In the reducing reaction step S130, the second reducing agent is added to the molten tin oxide through the heating step (S120) to produce metallic tungsten. In the heating step (S120), 100 parts by weight of molten tin oxide And 0.4 to 1.5 parts by weight of a second reducing agent.
상기 가열단계(S120)를 통해 용융된 주석산화물을 금속조석으로 제조하기 위해서는 반응로 내에서 용융된 주석산화물과 상기 제2환원제가 반응하는 환원반응이 이루어져야 하는데, 상기와 같은 환원반응의 효율을 높이기 위해 회전기능이 구비된 용해로를 사용하는 것이 바람직하다.In order to prepare the molten tin oxide as the metal tile through the heating step (S120), a reduction reaction in which the molten tin oxide and the second reducing agent react with each other must be performed in the reaction furnace. In order to increase the efficiency of the reduction reaction, It is preferable to use a melting furnace provided with a function for rotating the melt.
상기 제2환원제의 함량이 0.4 미만이면, 환원반응이 제대로 진행되지 않고, 상기 제2환원제의 함량이 1.5 중량부를 초과하게 되면 용융된 주석산화물에 함유된 여러 불순물이 금속조석에 인입될 수 있다.If the content of the second reducing agent is less than 0.4, the reduction reaction does not proceed properly. If the content of the second reducing agent exceeds 1.5 parts by weight, various impurities contained in the molten tin oxide may be introduced into the metal tide.
특히, 상기의 불순물 중에서는 철(Fe)의 인입을 주의해야 하는데, 철의 인입을 차단하기 위해서는 제2환원제의 함량뿐만 아니라, 용해로에서 환원반응을 진행할 때, 산화철(Fe0)의 형태로 용출되는 철 성분은 용해로 외부로 배출하는 것이 바람직하다.Particularly, among the above-mentioned impurities, it is necessary to pay attention to the inflow of iron (Fe). In order to block the inflow of iron, not only the content of the second reducing agent but also the amount of iron The iron component is preferably discharged to the outside of the melting furnace.
이때, 상기 제2환원제는 산화칼슘과 이산화규소가 1:1 비율로 결합한 형태인 규산석회(CaO-SiO2)를 사용하는 것이 바람직하다.At this time, it is preferable that the second reducing agent is calcium silicate (CaO-SiO 2 ) in which calcium oxide and silicon dioxide are combined in a ratio of 1: 1.
상기의 과정으로 이루어지는 금속조석제조단계(S100)를 거치면 주석의 정제법에 적합한 금속조석이 제공된다.The metal tide, which is suitable for the refining process of tin, is provided through the metal tongue making step S100 comprising the above process.
상기 환원반응단계를 아래에 나타내었다.The reduction reaction step is shown below.
SnO₂+ 2CO → Sn + 2CO₂SnO 2 + 2CO -> Sn + 2CO 2
SnO₂+ 2Fe → Sn + 2FeO (FeO의 계외 배출)SnO2 + 2Fe? Sn + 2FeO (out-of-phase release of FeO)
SnO + C → Sn + COSnO + C? Sn + CO
SnO + CO → Sn + CO₂
SnO + CO → Sn + CO2
상기 침전물분리단계(S200)는 상기 금속조석제조단계(S100)를 통해 제조된 금속조석을 질산용액에 투입하여 침전물과 질산용액 분리하는 단계로, 상기 금속조석을 질산용액에 투입한 다음 밀폐된 공간에서 산 용해법에 의하여 주석이 포함된 침전물을 분리한다.The sediment separation step (S200) is a step of separating the precipitate and the nitric acid solution by injecting the metal tide produced through the metal tongue preparation step (S100) into the nitric acid solution. The metal tide is introduced into the nitric acid solution, The tin-containing precipitate is separated by an acid dissolution method.
더욱 상세하게는, 상기 금속조석을 질산이 30 내지 60중량%의 농도로 포함된 질산용액에 투입하고, 25 내지 30℃의 온도에서 교반하여 용해한다. 상기 금속조석에 포한된 주석과 질산의 반응으로 침전물인 메타스태닉산(metastannic acid, H2SnO3)이 생성된다. More specifically, the metal tide is put into a nitric acid solution containing nitric acid at a concentration of 30 to 60 wt%, and is dissolved by stirring at a temperature of 25 to 30 캜. The reaction of tin and nitric acid in the metal tide produces a precipitate, metastannic acid (H 2 SnO 3 ).
상기 질산용액의 질산 농도가 30% 미만이면 질산과 주석이 반응하지 않아 침전물이 형성되지 않으며, 상기 질산용액의 농도가 60%를 초과하면 주석 이외의 다른 금속들도 질산과 반응하여 순수한 주석을 분리할 수 없다.If the nitric acid concentration of the nitric acid solution is less than 30%, nitric acid and tin do not react to form a precipitate, and when the concentration of the nitric acid solution exceeds 60%, other metals than tin also react with nitric acid to separate pure tin Can not.
상기 침전물분리단계(S200)를 아래 반응식으로 나타내었다.The precipitate separation step (S200) is represented by the following reaction formula.
Sn + 2HNO3 → H2SnO3 + NO + NO2
Sn + 2HNO 3 → H 2 SnO 3 + NO + NO 2
상기 중화 및 세척단계(S300)는 상기 침전물분리단계(S200)을 통해 분리된 침전물 메타스태닉산에 염기성 중화제를 첨가하여 pH를 조절하고, 원심분리기를 통해 침전물의 세척을 수행한다.In the neutralization and washing step (S300), a basic neutralizing agent is added to the precipitate metastatic acid separated through the precipitate separation step (S200) to adjust the pH, and the precipitate is washed through a centrifuge.
더욱 상세하게는, 상기 침전물에 함유되어 있는 폐산을 중화시키기 위해 가성소다 또는 과산화수소를 pH 4 내지 8, 바람직하게는 pH 6.5에 도달할 때까지 처리하여 중화하는 것이 바람직하다.
More specifically, in order to neutralize the waste acid contained in the precipitate, it is preferable to neutralize caustic soda or hydrogen peroxide by treating it until the pH reaches 4 to 8, preferably to pH 6.5.
상기 가공단계(S400)은 상기 중화 및 세척단계(S300)를 통해 세척된 침전물을 여과 및 건조를 통하여 이루어진다.The processing step (S400) is performed through filtration and drying of the precipitate washed through the neutralization and washing step (S300).
상기 여과는 여과지나 유리필터를 이용하여 이루어지나, 침전물에 존재하는 용액을 제거하는 것이라면 이에 한정되지는 않는다.The filtration is performed using a filter or a glass filter, but is not limited thereto as long as it removes the solution present in the precipitate.
상기 건조는 180 내지 200℃ 온도에서 2 내지 4시간 동안 하는 것이 바람직하다.
The drying is preferably performed at a temperature of 180 to 200 ° C for 2 to 4 hours.
상기의 가공단계(S400)가 완료되면, 금속조석제조단계(S100), 침전물분리단계(S200), 중화 및 세척단계(S300), 가공단계(S400)로 이루어지는 본 발명의 주석폐기물의 정련방법이 완료되며, 이러한 주석폐기물의 정련방법을 통해 정련된 주석은 철, 구리, 납 및 아연 등의 금속이 함유되지 않거나 그 함량이 매우 낮아 산업자원으로 재활용할 수 있는 탁월한 효과를 나타낸다.
When the above-mentioned processing step (S400) is completed, the refining method of the tin waste of the present invention comprising the steps of producing metal tide (S100), precipitate separation step (S200), neutralization and washing step (S300) The refined tin through the refining method of such tin waste has excellent effect that it can be recycled as an industrial resource because it contains no metal such as iron, copper, lead and zinc or its content is very low.
S100 ; 금속조석제조단계
S110 ; 성형단계
S120 ; 가열단계
S130 ; 환원반응단계
S200 ; 침전물분리단계
S300 ; 중화 및 세척단계
S400 ; 가공단계S100; Metal tide manufacturing phase
S110; Molding step
S120; Heating step
S130; Reduction reaction step
S200; Precipitate separation step
S300; Neutralization and washing steps
S400; Processing step
Claims (14)
A metal tide manufacturing step (S100) of producing tin sludge as metal tungsten; A sediment separation step (S200) for separating the precipitate and the nitric acid solution by injecting the metal tide produced through the metal tide production step (S100) into a nitric acid solution; Neutralizing and washing the precipitate separated through the precipitate separation step (S200) using a basic neutralizing agent (S300); And a step (S400) of filtering and drying the precipitate obtained through the neutralization and washing step (S300) to obtain solid tin (S400).
The method according to claim 1, wherein the metal tongue manufacturing step (S100) comprises: a forming step (S110) of mixing tin sludge with a binder and a first reducing agent to form tin oxide in the form of pellets or mono-type; A heating step (S120) of charging the tin oxide produced through the forming step (S110) into the melting furnace and heating the tin oxide; And a reducing reaction step (S130) in which the second reducing agent is added to the molten tin oxide through the heating step (S120) to produce a metallic tungsten.
The method according to claim 2, wherein the forming step (S110) comprises mixing 1 to 3 parts by weight of a binder and 0.5 to 1.5 parts by weight of a reducing agent in 100 parts by weight of tin sludge in powder form.
The method according to claim 2, wherein the binder comprises at least one selected from the group consisting of tapioca, molasses, wheat, corn, sodium silicate, bentonite and slaked lime.
The method according to claim 2, wherein the first reducing agent is at least one selected from the group consisting of coke powder, flour, starch and wood flour.
The method according to claim 2, wherein the heating step (S120) is performed at a temperature of 1230 to 1300 ° C.
The method according to claim 2, wherein the reduction reaction step (S130) comprises charging 0.4 to 1.5 parts by weight of a second reducing agent to 100 parts by weight of molten tin oxide through the heating step.
The method for refining tin sludge according to claim 2, wherein the second reducing agent is silicate lime.
The method according to claim 1, wherein the concentration of the nitric acid solution is 20 to 70%.
The method according to claim 1, wherein the precipitate separation step (S200) is performed at a temperature of 20 to 40 占 폚.
The method according to claim 1, wherein the precipitate formed from the precipitate forming step (S200) is neutralized to a pH of 4 to 8.
The method for refining tin sludge according to claim 1, wherein the basic neutralizing agent is caustic soda or hydrogen peroxide.
The method for refining tin sludge according to claim 1, wherein the filtration is performed using a filter paper or a glass filter.
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| CN108456779A (en) * | 2017-02-18 | 2018-08-28 | 唐翔 | Electroplating sludge, leather-making mud, metal solid waste produce metal and metallic compound technique |
| CN112011689A (en) * | 2019-05-30 | 2020-12-01 | 惠州Tcl环境科技有限公司 | Method for recovering substances from waste tin stripping waste liquid of nitric acid system |
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| KR20000058674A (en) * | 2000-06-23 | 2000-10-05 | 김주형 | The method of extracting tin of high purity from dregs |
| KR101054840B1 (en) * | 2009-09-29 | 2011-08-05 | 한양대학교 산학협력단 | Method for preparing tin oxide powder recycled indium tin oxide waste scrap |
| KR101314746B1 (en) * | 2011-03-28 | 2013-10-08 | 타운마이닝캄파니(주) | Recovery method of tin and nickel from iron scrap comprising tin and nickel compound |
| KR101169927B1 (en) * | 2012-02-21 | 2012-08-06 | (주)에이원엔지니어링 | Method for withdraing tin by dry refining from tin sludge |
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| CN112011689A (en) * | 2019-05-30 | 2020-12-01 | 惠州Tcl环境科技有限公司 | Method for recovering substances from waste tin stripping waste liquid of nitric acid system |
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