CN1325668C - Leaching method for complicated cupric sulfide aurin ore - Google Patents
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Abstract
本发明涉及一种湿法冶金技术领域，尤其是一种复杂硫化铜金精矿的浸出方法。该方法是将矿浆在常压氧化条件下搅拌浸出、萃取、氰化浸出一锌粉置换回收金银铜和浮选富集一热滤回收单质硫，在搅拌浸出工序中添加能改变硫化铜矿物表面活性的催化剂硝酸铁、硫酸铁、氯化铁、钒氧化物、锰化合物、钛化合物中的任一种或其组合，用量为0.05～1.0mol/L。本发明具有可在常压和低温下氧化浸出、技术条件容易控制、操作方便、无危险、生产成本低、金银铜浸出率高且杂质含量低、能综合回收硫、对环境友好等特点。The invention relates to the technical field of hydrometallurgy, in particular to a method for leaching complex copper-gold sulfide concentrates. The method is to leaching, extracting, and cyaniding the slurry under normal pressure oxidation conditions—zinc powder replacement and recovery of gold, silver and copper, flotation enrichment—hot filtration to recover elemental sulfur, and adding energy to change copper sulfide ore in the stirring and leaching process. The surface active catalyst is any one or combination of ferric nitrate, ferric sulfate, ferric chloride, vanadium oxide, manganese compound, titanium compound, and the dosage is 0.05-1.0 mol/L. The invention has the characteristics of oxidative leaching at normal pressure and low temperature, easy control of technical conditions, convenient operation, no danger, low production cost, high leaching rate of gold, silver and copper, low impurity content, comprehensive recovery of sulfur, and environmental friendliness.
Description
一.技术领域1. Technical field
本发明涉及一种湿法冶金技术领域，尤其是一种复杂硫化铜金精矿的浸出方法。The invention relates to the technical field of hydrometallurgy, in particular to a method for leaching complex copper-gold sulfide concentrates.
二.背景技术2. Background technology
业内人士认为复杂硫化铜金精矿是指矿物组成中含有黄铜矿、黄铁矿、铜蓝、闪锌矿、辉铜矿、砷黄铁矿、镍黄铁矿等组分的复杂矿。复杂硫化铜金精矿具有分布广、储量多、浸出难度大等特点。目前，处于研究阶段的复杂硫化铜金精矿的浸出方法较为集中在湿法氧化技术上，主要有：已公开的“高温高压全氧化技术”、“中温低压浸出技术”、“低温低压浸出技术”、“细菌氧化浸出技术”、“常规化学氧化技术”和与本发明较为接近的，在《有色金属》冶炼部分，2003(3)：20-21，41由蒋俊祥半公开的“高酸高氯常压催化氧化技术”六种为代表，所谓的高、中、低温分别界定在≥200℃、120～200℃、80～120℃，所谓的高、中、低压分别界定在3MPa、1.5～3MPa、0.5～1.5MPa。已公开的技术存在的问题：设备要求高、投资成本大、技术条件不易控制、操作不便、危险性大、贵金属回收困难，硫不能回收、生成的硫酸需中和处理、渣量大、成本高，不易实现工业化，有的技术方案中加入氯盐浓度高、对设备腐蚀严重，有的技术方案中氧化剂再生成本太高、浸出液难于处理，有的技术方案中矿石需要细磨、不能处理含砷硫化铜精矿、浸出时间长、动力消耗大等。半公开的技术仅披露了以浓硫酸、氯盐为浸出试剂并加入催化剂，但未披露所加的催化剂种类和用量，能使铜浸出率提高，但仍存在对设备腐蚀严重、氧气消耗多、浸出液硫酸和氯盐浓度高且难于回收铜等问题，仅处于实验室研究阶段。Industry insiders believe that complex copper-gold sulfide concentrates refer to complex minerals containing chalcopyrite, pyrite, copper blue, sphalerite, chalcocite, arsenopyrite, pentlandite and other components in the mineral composition. Complex copper-gold sulfide concentrates have the characteristics of wide distribution, large reserves, and difficult leaching. At present, the leaching methods of complex copper-gold sulfide concentrates in the research stage are relatively concentrated on wet oxidation technology, mainly including: the published "high temperature and high pressure full oxidation technology", "medium temperature and low pressure leaching technology", "low temperature and low pressure leaching technology ", "Bacterial Oxidation Leaching Technology", "Conventional Chemical Oxidation Technology" and those that are relatively close to the present invention, "High acid high Chlorine Atmospheric Pressure Catalytic Oxidation Technology" as representatives, the so-called high, medium and low temperature are respectively defined as ≥200℃, 120-200℃, 80-120℃, and the so-called high, medium and low pressure are respectively defined as 3MPa, 1.5～ 3MPa, 0.5~1.5MPa. Problems in the disclosed technology: high equipment requirements, large investment costs, difficult control of technical conditions, inconvenient operation, high risk, difficult recovery of precious metals, sulfur cannot be recovered, sulfuric acid produced needs to be neutralized, large amount of slag, high cost , it is not easy to realize industrialization, some technical schemes add chlorine salt with high concentration, which will seriously corrode the equipment, some technical schemes have too high oxidant regeneration cost, and the leachate is difficult to handle, and some technical schemes require fine grinding of ore, which cannot handle arsenic Copper sulfide concentrate, long leaching time, high power consumption, etc. The semi-disclosed technology only discloses the use of concentrated sulfuric acid and chlorine salt as leaching reagents and the addition of catalysts, but does not disclose the type and amount of catalysts added, which can increase the copper leaching rate, but there are still serious corrosion of equipment, high oxygen consumption, The high concentration of sulfuric acid and chloride salt in the leaching solution and the difficulty in recovering copper are only in the stage of laboratory research.
三.发明内容3. Contents of the invention
本发明的目的在于提供一种复杂硫化铜金精矿的浸出方法，使复杂硫化铜金精矿在低酸介质中迅速被氧气氧化，提高金银铜浸出率和综合回收硫，减少设备投资和生产成本。The object of the present invention is to provide a kind of leaching method of complex copper sulfide gold concentrate, make complex copper sulfide gold concentrate be oxidized rapidly by oxygen in low-acid medium, improve gold silver copper leaching rate and comprehensive recovery sulfur, reduce equipment investment and Cost of production.
为达到此目的，本发明主要采用如下方式完成：To achieve this goal, the present invention mainly adopts following mode to finish:
将矿浆在常压氧化条件下搅拌浸出、萃取、氰化浸出一锌粉置换回收金银铜和浮选富集-热滤回收单质硫，在搅拌浸出工序中添加能改变硫化铜矿物表面活性的催化剂硝酸铁、硫酸铁、氯化铁、钒氧化物、锰化合物、钛化合物中的任一种或其组合，用量为0.05～1.0mol/L。Stir leaching, extraction, cyanidation leaching of ore pulp under normal pressure oxidation conditions - zinc powder replacement recovery of gold, silver and copper and flotation enrichment - heat filtration recovery of elemental sulfur, adding in the stirring leaching process can change the surface activity of copper sulfide minerals The catalyst is any one of ferric nitrate, ferric sulfate, ferric chloride, vanadium oxide, manganese compound, titanium compound or a combination thereof, and the dosage is 0.05-1.0 mol/L.
搅拌浸出的浸矿试剂采用稀硫酸，并使萃余液和催化剂再循环使用。Dilute sulfuric acid is used as the leaching reagent for stirring and leaching, and the raffinate and catalyst are recycled.
搅拌浸出的搅拌最大线速度为4～5m/s。The maximum linear velocity of stirring for leaching is 4-5m/s.
在常压和60～100℃温度下搅拌，使得复杂硫化铜金精矿迅速被氧气氧化。Stirring at normal pressure and temperature of 60-100°C makes the complex copper-gold sulfide concentrate rapidly oxidized by oxygen.
本发明的具体内容还包括：The specific content of the present invention also includes:
复杂硫化铜金精矿的浸出方法，所述的催化剂用量为0.1～0.5mol/L。In the method for leaching complex copper-gold sulfide concentrates, the amount of catalyst used is 0.1-0.5 mol/L.
钒氧化物指的是三氧化钒、五氧化钒、三氯化钒。钛化合物指的是二氧化钛等。锰化合物指的是二氧化锰、锰酸钾、高锰酸钾。Vanadium oxide refers to vanadium trioxide, vanadium pentoxide, and vanadium trichloride. The titanium compound refers to titanium dioxide and the like. Manganese compounds refer to manganese dioxide, potassium manganate, and potassium permanganate.
本发明的优点：Advantages of the present invention:
1.在常压和低温下氧化浸出，技术条件容易控制、操作方便、无危险、生产成本低、金银铜浸出率高且杂质含量低、能综合回收硫。1. Oxidative leaching at normal pressure and low temperature, easy control of technical conditions, convenient operation, no danger, low production cost, high leaching rate of gold, silver and copper, low impurity content, and comprehensive recovery of sulfur.
2.添加的催化剂能使复杂硫化铜金精矿在低酸介质中迅速被氧气氧化，防腐要求低、设备投资省、氧气消耗少。2. The added catalyst can make complex copper sulfide gold concentrate rapidly oxidized by oxygen in low-acid medium, with low anti-corrosion requirements, low equipment investment and low oxygen consumption.
3.萃余液和催化剂可再循环使用，操作简便、对环境友好。3. Raffinate and catalyst can be recycled, easy to operate and friendly to the environment.
4.添加的催化剂市场上易购且价格不高、作用显著。4. The added catalyst is easy to buy in the market and the price is not high, and the effect is remarkable.
四.具体实施方式4. Specific implementation
下列实施例将进一步说明本发明。The following examples further illustrate the invention.
实施例1Example 1
用-0.074mm粒度占90％以上矿石、矿浆固体浓度10～40％、浸矿试剂采用0.1～1.0mol/L稀硫酸、通入浓度为21～96％的氧气、添加0.1～0.5mol/L硫酸铁、钒氧化物中的任一种或其组合的催化剂，在常压和60～100℃温度下浸出槽中搅拌浸出，搅拌最大线速度为4～5m/s，浸出时间为2～8小时，再经后续工序，实测：铜的浸出率＞95％、金的浸出率＞97％、银的浸出率＞93％、硫的回收率＞89％、杂质含量低、黄铁矿基本不被氧化、氧气消耗量50Nm3/t。Use -0.074mm particle size to account for more than 90% ore, ore pulp solid concentration 10-40%, use 0.1-1.0mol/L dilute sulfuric acid as the leaching reagent, feed oxygen with a concentration of 21-96%, add 0.1-0.5mol/L Catalysts of any one of iron sulfate, vanadium oxide or a combination thereof, stirred and leached in a leaching tank at a temperature of 60-100°C under normal pressure, the maximum linear velocity of stirring is 4-5m/s, and the leaching time is 2-8 Hours, and then through the follow-up process, measured: copper leaching rate> 95%, gold leaching rate> 97%, silver leaching rate> 93%, sulfur recovery> 89%, impurity content is low, pyrite basically no Oxygenated, oxygen consumption 50Nm 3 /t.
实施例2Example 2
其它条件同实施例1，只是添加硝酸铁、硫酸铁、氯化铁、钒氧化物、锰化合物、钛化合物中的任一种或其组合的催化剂，用量为0.05～1.0mol/L，浸出时间超过8小时，实测：铜、金、银的浸出率均达80％、硫的回收率达75％、杂质含量略高、黄铁矿基本不被氧化、氧气消耗量80Nm3/t。Other conditions are the same as in Example 1, except adding any one or combination of catalysts in ferric nitrate, ferric sulfate, ferric chloride, vanadium oxide, manganese compound, titanium compound, consumption is 0.05～1.0mol/L, leaching time After more than 8 hours, the actual measurement: the leaching rate of copper, gold and silver is up to 80%, the recovery rate of sulfur is up to 75%, the impurity content is slightly high, the pyrite is basically not oxidized, and the oxygen consumption is 80Nm 3 /t.
比较实验例1Comparative experiment example 1
其它条件同实施例1，添加上述催化剂1.5mol/L，浸出时间为2～8小时，铜、金、银的浸出率均＞80％、硫的回收率＞80％，萃取铜中夹带杂质较高，成本明显增加。Other conditions are the same as Example 1, add above-mentioned catalyst 1.5mol/L, leaching time is 2～8 hours, the leaching rate of copper, gold, silver is all > 80%, the recovery rate of sulfur > 80%, entrained impurity in extracting copper is less High, the cost increases significantly.
比较实验例2Comparative experiment example 2
其它条件同实施例1，添加上述催化剂0.03mol/L，浸出时间超过8小时，铜、金、银的浸出率不高、硫的回收率也低，不起催化作用Other conditions are the same as Example 1, add above-mentioned catalyst 0.03mol/L, leaching time surpasses 8 hours, the leaching rate of copper, gold, silver is not high, the recovery rate of sulfur is also low, does not have catalytic effect
比较实验例3Comparative experiment example 3
其它条件同实施例1，搅拌最大线速度为＜3m/s，剪切力减少氧气泡难以弥散浸出时间超过8小时，氧气消耗量明显增加，铜、金、银的浸出率和硫的回收率均不理想。Other conditions are the same as in Example 1, the maximum linear velocity of stirring is <3m/s, the shear force is reduced, the oxygen bubbles are difficult to disperse, the leaching time exceeds 8 hours, the oxygen consumption increases obviously, the leaching rate of copper, gold, silver and the recovery rate of sulfur Neither is ideal.
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Families Citing this family (13)
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| US9346062B2 (en) * | 2009-12-04 | 2016-05-24 | Barrick Gold Corporation | Separation of copper minerals from pyrite using air-metabisulfite treatment |
| CN102205264A (en) * | 2010-12-23 | 2011-10-05 | 紫金矿业集团股份有限公司 | Beneficiation method for increasing gold recovery rate of copper-zinc sulfide ore |
| US9683277B2 (en) | 2013-09-24 | 2017-06-20 | Likivia Process Metalúrgicos SPA | Process for preparing a ferric nitrate reagent from copper raffinate solution and use of such reagent in the leaching and/or curing of copper substances |
| CN105268558B (en) * | 2015-08-19 | 2019-01-11 | 江西理工大学 | A kind of method of the valuable component comprehensive utilization of the low cuprate complex copper-sulphide ores association of high-sulfur |
| CN106755999B (en) * | 2016-12-21 | 2018-11-23 | 武汉理工大学 | A kind of microwave reinforced leaching method of chalcopyrite |
| CN107287417B (en) * | 2017-07-04 | 2019-03-22 | 广西锰华科技投资有限公司 | The comprehensive recovering process of copper, gold, silver in a kind of copper-sulphide ores |
| CN108315553B (en) * | 2018-02-10 | 2020-05-12 | 中南大学 | A kind of leaching method of copper sulfide cobalt ore |
| CN112840048B (en) * | 2018-08-27 | 2022-03-15 | Fl史密斯公司 | Solid catalyst for medium and low temperature leaching applications and method thereof |
| CN109055762B (en) * | 2018-09-29 | 2020-06-30 | 阳谷祥光铜业有限公司 | Copper removal treatment method for copper-selenium-containing waste |
| CN111690820A (en) * | 2019-03-14 | 2020-09-22 | 北京利豪森矿业技术有限公司 | Atmospheric oxygen-enriched acid leaching method for copper-containing flotation gold concentrate |
| CN111411224B (en) * | 2020-05-15 | 2022-03-29 | 广东省资源综合利用研究所 | Beneficiation method for comprehensively recovering and combining silver and copper from low-grade manganese-containing ore |
| CN112760480B (en) * | 2020-12-22 | 2023-01-13 | 衢州华友钴新材料有限公司 | Method for improving oxygen pressure leaching efficiency of copper sulfide cobalt concentrate |
| CN114574711B (en) * | 2022-03-10 | 2024-04-23 | 中国有色桂林矿产地质研究院有限公司 | A method for oxidative leaching of copper sulfide ore |
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Effective date of registration: 20170830 Address after: 361000 Fujian province Xiamen torch hi tech Zone (Xiangan) Industrial Zone Fang Mountain Road No. 3 Patentee after: Xiamen Zijin Mining Technology Co., Ltd. Address before: 364200 Zijin building, No. 1 Zijin Road, Shanghang County, Fujian Province Patentee before: Zijin Mining-Industry Group Corp. |
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