CN100386450C - Combined Leaching Method of Low-grade Refractory Gold Ore - Google Patents
Combined Leaching Method of Low-grade Refractory Gold Ore Download PDFInfo
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- CN100386450C CN100386450C CNB2005100313577A CN200510031357A CN100386450C CN 100386450 C CN100386450 C CN 100386450C CN B2005100313577 A CNB2005100313577 A CN B2005100313577A CN 200510031357 A CN200510031357 A CN 200510031357A CN 100386450 C CN100386450 C CN 100386450C
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- 238000002386 leaching Methods 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000010931 gold Substances 0.000 claims abstract description 42
- 229910052737 gold Inorganic materials 0.000 claims abstract description 42
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 35
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000003570 air Substances 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims 2
- 235000011941 Tilia x europaea Nutrition 0.000 claims 2
- 239000004571 lime Substances 0.000 claims 2
- 239000002184 metal Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 230000008929 regeneration Effects 0.000 claims 1
- 238000011069 regeneration method Methods 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 239000007800 oxidant agent Substances 0.000 abstract description 7
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000605 extraction Methods 0.000 abstract description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 150000003863 ammonium salts Chemical class 0.000 abstract description 2
- 238000007796 conventional method Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000009854 hydrometallurgy Methods 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 5
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 4
- 239000007844 bleaching agent Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 3
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000005363 electrowinning Methods 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- -1 gold ion Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920005372 Plexiglas® Polymers 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- 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
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- Manufacture And Refinement Of Metals (AREA)
Abstract
本发明涉及一种湿法冶炼低品位难处理金矿的配合浸出方法,将矿石破碎后用低浓度的铵盐、氨水以及氧化剂配制配合浸出剂直接进行堆浸或破碎磨细后进行槽浸,生产出杂质含量低,金浓度高的浸出液。这种浸出液可以用常规的置换、活性炭吸附或树脂交换等方法提金,并再生配合浸出剂返回利用。该方法工艺简单,流程短,浸出速度快、浸出率较高、成本低、非氰化、无毒,是一种容易实现工业化生产并具有良好经济效益和环境效益的提金方法。The invention relates to a combined leaching method for hydrometallurgy of low-grade refractory gold ores. After the ore is crushed, a combined leaching agent is prepared with low-concentration ammonium salt, ammonia water and an oxidant, and the leaching agent is directly heap leached or broken and ground before tank leaching. A leach solution with low impurity content and high gold concentration is produced. This leaching solution can be extracted by conventional methods such as replacement, activated carbon adsorption or resin exchange, and regenerated to cooperate with the leaching agent for reuse. The method has the advantages of simple process, short process, fast leaching speed, high leaching rate, low cost, non-cyanide and non-toxicity, and is a gold extraction method that is easy to realize industrial production and has good economic and environmental benefits.
Description
[技术领域] [technical field]
本发明涉及有色冶金从金矿中配合浸出金的一种方法,特别是从低品位含铜金矿或载炭金矿中配合浸金的方法。The invention relates to a method for coordinating leaching gold from gold ores in nonferrous metallurgy, in particular to a method for coordinating and leaching gold from low-grade copper-bearing gold ores or carbon-carrying gold ores.
[背景技术] [Background technique]
对于低品位、难处理金矿的冶炼方法,主要可分为三类:第一类是传统的黄药-黑药联合浮选法获得金精矿,经焙烧,再用氰化物浸出,活性炭吸附,最后解吸,电积。这种方法回收率低,一般只有50%,而且成本高,流程长,存在二氧化硫烟气和氰化物的污染。第二类是采用低浓度氰化物溶液直接堆浸低品位金矿,然后采用活性炭柱吸附,再解吸,电积。这种方法优点是成本低,在美国等发达国家应用较为广泛。但该方法污染地下水源,对环境造成严重威胁。第三类,是采用低浓度硫代硫酸盐和氨水溶液直接堆浸低品位金矿,然后再置换、火法精炼。这种方法由于采用了毒性较低的硫代硫酸盐作为浸出剂,目前在世界上研究较多,但由于硫代硫酸盐不稳定,易分解,真正工业化的并不多。The smelting methods for low-grade and refractory gold ores can be mainly divided into three categories: the first category is the traditional xanthate-black medicine combined flotation method to obtain gold concentrate, which is roasted, then leached with cyanide, and activated carbon adsorption , and finally desorption, electrowinning. The recovery rate of this method is low, generally only 50%, and the cost is high, the flow process is long, and there is pollution of sulfur dioxide flue gas and cyanide. The second type is to use low-concentration cyanide solution to directly heap leach low-grade gold ore, then use activated carbon column to adsorb, then desorb and electrowinning. This method has the advantage of low cost and is widely used in developed countries such as the United States. However, this method pollutes groundwater sources and poses a serious threat to the environment. The third category is to use low-concentration thiosulfate and ammonia solution to directly heap leaching low-grade gold ore, followed by replacement and fire refining. Because this method uses less toxic thiosulfate as the leaching agent, there are currently many studies in the world, but because thiosulfate is unstable and easy to decompose, there are not many real industrializations.
[发明内容] [Content of the invention]
本发明的目的是提供一种低品位难处理金矿的配合浸出方法。The purpose of the present invention is to provide a method for coordinated leaching of low-grade refractory gold ores.
本发明的目的是通过以下堆浸或槽浸的技术方案来实现的:The purpose of the present invention is achieved through the following technical solutions of heap leaching or tank leaching:
首先将开采出的混合矿破碎成合格碎矿或继续细磨成矿粉,再按一定方法组堆或在搅拌槽内,实施含氧化剂的氨性铵盐溶液配合循环堆浸或槽浸,浸出剂成分:浓度为0.1~5mol/L氯化铵,浓度为0.1~0.5mol/L工业级氨水,堆浸时液固比为0.1~3L/Kg矿,氧化剂可以是空气与Cu2+、氧气与Cu2+、次氯酸钠、漂白粉或单一的Cu2+,氧化剂的加入量为:漂白粉为每公斤矿石加5g~100g;次氯酸钠每公斤矿石加1~25g;采用空气或氧气与Cu2+作氧化剂时,在不含铜矿石的配合浸出剂中配入0.005~0.05mol/L的Cu2+,含铜矿石的配合浸出剂不加Cu2+;单独用Cu2+作为氧化剂时,浸出剂中Cu2+的浓度为0.01~0.1mol/L。First, crush the mined mixed ore into qualified crushed ore or continue to finely grind it into ore powder, and then pile it up according to a certain method or in the stirring tank, implement oxidant-containing ammoniacal ammonium salt solution with cyclic heap leaching or tank leaching, leaching Agent composition: the concentration is 0.1-5mol/L ammonium chloride, the concentration is 0.1-0.5mol/L industrial grade ammonia water, the liquid-solid ratio is 0.1-3L/Kg ore during heap leaching, the oxidant can be air and Cu 2+ , oxygen With Cu 2+ , sodium hypochlorite, bleaching powder or single Cu 2+ , the amount of oxidant added is: bleaching powder is 5g-100g per kilogram of ore; sodium hypochlorite is 1-25g per kilogram of ore; air or oxygen and Cu 2+ are used as oxidant 0.005-0.05mol/L Cu 2+ is added to the compound leaching agent containing copper ore, and Cu 2+ is not added to the compound leaching agent containing copper ore; when Cu 2+ is used alone as the oxidant, the leaching The concentration of Cu 2+ in the agent is 0.01-0.1mol/L.
最后将合格的浸出液采用传统的置换或吸附方法提金和再生配合浸出剂。Finally, the qualified leaching solution is extracted by traditional displacement or adsorption methods and regenerated with the leaching agent.
在配合浸出过程中,发生的主要反应有:During the complex leaching process, the main reactions that take place are:
Au+kNH4Cl→AuClk j-k+k NH4 ++jeAu+kNH 4 Cl→AuCl k jk +k NH 4 + +je
式中:k为Cl-的配位数,j为相应金离子的价数。In the formula: k is the coordination number of Cl - , and j is the valence number of the corresponding gold ion.
氧化-还原反应为:The oxidation-reduction reaction is:
O2+2H2O+4e-→40H- O 2 +2H 2 O+4e - → 40H -
Cu2++e-→Cu+ Cu 2+ +e − →Cu +
C10-+H2O+2e-→Cl-+20H- C10 - +H 2 O+2e - →Cl - +20H -
本发明利用了浸出剂中的Cl-与金离子形成稳定配合物的原理和Cu2+对浸金具有催化或活化作用,由于Cu2+具有氧化性,而空气又很容易将Cu+氧化成Cu2+,从而形成一种氧化-还原循环机制。因此,用空气或氧气作氧化剂时,若金矿不含铜,则在配制配合浸出剂时配入0.005~0.05mol/L的Cu2+,含铜矿石的配合浸出剂中则不需要加Cu2+。The present invention utilizes the principle that Cl in the leaching agent forms a stable complex with gold ions and that Cu 2+ has a catalytic or activating effect on leaching gold, because Cu 2+ has oxidative properties, and the air is easy to oxidize Cu + into Cu 2+ , thus forming an oxidation-reduction cycle mechanism. Therefore, when air or oxygen is used as the oxidant, if the gold ore does not contain copper, 0.005-0.05mol/L Cu 2+ should be added when preparing the compound leaching agent, and there is no need to add Cu 2+ to the compound leaching agent containing copper ore. Cu 2+ .
本发明的生产过程中不产生烟气烟尘,大大降低了资源提取的综合成本和规模生产投资,结合金矿金浸出率≥65%、自然金矿金浸出率≥92%;能高效率、低成本、少投入,无污染地提取金,给难处理金矿金的回收利用提供了非氰化、无毒化的先进技术。In the production process of the present invention, no flue gas and dust are produced, which greatly reduces the comprehensive cost of resource extraction and scale production investment, and the gold leaching rate of combined gold mines is ≥ 65%, and the gold leaching rate of natural gold mines is ≥ 92%; Low cost, less investment, and non-polluting gold extraction provide non-cyanidation and non-toxic advanced technology for the recovery and utilization of gold from refractory gold mines.
[具体实施方式] [Detailed ways]
将开采的混合类型矿物破碎至粒度在0.5mm至20mm之间,进行堆浸。筑堆的堆高在5-8m,开始用预先配制的一定组成的配合浸出剂喷淋,接着用未达到合格浓度的浸出液循环喷淋,布液强度4~25L/(m2·h),浸出时间为50-150d,自然金矿浸出时间可稍短,结合金矿浸出时间可稍长。进行槽浸的金矿须磨细至140目以下,然后在搅拌槽中按2~6∶1的液固比,在20~60℃下配合浸出2~12h。The mined mixed type minerals are crushed to a particle size between 0.5mm and 20mm for heap leaching. The height of the heap is 5-8m, start spraying with a pre-prepared compound leaching agent of a certain composition, and then spray circularly with the leaching solution that has not reached the qualified concentration, the liquid distribution intensity is 4-25L/(m 2 ·h), The leaching time is 50-150d, the natural gold ore leaching time can be slightly shorter, and the combined gold ore leaching time can be slightly longer. The gold ore for tank leaching must be ground to below 140 mesh, and then leached in a stirred tank at a liquid-solid ratio of 2-6:1 at 20-60°C for 2-12 hours.
用以下非限定性实施例对本发明的方法的工艺条件作进一步的说明,实施例所述的百分比均是重量百分比。The process conditions of the method of the present invention are further illustrated with the following non-limiting examples, and the percentages described in the examples are all percentages by weight.
实施例1来自甘肃某低品位、难处理的含铜金矿,用常规的浮选法富集,金回收率仅为50%。该含铜金矿中的铜以氧化矿形式存在,其中的金以极微小的脉石型包裹金形式存在,该金矿化学成分见表1。Example 1 is from a low-grade, difficult-to-handle copper-bearing gold mine in Gansu, which is enriched by conventional flotation, and the gold recovery rate is only 50%. The copper in the copper-bearing gold ore exists in the form of oxide ore, and the gold in it exists in the form of extremely small gangue-type wrapped gold. The chemical composition of the gold ore is shown in Table 1.
表1.某低品位难处理含铜金矿的化学成分Table 1. Chemical composition of a low-grade refractory copper-bearing gold ore
*表示g/t * means g/t
其原矿颗粒粒度为30~0.1mm,用2mol/L NH4Cl,0.2mol/L NH4OH,采用Φ125×1500mm的有机玻璃柱,进行10Kg级柱浸,矿柱中加入漂白粉500g,浸出100d,金的浸出率为76.4%。The particle size of the raw ore is 30-0.1mm. Use 2mol/L NH 4 Cl, 0.2mol/L NH 4 OH, and use a plexiglass column of Φ125×1500mm to carry out 10Kg column leaching. Add 500g of bleaching powder to the ore column, and leaching for 100d , the gold leaching rate was 76.4%.
实施例2采用上述的低品位含铜的金矿,磨细至-200目>80%,取1Kg加入到8L的浸出槽中,同时加入20克漂白粉,再用含4mol/L NH4Cl和0.5mol/L NH4OH的配合浸出剂5L,在室温下搅拌浸出12h,金浸出率达到82.5%。Embodiment 2 adopts the above-mentioned low-grade copper-containing gold ore, grinds it to -200 mesh>80%, takes 1Kg and joins it in an 8L leaching tank, and adds 20 grams of bleaching powder at the same time, and then uses 4mol/L NH 4 Cl and 0.5mol/L NH 4 OH mixed leaching agent 5L, stirred and leached at room temperature for 12h, the gold leaching rate reached 82.5%.
由于含铜或载碳的低品位难处理金矿的蕴藏量很丰富,开发经济上合理,对环境友好,能够替代氰化法,适用于该类资源开发利用的简单有效的提金方法当具有重要的现实意义。Because the reserves of low-grade refractory gold ores containing copper or carbon are very rich, the development is economically reasonable, environmentally friendly, and can replace the cyanidation method. The simple and effective gold extraction method suitable for the development and utilization of such resources should have important practical significance.
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US5807421A (en) * | 1994-03-25 | 1998-09-15 | E. I. Du Pont De Nemours And Company | Hydrometallurgical extraction process |
CN1226605A (en) * | 1999-02-10 | 1999-08-25 | 昆明理工大学 | Technology for gold extraction by cyanide process with mixed auxiliary |
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CN1226605A (en) * | 1999-02-10 | 1999-08-25 | 昆明理工大学 | Technology for gold extraction by cyanide process with mixed auxiliary |
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