CN103243221B - Method for directly gathering gold by virtue of smelting of unmanageable gold ore molten pool containing arsenic and stibium - Google Patents

Method for directly gathering gold by virtue of smelting of unmanageable gold ore molten pool containing arsenic and stibium Download PDF

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CN103243221B
CN103243221B CN201310181632.8A CN201310181632A CN103243221B CN 103243221 B CN103243221 B CN 103243221B CN 201310181632 A CN201310181632 A CN 201310181632A CN 103243221 B CN103243221 B CN 103243221B
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gold
iron
smelting
antimony
sulfonium
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CN103243221A (en
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杨天足
刘伟锋
陈霖
张杜超
刘志楼
宾舒
宾万达
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Central South University
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Central South University
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Abstract

The invention discloses a method for directly gathering gold by virtue of smelting of an unmanageable gold ore molten pool containing arsenic and stibium. The method comprises the following steps of: adding unmanageable gold ore containing arsenic and stibium with ferric oxide slag to a certain high-temperature melt after mixing and dosing the unmanageable gold ore; then leading oxygen-enriched air to oxidize and smelt, directly returning the produced gold iron sulfide concentrate to a smelting process; entering a low antimony metal matte phase into a selective blowing process to further gather gold; controlling the blowing final point to enable gold to enter into an expensive iron matte phase, finally extracting the gold from the expensive iron matte phase; producing Sb2O3 smoke after dust collection in the blowing process; merging tail gas containing SO2 with smoke in the smelting process to prepare sulfuric acid; and returning an iron oxide slag produced in the blowing process to the smelting process to dose. Efficient gathering and recovering of gold in the unmanageable gold ore are achieved by smelting and selective blowing processes of the molten bath; direct enrichment ratio of the gold can achieve 92-95%; and the total recovery rate of the gold can achieve over 99.0%.

Description

A kind of method containing the direct Concentration of Gold of arsenic antimony difficult-treating gold mine bath smelting
Technical field
The present invention relates to pyrometallurgical processes in field of metallurgy, particularly contain the pyrometallurgy method of the direct Concentration of Gold of arsenic antimony difficult-treating gold mine bath smelting.
Background technology
Difficult-treating gold mine, is called again Refractory Au-ores or refractory gold conventionally, even if it refers to through fine grinding, can not effectively leach by conventional cyanide process the ore of most of gold.Therefore, usually said difficult-treating gold mine is for cyanide process, and some scholars think that the cyanide leaching of Gold in Ores is difficult-treating gold mine lower than 90%, can be called utmost point difficult-treating gold mine lower than 50%.Difficult-treating gold mine mainly contains particulate parcel gold mine, copper gold, contains antimony gold mine, Carbonaceous gold ore and contain calaverite etc., why difficult these ores are is mainly because there is the material of sulfide parcel or other influences cyaniding process, therefore, must first to ore, carry out the factor that pre-treatment is leached with separated metal or the gold of eliminating the effects of the act, gold wherein can be extracted by cyanide process.
In all difficult-treating gold mines, difficult-treating gold mine containing arsenic and antimony is again the most unmanageable in difficult-treating gold mine, its reserves are also maximum, its exploitation are global problems, this is mainly because mustard gold or inferior micro-gold are parcel or disseminated is present in sulphide ores, these sulfide are pyrite, mispickel and pyrrhotite normally, and even in some mineral deposits, most of gold can enter the lattice of pyrite and mispickel, with the state of submicroscopic gold, exists.Even ore is ground very carefully, can not make gold dissociate, the Cyanide Leaching effect extreme difference of gold.For this treating refractory As-containing gold ore, conventionally need before golden cyaniding, carry out pre-treatment, make to wrap up golden pyrite and mispickel and decompose, allow gold is exposed out to be contacted with cyanide solution, thereby improve golden cyanide leaching.
Obtained three kinds of the main oxidizing roasting method for the treatment of refractory As-containing gold ore pretreatment process, pressure oxidation method of industrial application and bacterial oxidation methods (poplar natural feet. precious metals metallurgy and product deep processing. press of Central South University, 2005 .).Oxidizing roasting method is to process main, the most widely used method of sulfide coated difficult-treating gold mine.Pyrite and mispickel are through oxidizing roasting, the oxidized formation of arsenic and sulphur As 2o 3and SO 2volatilization, the calcining of generation porous.The feature of oxidizing roasting method is strong to adaptability to raw material, along with the raising of flue gas acid preparing level, waste gas pollution control and treatment cost etc., is widely used simultaneously, and this method has obtained good application and popularization in China.The method that industry adopts at present has the methods such as two sections of boiling roasters, circulating boiling furnace roasting, shower roasting method and microwave calcining method, wherein two sections of fluidized bed roasting methods adopt the most extensive, the golden rate of recovery of bibliographical information is between 88~92%, in cyanidation tailings, gold content is 4g/t, and in actually operating, slag differing greatly containing golden index and report after the rate of recovery index of gold and cyaniding.Current domestic employing two-stage roasting art breading is containing arsenic golden ore concentrate hard to treat, calcining after cyaniding in cyanidation tailings gold content in a larger scope, fluctuate, containing gold, can change to 20g/t from 8g/t, the phase research of gold in cyanidation tailings be shown to the Fe that roasting generates 2o 3parcel gold again, therefore, when processing high arsenic fine gold ore, take into account that inclusion is opened in dearsenification desulfurization and forming Fe 2o 3time not wrap up gold be very difficult.
The in the situation that pressure oxidation method referring in High Temperature High Pressure acidity and has oxygen, the oxidized decomposition of pyrite and mispickel, the sulphur in concentrate is oxidized to vitriol, and arsenic is oxidized to arsenate through arsenite, and wrapped gold is exposed.Pressure oxidation method have oxidation thoroughly, gold leaching rate is high, environmental pollution is little, to advantages such as poisonous metal susceptibility are low, gold leaching rate is up to 95~97%, in cyanidation tailings, the content of gold is between 1.5~2.0g/t.But the method to equipment material require high, investment is large and silver raising recovery rate is low, processing cost is higher than roasting method, the domestic application example that there is no.Bacterial oxidation method refers under the condition existing on bacterium utilizes airborne oxygen to be oxidized pyrite and mispickel, the bacterium of using is optimum is thiobacillus ferrooxidant, thiobacillus ferrooxidant can oxygenolysis pyrite and mispickel, expose parcel gold wherein, the rate of recovery of the method can reach 92~95%, also there is the simple advantage of technique simultaneously, but have that oxidation cycle is long, environmental protection cost is high and the shortcoming such as adaptability to raw material is poor.
All drawbacks in view of the existence of biooxidized concentrate To Several Traditional Preconditioning Methods, new treatment process is developed, in the happy and auspicious Chinese patent ZL200910020494.9 of Cui Zhi, propose, by high arsenic fine gold ore after two-stage roasting removes arsenic and sulphur, secondary calcining and copper ore concentrates together add in oxygen-enriched bottom-blowing stove matte smelting output containing golden copper matte regulus, copper matte regulus is through blowing, output cathode copper after pyrorefining and electrorefining, last Jin Heyin (the Cui Zhixiang that reclaims from the anode sludge of copper electrolyzing refining, Shen Dianbang, Wang Zhi, Li Weiqun, Bian Ruimin. the theory and practice of oxygen-enriched bottom-blowing molten bath copper, China YouSe is metallurgical, 2010, 12 (6): 21~26. kings believe grace, high Zhenglin, Qu Shengli, Zhang Junfeng, Ma Shaowei, Zou Lin. the extracting method of high arsenic complicated golden ore concentrate multielement, Chinese patent, ZL200910020494.9, authorize day: on August 11st, 2011 .).Although this makes sulfonium, to catch golden method be the gold in can efficient recovery high arsenic fine gold ore calcining, but it adds copper smelting process as flux using the high high arsenic fine gold ore of thermal value after two-stage roasting, cause on the one hand the waste of the energy, on the other hand because the content of ferric oxide in calcining and silicon-dioxide is all higher, be difficult to realize it as the effect of copper smelting flux, this just requires the scale that expands copper smelting to alleviate its disadvantageous effect, and then large to the demand of copper ore concentrates, these shortcomings have seriously restricted applying of this technology.
Summary of the invention
In order to overcome the deficiency of traditional difficult-treating gold mine treatment process, the invention provides the direct Concentration of Gold of a kind of difficult-treating gold mine bath smelting, and the pyrometallurgy method that gold recovery is high, cost is low.
In order to achieve the above object, the technical solution used in the present invention is: containing joining slag type after arsenic antimony difficult-treating gold mine and oxidation scum mix, form in certain high-temperature fusant, then pass into oxygen-rich air oxidizing semlting, make most of gold enter low antimony iron sulfonium phase, and arsenic and sulphur oxidation enter flue gas, through gathering dust output As 2o 3flue dust, the SO after gathering dust 2flue gas is prepared sulfuric acid, and smelting slag carries out ore dressing processing after overcooling and ore grinding, output containing the direct Returning smelting process of golden iron sulphide concentrate.Low antimony iron sulfonium enters the further Concentration of Gold of selectivity converting process mutually, controls blow end point and makes gold enter your iron sulfonium phase, your iron sulfonium finally to extract mutually golden from, and converting process flue gas is output Sb after gathering dust 2o 3flue dust, containing SO 2tail gas and fusion process flue gas combination system sulfuric acid, the oxidation scum Returning smelting process batching of converting process output.Core of the present invention is by the continuous enrichment of gold containing in arsenic antimony biooxidized concentrate, first in bath smelting process, golden enrichment is entered to low antimony iron sulfonium, then in selectivity converting process output, is rich in your iron sulfonium of gold, your iron sulfonium finally to extract mutually golden from.
Concrete technological process and parameter are as follows:
1 bath smelting
Oxidation scum containing arsenic antimony difficult-treating gold mine and selectivity converting process output is joined in the high-temperature fusant of 1100~1300 ℃ to FeO/SiO in control high-temperature fusant 2ratio is stabilized in 1.5~2.2, adds a small amount of Wingdale to make CaO/SiO in high-temperature fusant simultaneously 2ratio is 0.1~0.4, continues to pass into concentration and is 21~60% oxygen-rich air and carry out oxidizing semlting, enters flue gas after making arsenic and sulphur oxidized, then through gathering dust output As 2o 3flue dust, the SO after gathering dust 2flue gas is prepared sulfuric acid, and the content of controlling iron in low antimony iron sulfonium is 40~50%, emits successively low antimony iron sulfonium and smelting slag, and low antimony iron sulfonium enters selectivity converting process, smelting slag through overcooling and levigate after ore dressing, output is containing golden iron sulphide concentrate Returning smelting process.
2 selectivity blowing
Low antimony iron sulfonium is carried out to the selectivity further Concentration of Gold that blows, control 1150~1300 ℃ of blowing temperature, continue to blast concentration and be 21~60% oxygen-rich air, and add appropriate amount of quartz sand, make low antimony iron sulfonium realize the expensive iron sulfonium of selective oxidation output, scum and flue gas, containing the higher direct Returning smelting process of scum of iron protoxide, make antimony and the oxidation of part sulphur enter flue gas, through gathering dust output Sb 2o 3flue dust, the SO after gathering dust 2flue gas and fusion process merge relieving haperacidity, by controlling iron level in your iron sulfonium, are 55~60%, make the enrichment of most of gold precipitation enter your iron sulfonium, and then extract gold from your iron sulfonium.
The present invention is applicable to process containing arsenic antimony difficult-treating gold mine, and its main component scope is (%): Au20~200g/t, Ag10~300g/t, As1.0~15.0, Sb0.5~10.0, S12~32, Fe15~35 and SiO by weight percentage 215~35, be also applicable to process the high-sulfur difficult-treating gold mine of other types.
The present invention and traditional difficult-treating gold mine method comparison, there is following advantage: 1, by bath smelting and selectivity converting process, realize efficiently concentrating and the recovery of gold in difficult-treating gold mine, the direct accumulation rate of gold can reach 92~95%, and the total yield of gold can reach more than 99.0%; 2, in bath smelting and selectivity converting process, realize the selective separation of arsenic and antimony, reached the object of material heat output full use; 3, this technique directly be take difficult-treating gold mine as raw material, utilizes low antimony iron sulfonium trapping gold, does not need to allocate a large amount of non-ferrous metal concentrate into, and Technological adaptability is wide; 4, adopt beneficiation method to reclaim the gold being mingled with in smelting slag, reduced the difficulty that fusion process is controlled golden recovery index; 5, stop the environmental problem of traditional treatment method, eliminated the potential hazard of prussiate, realized the comprehensive recovery of valuable element; 6, labour intensity of the present invention is low, the treatment time is short, cost is low.
Accompanying drawing explanation
Fig. 1: process flow diagram of the present invention.
Embodiment:
Embodiment 1:
Main component containing arsenic antimony difficult-treating gold mine is (%): Au55g/t, Ag80g/t, As8.0, Sb5.5, S23.4, Fe29.8 and SiO by weight percentage 225.6.It is in the high-temperature fusant of 1280 ℃ that the above-mentioned scum containing arsenic antimony difficult-treating gold mine, converting process and appropriate Wingdale are joined to temperature, controls FeO/SiO in high-temperature fusant 2=1.55, CaO/SiO 2=0.3, continue to pass into concentration and be 50% oxygen-rich air oxidizing semlting, the low antimony iron of output sulfonium, smelting slag and flue gas respectively, controlling iron level in low antimony iron sulfonium is 46%, in low antimony iron sulfonium, gold content is 134g/t, flue gas through the output of gathering dust mainly containing As 2o 3flue dust, acid exhaust after gathering dust, smelting slag is containing golden 3.0g/t, through overcooling and levigate after after ore dressing output containing golden iron sulphide concentrate Returning smelting process.Low antimony iron sulfonium send another one stove to carry out selectivity blowing, control 1280 ℃ of blowing temperature, continue to blast concentration and be 40% oxygen-rich air, and add appropriate amount of quartz sand, make low antimony iron sulfonium realize the expensive iron sulfonium of selective oxidation output, scum and flue gas, containing the higher direct Returning smelting process of scum of iron protoxide, make antimony and the oxidation of part sulphur enter flue gas, through gathering dust output Sb 2o 3flue dust, the SO after gathering dust 2flue gas and fusion process merge relieving haperacidity, by controlling iron level in your iron sulfonium, are 58%, make the enrichment of most of gold precipitation enter your iron sulfonium, and in your iron sulfonium, the content of gold is 468g/t, more further extracts Jin Heyin from your iron sulfonium.

Claims (2)

1. containing a method for the direct Concentration of Gold of arsenic antimony difficult-treating gold mine bath smelting, it is characterized in that comprising the following steps:
A bath smelting
By containing the joining in the high-temperature fusant of 1100~1300 ℃ containing the higher scum of iron protoxide of arsenic antimony difficult-treating gold mine and selectivity converting process output, FeO/SiO in control high-temperature fusant 2ratio is stabilized in 1.5~2.2, adds Wingdale to make CaO/SiO in high-temperature fusant simultaneously 2ratio is 0.1~0.4, continues to pass into concentration and is 21~60% oxygen-rich air and carry out oxidizing semlting, enters flue gas after making arsenic and sulphur oxidized, then through gathering dust output As 2o 3flue dust, the SO after gathering dust 2flue gas is prepared sulfuric acid, and the content of controlling iron in low antimony iron sulfonium is 40~50%, emits successively low antimony iron sulfonium and smelting slag, and low antimony iron sulfonium enters selectivity converting process, smelting slag through overcooling and levigate after ore dressing, output is containing golden iron sulphide concentrate Returning smelting process;
The blowing of B selectivity
Low antimony iron sulfonium is carried out to the selectivity further Concentration of Gold that blows, control 1150~1300 ℃ of blowing temperature, continue to blast concentration and be 21~60% oxygen-rich air, and add quartz sand, make low antimony iron sulfonium realize the expensive iron sulfonium of selective oxidation output, scum and flue gas, containing the higher direct Returning smelting process of scum of iron protoxide, make antimony and the oxidation of part sulphur enter flue gas, through gathering dust output Sb 2o 3flue dust, the SO after gathering dust 2flue gas and the fusion process SO after gathering dust 2flue gas merges relieving haperacidity, by controlling iron level in your iron sulfonium, is 55~60%, makes the enrichment of most of gold precipitation enter your iron sulfonium, and then extract gold from your iron sulfonium.
2. the method containing the direct Concentration of Gold of arsenic antimony difficult-treating gold mine bath smelting as claimed in claim 1, is characterized in that: the described main component scope containing arsenic antimony difficult-treating gold mine is by weight percentage: Au20~200g/t, Ag 10~300g/t, As1.0~15.0, Sb0.5~10.0, S12~32, Fe15~35 and SiO 215~35.
CN201310181632.8A 2013-05-16 2013-05-16 Method for directly gathering gold by virtue of smelting of unmanageable gold ore molten pool containing arsenic and stibium Expired - Fee Related CN103243221B (en)

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CN104313328B (en) * 2014-10-11 2016-11-02 中南大学 Lead and the method for gold is reclaimed based on difficult-treating gold mine sulfur melting bath melting solid with the reduction of lead containing sludge raw material
CN108152271B (en) * 2017-11-27 2020-08-25 西北矿冶研究院 Chemical separation analysis test method for gold in antimony electrolyte
CN108456777B (en) * 2018-03-27 2020-01-14 广西万仕智稀贵金属科技有限公司 Method for preparing rich noble lead from noble antimony
CN108823426A (en) * 2018-07-13 2018-11-16 中南大学 A kind of method of rich golden iron sulfonium melting back extraction Concentration of Gold
CN108823425A (en) * 2018-07-13 2018-11-16 中南大学 A kind of difficult-treating gold mine fused-extracting enrichment Method for extracting gold
CN110256079B (en) * 2019-06-26 2021-01-26 中国科学院地球化学研究所 Preparation method of high-purity compact arsenopyrite electrode
CN110373539B (en) * 2019-08-28 2021-02-19 中南大学 Method for strengthening gold enrichment of refractory gold ore by direct smelting
CN110777264A (en) * 2019-12-05 2020-02-11 蒋开喜 Method suitable for independent smelting of various complex gold concentrates
CN115369265B (en) * 2022-07-18 2023-07-14 湖南辰州矿业有限责任公司 Method for reducing gold-containing index of antimony matte of antimony-gold blast furnace

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CN101519731B (en) * 2009-04-10 2011-08-10 山东恒邦冶炼股份有限公司 Method for extracting high arsenic complicated golden ore concentrate multielement
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