CN110373539B - Method for strengthening gold enrichment of refractory gold ore by direct smelting - Google Patents
Method for strengthening gold enrichment of refractory gold ore by direct smelting Download PDFInfo
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Abstract
A method for strengthening gold enrichment of refractory gold ore by direct smelting comprises mixing and granulating sodium pyroantimonate and starch, mixing with refractory gold ore, introducing oxygen-enriched air at high temperature for oxidation smelting, reducing Sb (V) in the sodium pyroantimonate into metal by the starch, reacting with gold in the refractory gold ore, enriching in gold-enriched iron matte, and carrying out ore dressing treatment on smelting slag. The core of the invention is that the properties of sodium pyroantimonate which is low in high-temperature volatility and is easily reduced by starch are utilized, antimony and gold are primarily enriched in gold-rich iron matte after the action in the direct smelting process of refractory gold ore, the demand of the direct smelting process on antimony is greatly reduced, and the aim of directly smelting refractory gold to strengthen the gold enrichment is finally realized. The invention controls the mass percentage of antimony in the mixed material to be less than 1.0 percent, greatly reduces the consumption of antimony, has the direct yield of gold in the gold-rich iron matte to reach more than 99.0 percent, and has the advantages of strong raw material adaptability, high metal recovery rate and simple process flow.
Description
Technical Field
The invention relates to a gold metallurgy process in the field of nonferrous metallurgy, in particular to a pyrometallurgical method for directly smelting and strengthening enrichment gold by refractory gold.
Background
Gold is a scarce strategic metal and is widely applied to gold ornaments, currency storage and high-tech industries. The gold yield in 2018 in China is 401.12 tons, about more than 1/3 gold ores are produced from the refractory gold ores, and the proportion is still increased with the increasing consumption of high-quality resources. Refractory gold ore, also called refractory gold ore or refractory gold ore, refers to ore whose cyanidation leaching rate is still lower than 80% even after fine grinding gold, and mainly includes gold ore coated with particles, copper-containing gold ore, antimony-containing gold ore, carbon-containing gold ore and tellurium-containing gold ore, etc. The refractory gold ore containing arsenic is the most refractory and most stored in the refractory gold ore, and the development and utilization of the refractory gold ore are worldwide problems. This is mainly because fine gold particles or sub-micro gold particles are present in the sulfide minerals such as pyrite, arsenopyrite and pyrrhotite in a wrapped or impregnated state, and even if gold enters the crystal lattices of these minerals in a super-micro gold state, the gold cannot be dissociated even if the ore is finely ground, and the cyanidation leaching rate of gold is usually less than 50%. Therefore, the ore must be pretreated to separate the relevant metals or to eliminate factors affecting gold leaching so that the gold can be extracted by cyanidation.
The pretreatment method of refractory gold ore has been studied in many ways, but the two-stage roasting method, pressure oxidation method and bacterial oxidation method (yangtou, precious metal metallurgy and deep processing of products, university press of south and middle, 2005) are currently the most widely used in industry. The two-stage roasting method is to roast refractory As-containing gold ore in two-stage fluidized bed furnace to oxidize As and S to form As2O3And SO2Volatilizing to produce porous calcine. The method has the advantages of simple process and low treatment cost, is widely applied, has the leaching rate of gold of 75-92 percent, has the content of gold in cyanidation tailings of 4.0-20.0g/t, and has Fe in the roasting process2O3The secondary packing phenomenon causes great change of gold leaching rate, so when refractory gold ore is treated by the two-stage roasting method, arsenic removal and desulfurization are considered to be carried out, the inclusion is opened, and Fe is formed2O3It is very difficult to pack gold (Chuanban talks about pretreatment of refractory gold concentrate with high sulfur and arsenic by two-stage roasting method. Yunnan chemical industry, 2007, 34(5): 26-29.). The pressure oxidation method is characterized in that pyrite and arsenopyrite are oxidized and decomposed under the conditions of high temperature and high pressure acidity and oxygen, so that the coated gold is exposed. The method has the advantages of short treatment time, high gold leaching rate, low sensitivity to harmful metals and the like, the gold leaching rate is as high as 95-97%, and the gold content in the cyanidation tailings is 1.5-2.0 g/t. But has the defects of large investment, low silver recovery rate and high treatment cost (Qiutiun province, Nioniuhua, Zhang Qiang. the current situation and the progress of the pretreatment and leaching technology of the copper-containing gold ore which is difficult to treat. gold, 2005, 26(8): 30-34.). The bacterial oxidation method is to oxidize pyrite and arsenopyrite under the action of bacteria to fully expose the encapsulated gold (Zhang Ningcheng, Populong, rich Yao, Chensen, Zhang Shuo. bacterial oxidation-cyaniding leaching of gold ores with different arsenic types, Chinese non-ferrous metals academic newspaper 2011, 21(3): 694-699.). The bacterial oxidation method has the advantages of simple process, the leaching rate of gold is 92-95%, the content of gold in cyanidation tailings is 2.0-5.0g/t, but the disadvantages of long oxidation period, high environmental protection cost and the like existAnd (4) point.
Although the pretreatment methods of various refractory gold ores have advantages and disadvantages, technical personnel usually select the pretreatment method with better economic benefit by combining the characteristics of the refractory gold ores, thereby promoting the vigorous development of the gold smelting industry in China. However, during the pyrometallurgical smelting of heavy metals such as copper, nickel and lead, trace amounts of precious metals such as gold and silver in the concentrate are trapped in the matte phase or metal, and finally the precious metals are extracted from the anode slime, which indicates that the matte phase or metal can be used as a trapping agent for the precious metals (old view. discussion of the principle of precious metal trapping by base metals and matte in pyrometallurgy. china engineering science, 2007,9(5): 11-16.). Accordingly, metallurgists have attempted to utilize heavy metal pyrometallurgical systems to capture gold from refractory gold ores.
The refractory gold ore with high copper content can be directly matched into a copper concentrate smelting system for use (Cu)>12.0%) and the calcine after two-stage roasting is added into a copper or lead smelting system, and finally, gold is recovered from the anode mud. The process is applied to certain enterprises in Shandong China in 2012 (theory and practice of oxygen-enriched bottom blowing molten pool copper, Chinese nonferrous metallurgy, 2010,12(6): 21-26. Wang Xinen et al., extraction method of multiple elements of high-arsenic complex gold concentrate, ZL200910020494.9, grant day 2011-08-11.), namely, high-arsenic gold ore calcine is matched with a copper smelting system for treatment, namely, after the high-arsenic gold concentrate is roasted for two sections to remove arsenic and sulfur, the calcine and copper concentrate are added into an oxygen-enriched bottom blowing furnace for matte smelting to enable gold to enter copper matte, and finally, precious metal is recovered from anode mud of copper electrorefining. The design of the method for gold capture by matte is originally designed to use the calcine of refractory gold ore as the flux in the process of smelting heavy metals, but because of Fe in the calcine2O3And SiO2The content of (a) is high, the purpose as a flux cannot be achieved, and the scale of copper or lead smelting needs to be enlarged to eliminate the adverse effect thereof. In addition, the method also causes the loss of gold inclusions in the original metal smelting slag and the additional loss of main metals in the newly produced smelting slag, so that the subsequent treatment cost is greatly increased.
By taking the experience of enriching noble metals in the lead smelting process as a reference, researchers propose a method for treating refractory gold ores and lead-containing waste residues by a reduction sulfur-fixing smelting method (Liuwei and the like, a method for smelting and recovering lead and gold based on the refractory gold ores and the lead-containing waste residues through a reduction sulfur-fixing molten pool, ZL201410532819.2, Authority date 2016-11-02), namely, the refractory gold ores, lead-containing materials and an iron-containing sulfur-fixing agent are mixed and granulated, granules and a carbon reducing agent are smelted in an oxygen bottom blowing furnace, and finally, gold is recovered from crude lead. The method simultaneously produces three types of smelting slag, iron matte and crude lead in the smelting process, not only has high clarification and separation difficulty, but also has high demand on lead-containing waste slag and is easy to cause the dispersion loss of gold.
Based on the problems existing in the methods, the inventor of the patent proposes that the antimony-arsenic-containing refractory gold ore is treated by a molten pool smelting method (Yangtze foot, and the like), namely a method for directly smelting and enriching gold from antimony-arsenic-containing refractory gold ore, ZL201310181632.8, grant date: 2014-04-30.), namely the refractory gold ore is directly smelted to enrich gold into an iron matte phase, the iron matte is blown to further enrich gold in the precious iron matte, and finally, the effective enrichment of the gold is realized. The result of direct smelting gold enrichment of antimony-containing refractory gold ore with the components of Au48.0g/t, Sb4.20% and As3.50% shows that: the smelting product is clearly layered with the gold-rich iron matte and the smelting slag, the gold content in the gold-rich iron matte is 143.58g/t, and the direct yield of gold reaches more than 98.0 percent, which shows that the gold can be efficiently captured in the gold-rich iron matte during the direct smelting of special antimony-containing refractory gold ores.
Based on the principle that stibnite existing in refractory gold ore plays an important role in the efficient enrichment of gold in the direct smelting process, the aim of adding stibnite ash in the direct smelting of the refractory gold ore is achieved, and the direct yield of gold in gold-rich iron matte can reach more than 98.0% (Liuwei Feng et al, a method for extracting and enriching gold by melting refractory gold ore, 201810769193.5, application date: 2018, 7 and 13 days). However, because antimony sulfide and antimony oxide are highly volatile at high temperature, the content of antimony in the material needs to be increased to realize the high-efficiency enrichment of the gold, and meanwhile, antimony is expensive, and the introduction of a large amount of antimony compounds inevitably leads to the increase of the production cost. Therefore, the demand of antimony content in the direct smelting process of refractory gold ore needs to be reduced by research.
Disclosure of Invention
In order to overcome the defects of the traditional treatment method of refractory gold ores, the invention provides a pyrometallurgical method for strengthening and enriching gold by directly smelting refractory gold, which has high gold recovery rate and low cost.
In order to achieve the aim, the invention adopts the technical scheme that: mixing and granulating sodium pyroantimonate and starch, mixing the granulated sodium pyroantimonate and the starch with refractory gold ore, introducing oxygen-enriched air at high temperature for oxidizing smelting, reducing Sb (V) in the sodium pyroantimonate into metal by the starch, reacting with gold in the refractory gold ore, enriching the metal into gold-enriched iron matte, and carrying out ore dressing treatment on smelting slag. The core of the invention is that the properties of sodium pyroantimonate which is low in high-temperature volatility and is easily reduced by starch are utilized, antimony and gold are primarily enriched in gold-rich iron matte after the action in the direct smelting process of refractory gold ore, the demand of the direct smelting process on antimony is greatly reduced, and the aim of directly smelting refractory gold to strengthen the gold enrichment is finally realized.
The specific technological process and parameters are as follows:
1. granulating
Mixing sodium pyroantimonate and starch and then granulating; mixing sodium pyroantimonate, starch and water according to the weight ratio of 100: 5.0: 2.0-10.0, granulating, wherein the particle size of the prepared sodium pyroantimonate granules is 0.5-3.0mm, and the sodium pyroantimonate granules are used in the direct smelting process.
2. Direct smelting
Mixing refractory gold ore and sodium pyroantimonate granules, and smelting at high temperature to enrich gold in gold-rich iron matte; mixing refractory gold ore, sodium pyroantimonate granules and flux, controlling the mass percentage of antimony in the mixed material to be less than 1.0 percent, and controlling the FeO/SiO in the mixed material2The mass ratio of CaO to SiO in the mixed material is maintained between 1.2 and 1.4 to 12The mass ratio of the gold-rich iron matte to the molten slag is 0.45, the temperature of the mixed material is raised to 1150-1250 ℃, oxygen-rich air with the concentration of 65-80% is introduced for oxidation smelting, the reaction time is kept for 1.0-3.0h to enable the molten slag and the gold-rich iron matte to be clarified and separated, the gold-rich iron matte is used for further gold enrichment subsequently, the molten slag is sent for ore dressing treatment, and the smelting flue gas is used for preparing sulfuric acid.
According to the inventionThe refractory gold ore comprises the following main components in percentage by mass: fe15.0-35.0%, SiO25.0-30.0 percent of S, 10.0-35.0 percent of S and 1.0-200.0 g/t of Au1.0-200.0 g/t.
The sodium pyroantimonate of the invention contains NaSb (OH)6Is not less than 50.0% by mass.
The mass percentage of FeO in the iron ore is not less than 50.0 percent, and the mass percentage of CaO in the limestone is not less than 45.0 percent.
Compared with the traditional system treatment method of refractory gold ores, the method has the following advantages: 1. by utilizing the property of small high-temperature volatilization of sodium pyroantimonate, the sodium pyroantimonate is proposed to be used as an antimony source in the direct smelting process of refractory gold ores, the mass percentage content of antimony in the mixed material is controlled to be less than 1.0 percent, and the consumption of antimony is greatly reduced; 2. by utilizing the property that Sb (V) in the sodium pyroantimonate can be reduced into metal by starch, the sodium pyroantimonate and the starch are granulated and then smelted with refractory gold ore, and the direct yield of gold in the gold-iron-rich sulfonium is more than 99.0 percent; 3. the method has the advantages of strong raw material adaptability, high metal recovery rate and simple process flow.
Drawings
FIG. 1: the invention is a process flow diagram.
Detailed Description
Example 1:
the refractory gold ore comprises the following main components in percentage by mass: fe24.52% and SiO216.95%, S14.93% and Au33.50g/t; the sodium pyroantimonate comprises the following main components in percentage by mass: NaSb (OH)698.2 percent, 58.44 percent of FeO in the iron ore by mass and 48.5 percent of CaO in the limestone by mass.
Mixing sodium pyroantimonate, starch and water according to the weight ratio of 100: 5.0: 4.0, granulating, and keeping the particle size of sodium pyroantimonate granules to be 1.5 mm; then mixing the refractory gold ore, the sodium pyroantimonate granules and the flux, controlling the mass percentage of antimony in the mixed material to be less than 0.90 percent, and controlling the FeO/SiO in the mixed material2The mass ratio of CaO to SiO in the mixture is maintained at 1.4/12The mass ratio of (1) is 0.45, the temperature of the mixed material is raised to 1150-Oxidizing and smelting, keeping the reaction time for 2.0h to enable smelting slag and the gold-rich iron matte to be clarified and separated, wherein the gold content in the gold-rich iron matte reaches 128g/t, the gold content in the smelting slag is 0.2g/t, and the direct yield of gold is more than 99.5%.
Claims (1)
1. A method for strengthening enrichment of gold by direct smelting of refractory gold is characterized by comprising the following steps:
(1) granulating
Mixing sodium pyroantimonate, starch and water according to the weight ratio of 100: 5.0: 2.0-10.0, granulating, wherein the particle size of the prepared sodium pyroantimonate granules is 1.0-3.0mm, and the sodium pyroantimonate granules are used in the direct smelting process;
(2) direct smelting
Mixing refractory gold ore, sodium pyroantimonate granules and flux, controlling the mass percentage of antimony in the mixed material to be less than 1.0 percent, and controlling the FeO/SiO in the mixed material2The mass ratio of CaO to SiO in the mixed material is maintained between 1.2 and 1.4 to 12The mass ratio of the gold-rich iron matte to the molten slag is 0.45, the temperature of the mixed material is raised to 1150-1250 ℃, oxygen-rich air with the concentration of 65-80% is introduced for oxidation smelting, the reaction time is kept for 1.0-3.0h to enable the molten slag and the gold-rich iron matte to be clarified and separated, the gold-rich iron matte is used for further gold enrichment subsequently, the molten slag is sent for ore dressing treatment, and the smelting flue gas is used for preparing sulfuric acid.
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