CN102409183A - Gold extraction method by pre-oxidation and cyanide leaching of refractory gold concentrate - Google Patents
Gold extraction method by pre-oxidation and cyanide leaching of refractory gold concentrate Download PDFInfo
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Abstract
The invention discloses a gold extraction method by pre-oxidation and cyanide leaching of refractory gold concentrate, comprising the following steps: firstly mixing the refractory gold concentrate and a dispersing agent, grinding by a grinder; then mixing the oxidant and the grinded material, size mixing; then mixing and stirring the slurry with concentrated sulfuric acid, so as to perform more than a period of acid pre-oxidation reaction, reacting for more than one hour at a constant temperature, separating the solid and the liquid; then adjusting the pH value of the gold-bearing slag after the pre-oxidation, performing alkaline pretreatment for more than one hour; performing cyanide gold extraction on the slurry after alkaline pretreatment, passing oxygen or air during the cyanide process. The invention has advantages of low cost, simple operation, strong adaptability of raw material, high gold recovery rate, environmental pollution-free and easy industrial application.
Description
Technical field
The invention belongs to the gold extractive technique field of hydrometallurgy, relate in particular to a kind of indissoluble gold ore deposit and leach the method for carrying gold.
Background technology
The indissoluble gold ore deposit is called difficult-treating gold mine or obstinate gold mine usually again, can not use conventional cyanide process effectively to leach the wherein ore of most of gold even it is meant through fine grinding.Along with the large scale mining of gold mine, be prone to handle gold ore resource in the world and day by day reduce, difficult-treating gold mine will become the main Mineral Resources of gold industry from now on.According to incompletely statistics, at present in the explored gold reserve of China, have 30% to be difficult-treating gold mine, it mainly is distributed in areas such as the Liao Dynasty, Hunan, osmanthus, Guizhou Province, sweet, Anhui, Ji.The development and use difficult-treating gold mine has become a vital task of gold industry.
Verified in the gold geologic reserve in China, had approximately to belong to pyrite/arsenopyrite coated indissoluble gold ore deposit about 1000t, it is one of main indissoluble gold ore deposit.Golden embedding cloth in this type gold mine is among pyrite and mispickel lattice, and wherein high-load sulphur and arsenic leach very harmful to cyaniding; Must carry out pre-treatment to it in the industry, open parcel, remove the material that sulphur and arsenic etc. influence cyaniding simultaneously, can effectively leach and carry gold gold.At present, the method for pre-oxidizing of having used in the industry has: roasting method, high-pressure oxidation method, biological pre-oxidation method, chemical preoxidation etc., but all there is certain deficiency in these methods.For example, roasting method causes burning easily, forms caking, hinder gold and further leach, and along with the raising of environmental requirement, the waste gas pollution control and treatment cost improves, and its range of application is restricted; The high-pressure oxidation method is operated under HTHP, and equipment material requires high, and investment cost is big, and undesirable to containing the higher material treatment effect of organic carbon; The available bacterial classification of bacterial oxidation method is limited, and reaction time is long, guarantee that bacteria live and breeding make reaction conditions comparatively harsh.Recent decades; Continuous research along with the scientific worker; The method that chemistry pre-oxidation treatment method nitric acid catalytic oxidation (referring to CN1099071A Chinese patent document), chlorination have successively occurred and adopted chemical substances such as superoxide, permanganate, SRM 935a, perchlorate, hypochlorite, ozone to carry out preoxidation; But these methods are because problems such as equipment, operation or cost rest on the laboratory study stage basically.
The two ore deposit methods leachings of pyrite/Manganse Dioxide are applied to the pyrolusite wet processing the earliest and produce manganous sulfate (CN1058201A Chinese patent document), and industrial application has formed the more sophisticated technology of a cover for many years.Pyrolusite oxidation of sulfureted miner skill was applied to the oxidation extract technology of other metal sulfide afterwards; Like the hydrometallurgy of zinc sulfide ore, indium sulfide concentrate (specifically can referring to CN1095766A Chinese patent document and CN101113491A Chinese patent document), but do not see to be useful on and extract the relevant report of smelting gold mine.
Summary of the invention
The technical problem that the present invention will solve is the deficiency that overcomes prior art, provides that a kind of cost is low, simple to operate, adaptability to raw material is strong, gold recovery is high, environment friendly and pollution-free and refractory gold concentrate preoxidation-cyaniding that be easy to industrial application leaches the method for carrying gold.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is that the method for carrying gold is leached in a kind of refractory gold concentrate preoxidation-cyaniding, may further comprise the steps:
(1) fine grinding:, mixed material is fully levigate with grinding machine with said refractory gold concentrate and dispersant;
(2) acid preoxidation: oxygenant and material after step (1) fine grinding mixed by a certain percentage size mixing; The disposed slurry of will sizing mixing then mixes stirring and carries out the acid preoxidation reaction more than a section with the vitriol oil; More than the isothermal reaction time 1h, after finishing, reaction carries out solid-liquid separation; The manganese oxidation liquid that contains after the solid-liquid separation can be used for manufacture manganous sulfate, electrolytic manganese or electrolysis MnO after purifying
2
(3) alkaline pre-treatment: what will after the acid preoxidation of step (2), obtain contains gold mine slag adjust pH to 7～14, then more than pre-treatment 1h under this condition;
(4) cyaniding is leached: will carry out cyanidation gold-extractedly through the alkaline pretreated ore pulp of step (3), cyaniding process aerating oxygen or air are accomplished the golden process of putting forward that leaches behind the cyanogenation.
The method of carrying gold is leached in above-mentioned refractory gold concentrate preoxidation-cyaniding, and the essential substance in the said refractory gold concentrate is preferably pyrite/arsenopyrite coated refractory gold concentrate.Preferably more than 10g/t, S content is preferably 1%～30% for Au content in said pyrite/arsenopyrite coated refractory gold concentrate, and As content is preferably 1%～25%.
The method of carrying gold is leached in above-mentioned refractory gold concentrate preoxidation-cyaniding; In the said step (1); Said dispersion agent is preferably Sodium hexametaphosphate 99, sodium lignosulfonate, sodium tartrate or Trisodium Citrate, and the addition of said dispersion agent preferably adds 0.5kg～20kg by refractory gold concentrate per ton.
The method of carrying gold is leached in above-mentioned refractory gold concentrate preoxidation-cyaniding; In the said step (1); Said grinding machine is preferably rod mill, ball mill, tower grinding machine or agitating ball mill, said refractory gold concentrate through abundant levigate after grain graininess preferably satisfy-45 μ m more than 95%.
The method of carrying gold is leached in above-mentioned refractory gold concentrate preoxidation-cyaniding, and in the said step (2), said acid preoxidation reaction process is preferably one-part form reaction completion or divides two-stage reaction to accomplish.When said acid preoxidation reaction process was one-part form reaction completion, said oxygenant was preferably pyrolusite or the dioxide ore for manganese (MnO in pyrolusite or the dioxide ore for manganese
2Content generally can reach 30%～80%, down together), the mass ratio of said oxygenant and said refractory gold concentrate preferably satisfies 5: (1～20); The mass ratio of the said vitriol oil and said oxygenant is preferably (20～1): 5.When said acid preoxidation reaction process was accomplished for dividing two-stage reaction: the oxygenant in first section reaction was preferably pyrolusite or dioxide ore for manganese; The mass ratio of said preferred oxidant and said refractory gold concentrate satisfies 5: (1～20), and the mass ratio of the said vitriol oil and said oxygenant is preferably (20～1): 5; Second section reaction is meant first section reaction finished and oxidation sludge after solid-liquid separation reacts with the oxygenant and the vitriol oil that replenish again; Oxygenant in second section reaction is preferably pyrolusite, dioxide ore for manganese, nitric acid, potassium permanganate or hypochlorite; The addition of said oxygenant is preferably 1%～40% (more preferably 1%～30%) of said oxidation sludge quality, and the said vitriol oil that replenishes again is preferably (20～1) with the mass ratio of the oxygenant that replenishes again: 5.Show that through our experiment if elemental sulfur content＞0.5% o'clock in the oxidation sludge can divide two sections to carry out acid preoxidation, perhaps in follow-up step (3), carry out alkaline preoxidation, preoxidation process all preferably carries out under condition of normal pressure.
The method of carrying gold is leached in above-mentioned refractory gold concentrate preoxidation-cyaniding; In the said acid preoxidation reaction process; The liquid-solid ratio of reaction is preferably (1～8): 1 (more preferably (3～8): 1); Temperature of reaction is preferably 40 ℃～105 ℃ (more preferably 60 ℃～100 ℃), and spent acid concentration is preferably 10g/L～60g/L in the control reaction system, and the reaction times is preferably 1h～48h.
The method of carrying gold is leached in above-mentioned refractory gold concentrate preoxidation-cyaniding, and in the said step (3), the adjustment agent that the adjusting of said pH value is preferably used is quicklime, sodium hydroxide or calcium hydroxide.
The method of carrying gold is leached in above-mentioned refractory gold concentrate preoxidation-cyaniding, also can be attended by oxidizing reaction simultaneously in the alkaline preprocessing process of said step (3), and the oxygenant that uses in this oxidizing reaction is oxygen, air, sodiumperoxide or calcium superoxide; The ventilation flow rate of said oxygen or air is preferably 0.1 m
3/ h～1.5m
3/ h, the addition of said sodiumperoxide or calcium superoxide are preferably said 1%～40% (more preferably 1%～30%) that contains gold mine slag amount.If what obtain after the acid preoxidation contains in the gold mine slag elemental sulfur content higher (for example＞0.5% o'clock), can in alkaline preprocessing process, start oxidizing reaction simultaneously.
The method of carrying gold is leached in above-mentioned refractory gold concentrate preoxidation-cyaniding, and the temperature of reaction during said alkaline pre-treatment preferably is controlled at 15 ℃～80 ℃, and the alkaline pretreated time preferably is controlled at 1h～24h.
The method of carrying gold is leached in above-mentioned refractory gold concentrate preoxidation-cyaniding; In the said step (4), the reaction conditions of said cyanogenation is preferably: the pH value of reaction system is controlled at 9～12, and the liquid-solid ratio of reaction system is controlled at (0.5～5): 1; The addition of the prussiate of using in the reaction adds 1kg～20kg by said ore pulp per ton; The time of cyanogenation is controlled at 8h～96h, and the temperature of cyanogenation is controlled at 10 ℃～50 ℃, and the ventilation flow rate of said oxygen or air is 0.1 m
3/ h～1.5m
3/ h.
Compared with prior art; The invention provides a kind of refractory gold concentrate preoxidation-cyaniding and leach the method for carrying gold; Its main thought is with behind pyrite/ultra-fine mill of arsenopyrite coated refractory gold concentrate; Mix with oxygenants such as dioxide ore for manganese, in sulfuric acid medium, carry out the normal pressure preoxidation of refractory gold concentrate, utilize MnO
2With FeS
2(FeAsS) characteristic of Oxidizing and Reducing Agents each other makes the manganese oxide reduction of dissolved get into solution, and oxygenolysis all takes place for pyrite and arsenopyrite, and the gold that wherein is wrapped comes out; After the solid-liquid separation on ore pulp, send the manganese smelting system behind oxidation liquid iron purification, the arsenic, produce manganese metal or Manganse Dioxide; Oxidation sludge then passes through liquid-solid separation after the further oxide treatment, contain the gold mine slag and make slurry, adjustment pH, through cyaniding leach carry gold after gold leaching rate can reach more than 90%.Compared with prior art; The inventive method is a wet processing; Its advantage is: utilize dioxide ore for manganese and pyrite/these two types of mineral of arsenopyrite type indissoluble gold ore deposit characteristics of oxygenant, reductive agent each other; Reach the purpose that reclaims manganese, gold simultaneously, for this type of pyrite/arsenopyrite coated indissoluble gold ore deposit handle provide a kind of simple to operate, control condition is gentle, lower-cost normal pressure wet method leaches gold extraction technology.Than existing other technologies, there are not problems such as arsenical fume pollution in method of the present invention, and cost is low, and simple to operate, adaptability to raw material is strong, and gold recovery is high, is easy to industrial application.
Description of drawings
Fig. 1 is the process flow sheet of the inventive method.Manganese oxide ore shown in the figure contains oxidants such as pyrolusite or dioxide ore for manganese, and the acid pre-oxidation among the figure can be selected one-part form reaction or two-part reaction based on specific embodiment, and the frame of broken lines among the figure is represented optional step.
Embodiment
Below in conjunction with Figure of description and specific embodiment the present invention is further described.
Embodiment 1:
The method of carrying gold is leached in a kind of refractory gold concentrate preoxidation-cyaniding as shown in Figure 1 of the present invention; Essential substance in the refractory gold concentrate of being selected for use is pyrite/arsenopyrite coated refractory gold concentrate, and the Au content in this pyrite/arsenopyrite coated refractory gold concentrate reaches 76.55g/t, and S content is that 17.4% (percentage ratio in the composition proportion if no special instructions; All represent massfraction); As is 3.44%, and Fe is 21.95%, and its key step is as follows.
1. fine grinding: get above-mentioned refractory gold concentrate 50g and mix with the 0.5g sodium lignosulfonate, with grinding machine (rod mill, ball mill, tower grinding machine or agitating ball mill all can) that mixed material is fully levigate to 95% through 25 μ m.
2. acid preoxidation: with oxygenant pyrolusite (MnO in the staple
252%, Fe 5.72%) mix by 2: 1 mass ratio with material after step 1 fine grinding and size mixing, the disposed slurry of will sizing mixing then mixes with the vitriol oil to stir and carries out the acid preoxidation reaction of one-part form, and the mass ratio of sulfuric acid and oxygenant was controlled at 1: 1.5; In the acid preoxidation reaction process, the liquid-solid ratio of reaction is adjusted into 4: 1, and temperature of reaction is controlled at 95 ℃, and spent acid concentration is controlled at 50g/L in the reaction system, and the isothermal reaction time is 20h.After finishing, reaction carries out solid-liquid separation; The manganese oxidation liquid that contains after the solid-liquid separation can be used for manufacture manganous sulfate, electrolytic manganese or electrolysis MnO after purifying
2Filter residue after the filtration carries out subsequent disposal after washing.
3. alkaline pre-treatment: what will after the acid preoxidation of step 2, obtain contains gold mine slag adjust pH to 10, and the adjustment agent that the adjusting of pH value is selected for use is lime (staple is quicklime and calcium hydroxide), then room temperature (for example 25 ℃) pre-treatment 2h.
4. cyaniding is leached: will carry out cyanidation gold-extracted through the alkaline pretreated ore pulp of step 3; The reaction conditions of cyanogenation is: the pH value of reaction system is controlled at 10, and the liquid-solid ratio of reaction system was controlled at 3: 1, and the addition of the prussiate of using in the reaction adds 5kg by said ore pulp per ton; The time of cyanogenation is controlled at 24h; The temperature of cyanogenation is controlled at 35 ℃, blasts air with pneumatic pump in the cyaniding process, the ventilation flow rate 1m of air
3/ h, cyanogenation finish the back and accomplish the golden process of putting forward that leaches.
The aforesaid method of employing present embodiment and direct cyanide process leach the simultaneous test of carrying gold to the pyrite/arsenopyrite coated refractory gold concentrate of present embodiment; The result shows; Directly the gold leaching rate of cyanide process is merely 25.9%; And the method that adopts above-mentioned present embodiment leach carry gold after, the gold the cyaniding leaching yield reach 90%.
Embodiment 2:
The method of carrying gold is leached in a kind of refractory gold concentrate preoxidation-cyaniding as shown in Figure 1 of the present invention; Essential substance in the refractory gold concentrate of being selected for use is pyrite/arsenopyrite coated refractory gold concentrate; Au content in this pyrite/arsenopyrite coated refractory gold concentrate reaches 43.43g/t, and S content is 19%, and As is 5.86%; Fe is 21.90%, and its key step is as follows.
1. fine grinding: get above-mentioned refractory gold concentrate 50g and mix with the 0.75g sodium lignosulfonate, with grinding machine (rod mill, ball mill, tower grinding machine or agitating ball mill all can) that mixed material is fully levigate to 95% through 45 μ m.
2. acid preoxidation: oxygenant pyrolusite (the manganese ore composition is with embodiment 1) and material after step 1 fine grinding mixed by 2.4: 1 mass ratio size mixing, the disposed slurry of will sizing mixing then mixes with the vitriol oil to stir and carries out the acid preoxidation reaction of two-part.In first section reaction, the mass ratio of sulfuric acid and oxygenant was controlled at 1: 1.3; In the acid preoxidation reaction process, the liquid-solid ratio of reaction is adjusted into 3: 1, and temperature of reaction is controlled at 85 ℃, and spent acid concentration is controlled at 20g/L in the reaction system, and the isothermal reaction time is 12h.After finishing, reaction carries out solid-liquid separation; The manganese oxidation liquid that contains after the solid-liquid separation can be used for manufacture manganous sulfate, electrolytic manganese or electrolysis MnO after purifying
2Filter residue after the filtration carries out second section reaction again.In second section acid preoxidation reaction process; Allocate first section acid preoxidation slag into oxidant potassium permanganate (addition of potassium permanganate be oxidation sludge quality 20%), add the vitriol oil (guaranteeing that the spent acid amount is 30g/L) again, the adjustment liquid-solid ratio is 5: 1; Temperature of reaction is controlled at 85 ℃; Constant temperature stirs 12h, filters and the washing filter residue, and filter residue carries out follow-up processing.
3. alkaline pre-treatment: what will after the acid preoxidation of step 2, obtain contains gold mine slag adjust pH to 10, and the adjustment agent that the adjusting of pH value is selected for use is lime (staple is quicklime and calcium hydroxide), then pre-treatment 2h at room temperature.
4. cyaniding is leached: will carry out cyanidation gold-extracted through the alkaline pretreated ore pulp of step 3; The reaction conditions of cyanogenation is: the pH value of reaction system is controlled at 10, and the liquid-solid ratio of reaction system was controlled at 4: 1, and the addition of the prussiate of using in the reaction adds 6kg by said ore pulp per ton; The time of cyanogenation is controlled at 72h; (for example 25 ℃～30 ℃) cyaniding blasts air with pneumatic pump in the cyaniding process, the ventilation flow rate 1m of air under the room temperature
3/ h, cyanogenation finish the back and accomplish the golden process of putting forward that leaches.
The aforesaid method of employing present embodiment and direct cyanide process leach the simultaneous test of carrying gold to the pyrite/arsenopyrite coated refractory gold concentrate of present embodiment; The result shows; Directly the gold leaching rate of cyanide process is merely 10.5%; And the method that adopts above-mentioned present embodiment leach carry gold after, the gold the cyaniding leaching yield reach 91.5%.
Embodiment 3:
The method of carrying gold is leached in a kind of refractory gold concentrate preoxidation-cyaniding as shown in Figure 1 of the present invention; Essential substance in the refractory gold concentrate of being selected for use is pyrite/arsenopyrite coated refractory gold concentrate; Au content in this pyrite/arsenopyrite coated refractory gold concentrate reaches 64.34g/t, and S content is 31.1%, and As is 10.81%; Fe is 36.19%, and its key step is as follows.
1. fine grinding: get above-mentioned refractory gold concentrate 50g and mix with the 0.15g sodium tartrate, with grinding machine (rod mill, ball mill, tower grinding machine or agitating ball mill all can) that mixed material is fully levigate to 95% through 38 μ m.
2. acid preoxidation: oxygenant pyrolusite (composition is with embodiment 1) and material after step 1 fine grinding mixed by 3: 1 mass ratio size mixing; The disposed slurry of will sizing mixing then mixes stirring and carries out the acid preoxidation reaction of one-part form with the vitriol oil, the mass ratio of sulfuric acid and oxygenant was controlled at 1: 1.5; In the acid preoxidation reaction process, the liquid-solid ratio of reaction is adjusted into 2: 1, and temperature of reaction is controlled at 95 ℃, and spent acid concentration is controlled at 40g/L in the reaction system, and the constant temperature stirring reaction time is 12h.After finishing, reaction carries out solid-liquid separation; The manganese oxidation liquid that contains after the solid-liquid separation can be used for manufacture manganous sulfate, electrolytic manganese or electrolysis MnO after purifying
2Filter residue after the filtration carries out subsequent disposal after washing.
3. alkaline pre-treatment: what will after the acid preoxidation of step 2, obtain contains gold mine slag adjust pH to 8; The adjustment agent that the adjusting of pH value is selected for use is lime (staple is quicklime and calcium hydroxide); In alkaline preprocessing process, also be attended by oxidizing reaction simultaneously; The oxygenant that uses in the oxidizing reaction is sodiumperoxide, and the consumption of sodiumperoxide is 10% for containing gold mine slag amount, then pre-treatment 10h under 45 ℃ of temperature.
4. cyaniding is leached: will carry out cyanidation gold-extracted through the alkaline pretreated ore pulp of step 3; The reaction conditions of cyanogenation is: the pH value of reaction system is controlled at 11, and the liquid-solid ratio of reaction system was controlled at 3: 1, and the addition of the prussiate of using in the reaction adds 4kg by said ore pulp per ton; The time of cyanogenation is controlled at 48h; Cyaniding under the normal temperature blasts air with pneumatic pump in the cyaniding process, the ventilation flow rate 1m of air
3/ h, cyanogenation finish the back and accomplish the golden process of putting forward that leaches.
The aforesaid method of employing present embodiment and direct cyanide process leach the simultaneous test of carrying gold to the pyrite/arsenopyrite coated refractory gold concentrate of present embodiment; The result shows; Directly the gold leaching rate of cyanide process is 0; And the method that adopts above-mentioned present embodiment leach carry gold after, the gold the cyaniding leaching yield reach 94.34%.
Embodiment 4:
The method of carrying gold is leached in a kind of refractory gold concentrate preoxidation-cyaniding as shown in Figure 1 of the present invention; Essential substance in the refractory gold concentrate of being selected for use is pyrite/arsenopyrite coated refractory gold concentrate; Au content in this pyrite/arsenopyrite coated refractory gold concentrate reaches 50.33g/t, and S content is 20.85%, and As is 7.43%; Fe is 25.48%, and its key step is as follows.
1. fine grinding: get above-mentioned refractory gold concentrate 50g and mix with the 0.3g Trisodium Citrate, with grinding machine (rod mill, ball mill, tower grinding machine or agitating ball mill all can) that mixed material is fully levigate to 95% through 38 μ m.
2. acid preoxidation: oxygenant pyrolusite (composition is with embodiment 1) and material after step 1 fine grinding mixed by 3: 1 mass ratio size mixing; The disposed slurry of will sizing mixing then mixes stirring and carries out the acid preoxidation reaction of one-part form with the vitriol oil, the mass ratio of sulfuric acid and oxygenant was controlled at 1: 1.5; In the acid preoxidation reaction process, the liquid-solid ratio of reaction is adjusted into 2: 1, and temperature of reaction is controlled at 95 ℃, and spent acid concentration is controlled at 50g/L in the reaction system, and the constant temperature stirring reaction time is 12h.After finishing, reaction carries out solid-liquid separation; The manganese oxidation liquid that contains after the solid-liquid separation can be used for manufacture manganous sulfate, electrolytic manganese or electrolysis MnO after purifying
2Filter residue after the filtration carries out subsequent disposal after washing.
3. alkaline pre-treatment: what will after the acid preoxidation of step 2, obtain contains gold mine slag adjust pH to 10; The adjustment agent that the adjusting of pH value is selected for use is lime (staple is quicklime and calcium hydroxide); In alkaline preprocessing process, also be attended by oxidizing reaction simultaneously; The oxygenant that uses in the oxidizing reaction is calcium superoxide, and the consumption of calcium superoxide is 20% for containing gold mine slag amount, then pre-treatment 24h under 50 ℃ of temperature.
4. cyaniding is leached: will carry out cyanidation gold-extracted through the alkaline pretreated ore pulp of step 3; The reaction conditions of cyanogenation is: the pH value of reaction system is controlled at 10, and the liquid-solid ratio of reaction system was controlled at 4: 1, and the addition of the prussiate of using in the reaction adds 3kg by said ore pulp per ton; The time of cyanogenation is controlled at 48h; Cyaniding under the normal temperature blasts air with pneumatic pump in the cyaniding process, the ventilation flow rate 1m of air
3/ h, cyanogenation finish the back and accomplish the golden process of putting forward that leaches.
The aforesaid method of employing present embodiment and direct cyanide process leach the simultaneous test of carrying gold to the pyrite/arsenopyrite coated refractory gold concentrate of present embodiment; The result shows; Directly the gold leaching rate of cyanide process is merely 7.5%; And the method that adopts above-mentioned present embodiment leach carry gold after, the gold the cyaniding leaching yield reach 90.7%.
Embodiment 5:
The method of carrying gold is leached in a kind of refractory gold concentrate preoxidation-cyaniding as shown in Figure 1 of the present invention; Essential substance in the refractory gold concentrate of being selected for use is pyrite/arsenopyrite coated refractory gold concentrate; The staple and the proportioning of this pyrite/arsenopyrite coated refractory gold concentrate are identical with embodiment 4, and its key step is as follows.
1. fine grinding: get above-mentioned refractory gold concentrate 50g and mix with the 0.60g sodium tartrate, with grinding machine (rod mill, ball mill, tower grinding machine or agitating ball mill all can) that mixed material is fully levigate to 95% through 38 μ m.
2. acid preoxidation: oxygenant pyrolusite (composition is with embodiment 1) and material after step 1 fine grinding mixed by 3: 1 mass ratio size mixing; The disposed slurry of will sizing mixing then mixes stirring and carries out the acid preoxidation reaction of one-part form with the vitriol oil, the mass ratio of sulfuric acid and oxygenant was controlled at 1: 1.5; In the acid preoxidation reaction process, the liquid-solid ratio of reaction is adjusted into 2: 1, and temperature of reaction is controlled at 95 ℃, and spent acid concentration is controlled at 50g/L in the reaction system, and the constant temperature stirring reaction time is 12h.After finishing, reaction carries out solid-liquid separation; The manganese oxidation liquid that contains after the solid-liquid separation can be used for manufacture manganous sulfate, electrolytic manganese or electrolysis MnO after purifying
2Filter residue after the filtration carries out subsequent disposal after washing.
3. alkaline pre-treatment: what will after the acid preoxidation of step 2, obtain contains gold mine slag adjust pH to 12; The adjustment agent that the adjusting of pH value is selected for use is lime (staple is quicklime and calcium hydroxide); In alkaline preprocessing process, also be attended by oxidizing reaction simultaneously; The oxygenant that uses in the oxidizing reaction is oxygen, and the ventilation flow rate of oxygen is 0.1 m
3/ h～1.5m
3/ h, pre-treatment 16h under 75 ℃ of temperature then.
4. cyaniding is leached: will carry out cyanidation gold-extracted through the alkaline pretreated ore pulp of step 3; The reaction conditions of cyanogenation is: the pH value of reaction system is controlled at 11.5, and the liquid-solid ratio of reaction system was controlled at 5: 1, and the addition of the prussiate of using in the reaction adds 6kg by said ore pulp per ton; The time of cyanogenation is controlled at 24h; The temperature of cyanogenation is controlled at 35 ℃, blasts air with pneumatic pump in the cyaniding process, the ventilation flow rate 1m of air
3/ h, cyanogenation finish the back and accomplish the golden process of putting forward that leaches.
The aforesaid method of employing present embodiment and direct cyanide process leach the simultaneous test of carrying gold to the pyrite/arsenopyrite coated refractory gold concentrate of present embodiment; The result shows; Directly the gold leaching rate of cyanide process is merely 7.5%; And the method that adopts above-mentioned present embodiment leach carry gold after, the gold the cyaniding leaching yield reach 92.3%.
Claims (10)
1. the method for carrying gold is leached in refractory gold concentrate preoxidation-cyaniding, may further comprise the steps:
(1) fine grinding:, mixed material is fully levigate with grinding machine with said refractory gold concentrate and dispersant;
(2) acid preoxidation: oxygenant and material after step (1) fine grinding mixed by a certain percentage size mixing; The disposed slurry of will sizing mixing then mixes stirring and carries out the acid preoxidation reaction more than a section with the vitriol oil; More than the isothermal reaction time 1h, after finishing, reaction carries out solid-liquid separation;
(3) alkaline pre-treatment: what will after the acid preoxidation of step (2), obtain contains gold mine slag adjust pH to 7～14, then more than pre-treatment 1h under this condition;
(4) cyaniding is leached: will carry out through the alkaline pretreated ore pulp of step (3) cyanidation gold-extracted, cyaniding process aerating oxygen or air.
2. the method for carrying gold is leached in refractory gold concentrate preoxidation according to claim 1-cyaniding; It is characterized in that; Essential substance in the said refractory gold concentrate is pyrite/arsenopyrite coated refractory gold concentrate; Au content in said pyrite/arsenopyrite coated refractory gold concentrate is more than 10g/t, and S content is 1%～30%, and As content is 1%～25%.
3. the method for carrying gold is leached in refractory gold concentrate preoxidation according to claim 1-cyaniding; It is characterized in that; In the said step (1); Said dispersion agent is Sodium hexametaphosphate 99, sodium lignosulfonate, sodium tartrate or Trisodium Citrate, and the addition of said dispersion agent adds 0.5kg～20kg by refractory gold concentrate per ton.
4. the method for carrying gold is leached in refractory gold concentrate preoxidation according to claim 1-cyaniding; It is characterized in that; In the said step (1); Said grinding machine is rod mill, ball mill, tower grinding machine or agitating ball mill, said refractory gold concentrate through abundant levigate after 95% above grain graininess less than 45 μ m.
5. the method for carrying gold is leached in refractory gold concentrate preoxidation according to claim 1-cyaniding, it is characterized in that, in the said step (2), said acid preoxidation reaction process is that the one-part form reaction is accomplished or the branch two-stage reaction is accomplished;
When said acid preoxidation reaction process was one-part form reaction completion, said oxygenant was pyrolusite or dioxide ore for manganese, and the mass ratio of said oxygenant and said refractory gold concentrate satisfies 5: (1～20); The mass ratio of the said vitriol oil and said oxygenant is (20～1): 5;
When said acid preoxidation reaction process was accomplished for dividing two-stage reaction: the oxygenant in first section reaction was pyrolusite or dioxide ore for manganese; The mass ratio of said oxygenant and said refractory gold concentrate satisfies 5: (1～20), the mass ratio of the said vitriol oil and said oxygenant are (20～1): 5; Second section reaction is meant first section reaction finished and oxidation sludge after solid-liquid separation reacts with the oxygenant and the vitriol oil that replenish again; Oxygenant in second section reaction is pyrolusite, dioxide ore for manganese, nitric acid, potassium permanganate or hypochlorite; The addition of said oxygenant is 1%～40% of a said oxidation sludge quality, and the said vitriol oil that replenishes again is (20～1) with the mass ratio of the oxygenant that replenishes again: 5.
6. leach the method for carrying gold according to claim 1 or 5 described refractory gold concentrate preoxidation-cyaniding; It is characterized in that; In the said acid preoxidation reaction process, the liquid-solid ratio of reaction is (1～8): 1, and temperature of reaction is 40 ℃～105 ℃; Spent acid concentration is 10g/L～60g/L in the control reaction system, and the reaction times is 1h～48h.
7. the method for carrying gold is leached in refractory gold concentrate preoxidation according to claim 1-cyaniding, it is characterized in that in the said step (3), the adjustment agent that the adjusting of said pH value is selected for use is quicklime, sodium hydroxide or calcium hydroxide.
8. the method for carrying gold is leached in refractory gold concentrate preoxidation according to claim 1-cyaniding; It is characterized in that; Also be attended by oxidizing reaction in the alkaline preprocessing process of said step (3) simultaneously, the oxygenant that uses in this oxidizing reaction is oxygen, air, sodiumperoxide or calcium superoxide; The ventilation flow rate of said oxygen or air is 0.1 m
3/ h～1.5m
3/ h, the addition of said sodiumperoxide or calcium superoxide are said 1%～40% of the gold mine slag amount that contains.
9. leach the method for carrying gold according to claim 1,7 or 8 described refractory gold concentrate preoxidation-cyaniding, it is characterized in that, the temperature of reaction during said alkaline pre-treatment is controlled at 15 ℃～80 ℃, and the alkaline pretreated time is controlled at 1h～24h.
10. the method for carrying gold is leached in refractory gold concentrate preoxidation according to claim 1-cyaniding; It is characterized in that; In the said step (4), the reaction conditions of said cyanogenation is: the pH value of reaction system is controlled at 9～12, and the liquid-solid ratio of reaction system is controlled at (0.5～5): 1; The addition of the prussiate of using in the reaction adds 1kg～20kg by said ore pulp per ton; The time of cyanogenation is controlled at 8h～96h, and the temperature of cyanogenation is controlled at 10 ℃～50 ℃, and the ventilation flow rate of said oxygen or air is 0.1 m
3/ h～1.5m
3/ h.
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