CN102312091A - Method for leaching low-grade gold in high-arsenic sulfur concentrate acid-making cinder by microorganism preoxidation - Google Patents
Method for leaching low-grade gold in high-arsenic sulfur concentrate acid-making cinder by microorganism preoxidation Download PDFInfo
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- CN102312091A CN102312091A CN201010217249XA CN201010217249A CN102312091A CN 102312091 A CN102312091 A CN 102312091A CN 201010217249X A CN201010217249X A CN 201010217249XA CN 201010217249 A CN201010217249 A CN 201010217249A CN 102312091 A CN102312091 A CN 102312091A
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- gold
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- leaching
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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
Abstract
The invention relates to a method for leaching low-grade gold in high-arsenic sulfur concentrate acid-making cinder by microorganism preoxidation, which has the main contents that bacterium preoxidation is utilized to leach the gold in the high-arsenic sulfur concentrate acid-making cinder, and the technology has the core that by taking various microorganisms, such as Thiobacillus ferrooxidans, sulfolobus and the like, under an acid condition, carbonate, sulfide, irony matter and part of silicate packing the gold are unpacked through oxygen in air, and are oxidized into sulfate, subsulphate or arsenate to achieve the goal of exposing the gold. After the gold is exposed, by taking the dilute sulphuric acid solution of thiourea as a leaching agent, under normal temperature and normal pressure, agitation leaching is carried out on pre-oxidized slag under the condition that the pH value is 1.3-1.8; 70-85 percent of gold is leached, and after solid-liquid separation is ended, a gold-contained solution can be extracted by using a traditional gold extraction process. The method of thiourea gold leaching after bacterium preoxidation has the characteristics that the toxicity is low; the solution in which the gold is removed is easy to treat, can be recycled, and can be produced by using a pollution discharge-free process flow; the gold and silver dissolution velocity is high; and the solution is not sensitive to the harmful impurities of base metals (Cu, As, Sb and Pb).
Description
Technical field
This project belongs to metallurgical technology field, is a kind of microbial metallurgy new technology.
Technical background
The gold of high arsenic difficult-treating gold mine or be embedded in arsenopyrite, pyrite or be deposited in the sulfide mineral intercrystalline with micro-fine-grained gold, or goldc grains is wrapped in the sulfide mineral with insoluble bodily form formula, it is bigger to leach difficulty, and it is main leaching with cyanide process after the preoxidation usually.Domestic a lot of mechanism and enterprise have obtained certain effect.
Contain the gold in the arsenic golden slag hard to manage in chemical industry, the melting waste slag, with complex way be wrapped in carbonate, sulfide, iron compound, silicate in, it is very big to leach difficulty; Domestic research institution takes roasting pre-treatment, wet method pressure oxidation pre-treatment, Microwave Pretreatment cyanide gold-leaching, alkali to soak method such as arsenic removal pre-treatment cyaniding leaching it to be carried out pre-treatment, destroy carbonate, sulfide, irony thing, the silicate of parcel gold, make gold be able to expose; Improve leaching yield; However, leaching yield is still lower, even the economic worth of the gold in the high arsenic waste residue is more considerable; But be difficult to exploitation, major part contains the low-grade slag of gold below 3% and can only discard.Major cause one is that traditional cyanide process is relatively poor to this material leaching effect, about 30-40% leaching yield, and resource utilization is too low, the nothing exploitation is worth; The 2nd, the selection of technology need be considered environment protection, and whether the environmental practice of technical process can better be controlled, and how innoxious waste residue is, how waste water is handled etc. all is sensitive issue very.
Utilize sulphur concentrate fluidized bed roasting acid-making process, the smoke dust washing can produce the arsenic-containing waste residue that contains golden 1-5 gram, is commonly called as relieving haperacidity and burns slag.Such gold that burns in the slag is wrapped up by carbonate, silicate, irony thing etc. repeatedly, and parcel is very tight, and it is big to leach difficulty, and the cyaniding leaching yield is in 30%, and recovery value is low, becomes a great problem of smelting the boundary.
Summary of the invention
The present invention to the effect that utilizes bacterium preoxidation to leach gold in the high pozzuolite concentrate relieving haperacidity burning slag; This technological core is to utilize multiple mikrobes such as thiobacillus ferrooxidant and sulfolobus; Under acidic conditions, carbonate, sulfide, irony thing and the part silicate that will wrap up gold through airborne oxygen unpack, and are oxidized to vitriol; Subsulphate or arsenate reach the purpose of exposed gold.
The effect of bacterium comes down to the oxidation of catalysis ferrous ion and reduced sulfur material, and bacterium self then obtains to keep the required energy of its growth from the oxidizing reaction of this heat release, has promoted its growth and breeding.General Study thinks that bacterial oxidation mechanism comprises direct oxidation, 2 kinds of indirect oxidations, and wherein the direct oxidation effect of bacterium is main.
Direct oxidation: the oxygenizement that bacteriogenic enzyme contacts with the material surface.
4Fe
2++O
2+4H
+＝4Fe
3++2H
2O
4FeAsS+13O
2+6H
2O＝4Fe
2++12H
++4ASO
4 3-+4SO
4 2-
Indirect oxidation:
FeS
2+2Fe
3+＝3Fe
2++2S
4Fe
2++O
2+4H
+＝4Fe
3++2H
2O
HAsO
2+2Fe
3++2H
2O＝AsO
4 3-+2Fe
2++5H
+
2S+3O
2+2H
2O＝4H
++2SO
4 2-
4FeAsS+8Fe
3++6H
2O+5O
2＝4ASO
4 3-+12Fe
2++4S+12H
+
4Fe
2++O
2+4H
+＝4Fe
3++2H
2O
CaCO
3+H
+→Ca
2++HCO
3 -
CaCO
3+H
2CO
3→Ca
2++2HCO
3 -
Visible from above reaction, bacterium is leached can constantly produce ferric sulphate and sulfuric acid, and the Fe in the ore, S and As are oxidized into Fe through bacterial oxidation
3+, SO
4 2-And AsO
4 3-, in whole oxidising process, both needed oxygen, also need acid, in oxidising process, also generate acid simultaneously.The acid that microbial metabolism produces makes carbonate decomposition: breathe the CO that produces
2Dissolving produces H
2CO
3Thereby, quicken the decomposition of carbonate, the acid that microbial metabolism produces also can make silicate decompose, and makes it generate the free silicon hydroxide.Series reaction has been untied golden parcel, gold is exposed be easy to dissolve to soak.
Leach with cyaniding after can adjusting the pH value of solution after gold exposes, but, adopt thiocarbamide to soak gold, can obtain that speed is fast, leaching yield is high, the simple effect of technology because the cyanide gold-leaching time is long, speed is slow, and front end solution pH value is 1.5-2.5 in addition.
Under the condition that the microbiological oxidation agent exists, gold dissolves in the sour sulfur urea solution:
Au+2SC(NH
2)
2＝Au[SC(NH
2)
2]
2 ++e
Bacterium makes iron be in high valence state, Fe in the solution
3+In the majority, and the high price molysite is renewable.With Fe
3+With dissolved oxygen be that the chemical equation that the thiocarbamide of oxygenant dissolves gold can be expressed as:
Fe
3++Au+2SC(NH
2)
2＝Au[SC(NH
2)
2]
2 ++Fe
2+
Au+2SC(NH
2)
2+1/4O
2+H
+＝Au[SC(NH
2)
2]
2 ++1/2H
2O
Consider from the stability of thiocarbamide, during thiourea gold extraction, adopt the dilution heat of sulfuric acid of thiocarbamide to make leaching agent, and should note adding earlier sour after vulcanization urea, the thiocarbamide hydrolysis was lost efficacy.Acidity of medium is relevant with thiourea concentration, and acidity is reducing with the thiourea concentration raising, and PH values little 1.5 is advisable under normal temperature thiocarbamide consumption condition, but acidity should not be too big, otherwise can increase the molten amount of acid of impurity.
The leaching yield of gold generally improves with the increase of thiocarbamide consumption.The thiocarbamide consumption is different with raw material Gold Content.Its unit consumption (kg/ton) is the 2-6 kilogram.
The characteristics of thiocarbamide method are that toxicity is low, and solution is prone to handle behind the degold, renewable reusing, and available not blowdown technical process is produced; The gold and silver dissolution rate is fast; Insensitive to base metal (Cu, As, Sb, Pb) detrimental impurity.
The present invention includes following process step:
(1) microbial culture: in having the oxidation trough of whipping appts, microbionation to substratum, is carried out enlarged culturing; Inoculum size is by volume: strain liquid: substratum worker=1: 10～20; Culture temperature is 20～40 ℃, and medium pH value is 1.0～2.0, incubation time 12～24 hours.Plant bacterium and adopt the mode of segmentation kind bacterium: using with a kind of bacterium at first is master's acid waste water (bacterial classification source); Increase other bacterial classifications of inoculation again.
(2) slag is soaked in bacterium preoxidation: sulphur concentrate fluidized bed roasting cigarette ash washing slag is joined in the bacteria oxidation tank, and the pulp density in the groove is 10～20%, fills air and stirring, and aeration quantity is 0.5～0.8m
3/ h; The stirring revolution is 1000～1500rpm, and temperature remains on 25～40 ℃, and using concentration is that 30～40% sulfuric acid adjustment pH value is 1.0～2.0; Oxidization time is 3-4 hour; The time of oxidation is relevant with the pulp density of slag roasting content, granularity and bacterial oxidation, and the condition of controlling above-mentioned leaching system leaches, and the acidity of periodic monitor system, current potential;
(3) thiocarbamide soaks gold
Consumption according to 2.0-2.9kg/t adds thiocarbamide, continues agitation leach and dissolves gold.Leaching yield can reach 70%-85%.The high more leaching yield of gold content is high more in the burning slag.Reach the 5G/ ton when above at Gold Content, leaching yield can reach more than 90%.
(4) solid-liquid separation: the ore pulp in the oxidation trough is carried out solid-liquid separation, obtain containing golden leach liquor and waste residue.
(5) extract gold: the golden leach liquor that contains that obtains extracts golden with methods such as method conventional in the hydrometallurgy such as carbon absorption, IX, iron zinc displacement gold.
The bacterial classification that the present invention adopts is for having a liking for the ferrous thiobacillus of acid oxidase (Acidithiobacillus ferrooxidans; Be called for short the A.f bacterium), have a liking for acid oxidase sulphur thiobacillus (Acidithiobacillus thiooxidans is called for short the A.t bacterium), iron protoxide hook end spirobacteria (Leptospirillum ferrooxidans is called for short the L.f bacterium), have a liking for acid heat thiobacillus thiooxidant (Acidithiobacillus Caldus is called for short the A.C bacterium), have a liking for acid and have a liking for warm sulfolobus solfataricus (Sulfolobus Acidocaldarius) and have a liking in high temperature oxidation sulfide sulfur bacillus (Acidibacillus thermosulfidooxidans), the sulfolobus etc. two or more.The culture of strains base comprises a kind of or mixing in Leathen, 9K, Wakesman, ONM or the Colmer substratum, nutrition base pH 1.3-2.5, and magnesium and calcium ion are provided by slag charge itself.
This leaching scheme has following advantage: (1) carbonate, sulfide, irony thing parcel Jin Junneng unpack in bacterium leaching system; (2) the thiocarbamide immunity from interference is strong, leaches soon the about 2-3h of agitation leach; (3), need not add other paramedicineses such as oxygenant because of there being bacterial oxidation ferrous; (4) suitably adjustment is filled a prescription, and when the heterotrophic bacterium in the autotrophic bacteria bred in a large number, the amino acid itself that secondary metabolism produces also had stronger molten gold effect, particularly aspergillus tubigensis, and also existing abroad be correlated with " pure biotechnological formulation " soaks golden patent; (5) in the stirring system, the application conditions of thiocarbamide is easy to control, may command reasonable cost.
Embodiment
Specific embodiment 1. contains arsenic 4.1%, and the relieving haperacidity of golden 2.3g/ ton is burnt slag and adopted bacterium preoxidation-thiocarbamide to soak gold-activated carbon absorption-desorption-electrodeposition flow process, silver content 25g/ ton in this slag charge, and copper content 0.12%, accompanying drawing is seen in technical process.
More single for mineral composition, silver, copper and the lower burning slag of other heavy metal content should be selected this flow process except that gold.Because this flow process is owing to adopt active carbon absorption technology; The concentration of gold in the leach liquor and the concentration of oxygen all there is not strict requirement; Therefore looser to the ratio of technical qualification, be easy to grasp, and because ore is formed simple; The content of silver and other metal is few in the leach liquor, and is few with the composition of golden competitive adsorption.Therefore the efficient and the capacity of charcoal absorption gold are higher, and the consumption of gac is also less.Because gac can be recycled, the consumption of gac is also less simultaneously.The result proves that adsorption rate can reach 97-98%.Main technique condition in the enforcement is following.
(1) microbial culture: in having the oxidation trough of whipping appts; The thiobacillus ferrooxidant bacterium is seeded in the substratum; Carry out enlarged culturing, inoculum size is by volume: strain liquid: substratum=1: 10～20, culture temperature are 25 ℃; Medium pH value is 1.0～2.0, incubation time 12 hours; Again according to other needs bacterial classification of material situation inoculation.
(2) bacterium preoxidation: slag is burnt in relieving haperacidity join in the bacteria oxidation tank, the pulp density in the groove is 10～30%, fills air and stirring, and aeration quantity is 0.3～0.8m
3/ h, the stirring revolution is 1500rpm, and temperature remains on 25 ℃, and using concentration is that 30～40% sulfuric acid adjustment pH value is 1.0～2.0, and oxidization time is 4-6 hour, the condition of controlling the leaching system leaches, and the acidity of periodic monitor system, current potential.
(3) thiocarbamide soaks gold: add thiocarbamide, according to 0.25-0.3Kg/100kg control consumption, continue to stir the golden pass into solution of 71%-80% 1 hour-2 hours.
(4) solid-liquid separation: the ore pulp in the oxidation trough is carried out solid-liquid separation, obtain containing golden leach liquor and waste residue, thiocarbamide soaks golden leaching yield and can reach 71%-85% after the bacterium preoxidation.
(5) carbon absorption is resolved back solution electrodeposition and is carried gold.The carbon adsorption rate reaches 97%, and absorption back solution returns and utilizes.
Claims (3)
1. the method that the high arsenic of sulphur concentrate relieving haperacidity burns low-grade gold in the slag is leached in a mikrobe preoxidation.This method is to the effect that utilized multiple mikrobes such as thiobacillus ferrooxidant and sulfolobus; Under acidic conditions; Carbonate, sulfide, irony thing and the part silicate that will wrap up gold through airborne oxygen unpack, and are oxidized to vitriol, subsulphate or arsenate; Reach the purpose of exposed gold, and utilize thiocarbamide that gold is leached.
2. according to claim 1; The bacterial classification that is adopted is for having a liking for the ferrous thiobacillus of acid oxidase (Acidithiobacillus ferrooxidans; Be called for short the A.f bacterium), have a liking for acid oxidase sulphur thiobacillus (Acidithiobacillus thiooxidans is called for short the A.t bacterium), iron protoxide hook end spirobacteria (Leptospirillum ferrooxidans is called for short the L.f bacterium), have a liking for acid heat thiobacillus thiooxidant (Acidithiobacillus Caldus is called for short the A.C bacterium), have a liking for acid and have a liking for warm sulfolobus solfataricus (Sulfolobus Acidocaldarius) and have a liking for two or more the combination in high temperature oxidation sulfide sulfur bacillus (Acidibacillus thermosulfidooxidans), the sulfolobus etc.The culture of strains base comprises a kind of or mixing in Leathen, 9K, Wakesman, ONM or the Colmer substratum, and magnesium and calcium ion are provided by slag charge itself.
3. according to claim 1, the thiocarbamide that is adopted soaks under the state that golden pH value is controlled at 1.3-2.0, can realize efficiently leaching fast.
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|---|---|---|---|
| CN201010217249XA CN102312091A (en) | 2010-07-05 | 2010-07-05 | Method for leaching low-grade gold in high-arsenic sulfur concentrate acid-making cinder by microorganism preoxidation |
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|---|---|---|---|
| CN201010217249XA CN102312091A (en) | 2010-07-05 | 2010-07-05 | Method for leaching low-grade gold in high-arsenic sulfur concentrate acid-making cinder by microorganism preoxidation |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105087929A (en) * | 2015-05-26 | 2015-11-25 | 中国科学院过程工程研究所 | Method for treating arsenic-containing gold ore through deep sea acidophilic microorganisms |
| CN107418913A (en) * | 2017-06-14 | 2017-12-01 | 湖南省农业生物技术研究中心 | A kind of application of the microorganism formulation of Efficient Conversion Heavy Metals in Contaminated Soils cadmium |
| CN113293299A (en) * | 2021-05-07 | 2021-08-24 | 云南省生态环境科学研究院 | Resource utilization method for arsenic-containing hazardous waste |
| CN116790900A (en) * | 2023-07-10 | 2023-09-22 | 山东大学 | Environment-friendly gold extraction method combining microorganism and gold extraction agent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1050593B1 (en) * | 1999-05-05 | 2003-07-30 | Boliden Contech AB | Two-stage bioleaching of sulphidic materials containing metal values and arsenic |
| CN1544665A (en) * | 2003-11-24 | 2004-11-10 | 长春黄金研究院 | Biological oxidation and thiourea resin slurry method gold extraction technology for difficultly leachable gold concentrate |
-
2010
- 2010-07-05 CN CN201010217249XA patent/CN102312091A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1050593B1 (en) * | 1999-05-05 | 2003-07-30 | Boliden Contech AB | Two-stage bioleaching of sulphidic materials containing metal values and arsenic |
| CN1544665A (en) * | 2003-11-24 | 2004-11-10 | 长春黄金研究院 | Biological oxidation and thiourea resin slurry method gold extraction technology for difficultly leachable gold concentrate |
Non-Patent Citations (1)
| Title |
|---|
| 周文波: "金的提取技术", 《矿业快报》, no. 440, 28 February 2006 (2006-02-28) * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105087929A (en) * | 2015-05-26 | 2015-11-25 | 中国科学院过程工程研究所 | Method for treating arsenic-containing gold ore through deep sea acidophilic microorganisms |
| CN107418913A (en) * | 2017-06-14 | 2017-12-01 | 湖南省农业生物技术研究中心 | A kind of application of the microorganism formulation of Efficient Conversion Heavy Metals in Contaminated Soils cadmium |
| CN113293299A (en) * | 2021-05-07 | 2021-08-24 | 云南省生态环境科学研究院 | Resource utilization method for arsenic-containing hazardous waste |
| CN116790900A (en) * | 2023-07-10 | 2023-09-22 | 山东大学 | Environment-friendly gold extraction method combining microorganism and gold extraction agent |
| CN116790900B (en) * | 2023-07-10 | 2024-02-23 | 山东大学 | Environment-friendly gold extraction method combining microorganism and gold extraction agent |
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Application publication date: 20120111 |