A kind of method utilizing high arsenic ion toleration leaching microbacteria to carry out arsenic-bearing refractory gold ore microbe-preoxidation gold
Technical field
The invention belongs to Biohydrometallurgy technical field.It is specifically related to a kind of technique utilizing high arsenic ion toleration leaching microbacteria to carry out arsenic-bearing refractory gold ore microbe-preoxidation gold.
Background technology
The gold ore resource in China's Dian Qian Gui " Golden Triangle " area, mainly based on arsenic-bearing refractory gold ore, is often contaminated in the sulphide ore such as mispickel, pyrite with the form of micro-or secondary micro-even Lattice Gold.Such ore deposit belongs to dual pole difficult mining seam, conventional cyanidation extraction of gold process is adopted to process, the leaching rate of gold is very low, it is primarily due to be wrapped up by arseno-bearing sulfide with atomic fine particle form at this kind of Gold in Ores, in cyanidation-leaching process, gold is difficult to combine with leaching medicament, and the sulfide dissolubility of the arsenic formed in solution is higher, the cyanide in solution and dissolved oxygen can be consumed in a large number during cyaniding, and can " robbing gold " phenomenon of complex of ADSORPTION OF GOLD containing carbon matrix when cyanide gold-leaching.
Adopting such mineral of microbe-preoxidation gold PROCESS FOR TREATMENT is a kind of effective process.China's Refractory Au-ores microbiological oxidation Study on pretreatment is from Institute of Microorganism, Academia Sinica's early start.For over ten years, China's Refractory Au-ores PREPROCESSING OF A REFRACTORY GOLD research and development quickly, achieves some breakthroughs.Within 2000, build up first cyanidation gold-extracted factory of PREPROCESSING OF A REFRACTORY GOLD (50t/d) of China in Yantai, indicated that the antibacterial pretreating process of China's Refractory Au-ores turns to industrialized production from the scientific research stage.Hereafter sky, Liaoning profit, Benxi, Liaoning, Xinjiang Axi Gold-Workings also establish biological pre-oxidation factory, and treatment scale reaches 100t concentrate/d.Adopt the Biohydrometallurgy technology of domestic research and development but without relevant industrial applications report at present.
Summary of the invention
For solving above-mentioned technical problem, the present invention provides a kind of method utilizing high arsenic ion toleration leaching microbacteria to carry out arsenic-bearing refractory gold ore microbe-preoxidation gold, the efficient leaching microbacteria of resistance to arsenic can be obtained by the method, utilize this leaching microbacteria to carry out arsenic-bearing refractory gold ore microbe-preoxidation gold PROCESS FOR TREATMENT, the effect of separating by extraction >=60% in Gold Concentrate under Normal Pressure, sulfur oxidation rate >=40%, cyanide leaching rate of gold >=80% can be reached.
For achieving the above object, the present invention is by the following technical solutions:
A kind of method utilizing high arsenic ion toleration leaching microbacteria to carry out arsenic-bearing refractory gold ore microbe-preoxidation gold, comprises the steps:
(1) being inoculated in 3K culture medium by original for arsenic-bearing refractory gold ore leaching microbacteria and cultivate, regulating medium pH value is 1.7~1.9, and cultivation temperature is 28~32 DEG C, and through 2-4 time with culture medium switching, incubation time reaches 800~900 hours, and microorganism reaches 106The cell/ml order of magnitude;
(2) being transferred in sulfuricum culture-medium by the culture fluid obtained in step (1) and cultivate, regulating medium pH value is 3.8~4.2;Cultivation temperature is 28~32 DEG C, transfers with culture medium through 2-4 time, improves its oxidability to sulfur, and incubation time reaches 660~700 hours, and microorganism reaches 106The cell/ml order of magnitude;Consisting of of this sulfuricum culture-medium: NH4Cl, 0.10 weight portion;KH2PO4, 3 weight portions;MgCl2·6H2O, 0.10 weight portion;CaCl2·2H2O, 0.14 weight portion;Sulfur powder, 10 weight portions;Distilled water, 1000 weight portions;
(3) being transferred in 3K culture medium by the cultivation bacterium solution obtained in step (2), regulating medium pH value is 1.7~1.9;Add the arsenic sulfide immobilization microcapsule that can slowly dissolve, discharge free arsenic ion in batches to cultivate, the addition of this arsenic sulfide immobilization microcapsule is calculated as the 0.1~0.2% of culture gross weight with arsenic sulfide weight, it is that in 1.7~1.9 environment, arsenic sulfide immobilization microcapsule slowly dissolves at pH value, discharge free arsenic ion, controlling free arsenic ion concentration in culture fluid by this microcapsule is 0.2~1.0g/L, improve its tolerance to arsenic, incubation time reaches 700~800 hours, cultivation temperature is 28~32 DEG C, and microorganism maintains 106The cell/ml order of magnitude;
(4) the cultivation bacterium solution obtained in step (3) is transferred in screening culture medium cultivates, regulating medium pH value is 3.8~4.2, incubation time 80~120 hours, cultivation temperature is 28~32 DEG C, this screening culture medium is with step (2) described sulfuricum culture-medium for substrate, adds arsenic oxide 1.6g/L;
(5) the cultivation bacterium solution obtained in step (4) adds arsenic-bearing refractory gold ore flotation concentrate breeze, breeze amount is culture gross weight 5%~10% added, regulating medium pH value is 1.7~1.9, cultivation temperature is 28~32 DEG C, incubation time 200~300 hours, improves this leaching microbacteria adaptability to sample ore;
(6) check separating by extraction and the sulfur oxidation rate of leaching microbacteria in the cultivation bacterium solution that step (5) obtains, if not up to preset standard, then repeat (3)~(5) step 4-6 time, it is thus achieved that bacteria concentration is 106~108The adaptability domestication leaching microbacteria population of cell/ml;
(7) adding the leaching microbacteria of resistance to arsenic obtained through step (6) in gold ore flotation concentrate pulp, carry out biological pre-oxidation, regulating pre-oxidation system pH is 1.7~1.9, and Pre oxidation is 28~32 DEG C, and preoxidation time is 12~18 days;
(8) the pre-oxidation system that step (7) is obtained carries out solid-liquid separation operation, respectively obtain oxidation solution and oxidizing slag, oxidation solution returns step (7), recycles leaching microbacteria therein and residual acid, and oxidizing slag enters cyanide gold-leaching operation.
Method as above, it is characterised in that the consisting of of 3K culture medium in described step (1): (NH4)2SO4, 3 weight portions;MgSO4·7H2O, 0.5 weight portion;K2HPO4, 0.5 weight portion;Ca(NO3)2, 0.01 weight portion;KCl, 0.1 weight portion;FeSO4·7H2O, 14.4 weight portions;Distilled water, 950 weight portions;Wherein, this FeSO4·7H2O adopts filtration sterilization, and all the other components adopt high pressure steam sterilization;The pH value of this 3K culture medium is 1.7~1.9.
Method as above, it is preferable that the capsule material of the arsenic sulfide immobilization microcapsule of described step (3) is sodium alginate chitosan and carboxymethyl cellulose.
Method as above, it is preferable that the preset standard of described step (6) separating by extraction and sulfur oxidation rate is separating by extraction >=60%, sulfur oxidation rate >=45%.
Method as above, it is preferable that in described step (7), initial pulp density is (5~15) wt%;The volume ratio of the leaching microbacteria of the resistance to arsenic bacterium solution that step (6) obtains and initial ore pulp is (10~20): 100.
Method as above, it is preferable that arsenic content >=1.5wt% in described arsenic-bearing refractory gold ore.
The invention have the benefit that in the microcapsule applied in the inventive method, arsenic sulfide can be dissolved in culture fluid by slow releasing arsenic ion, making arsenic ion concentration range in solution is 0.2g/L~1.0g/L.Thus affecting the normal metabolic processes of leaching microbacteria, reach the purpose of leaching microbacteria screening domestication.Adaptability domestication leaching microbacteria population after screening domestication, its optimum growth temp is at 28~32 DEG C, optimum growh pH value is 1.7~1.9, this microorganism can be used for arsenic-bearing refractory gold ore concentrate or microbe-preoxidation gold technique, makes mineral biological pre-oxidation separating by extraction >=60%, sulfur oxidation rate >=40%.This leaching microbacteria screening domestication efficiency is high, stronger to leaching gold mine pre-oxidation treatment ability containing arsenic difficulty.
Accompanying drawing explanation
Fig. 1 is the leaching microbacteria of resistance to arsenic domestication flow chart.
Fig. 2 is biological pre-oxidation flow chart.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, following illustrated embodiment is for ease of being more fully understood that the present invention, but it is not used to limit the scope of the present invention, the present invention can be made various amendment or change by those skilled in the art, and these equivalent form of values fall within the application claims limited range equally.Experimental technique in following embodiment, if no special instructions, is conventional method.Experiment material used in following embodiment, if no special instructions, is and is commercially available from routine biochemistry reagent shop.
Embodiment 1
In this example, sample ore picks up from the concentrate that Guizhou gold mine efficient flotation separation obtains, and in sample ore, gold grade is 18.75g/t, and arsenic content is 1.83%, and sulfur content is 33.75%.Original leaching microbacteria picks up from this ore deposit pit water, and this pit water pH value is 4.5, and in water, microbial population is generally with Acidithiobacillus ferrooxidans, acidophilia's thiobacillus thiooxidans, the micro-spirillum of acidophilia's ferrous oxide is main, and containing vibrio partly and archeobacteria, and part heterotrophism flora.
(1) preliminary cultivation (in Fig. 1 step 1)
Each shaking flask dress 3K culture medium 100ml, inoculates gold mine effluent by the volume ratio of 3K culture medium 20%.Regulating initial pH value of medium with 10% dilute sulfuric acid is 1.8, is regulated by 10% dilute sulfuric acid and maintain solution ph 1.7~1.9 in incubation.Horizontal blank gas bath shaking table is cultivated, and rotating speed is 150 revs/min, and cultivation temperature is 30 DEG C.Culture fluid becomes pistac after cultivating 5 days, and then liquid color somewhat deepens, and within about 10 days, occurs a little muddy, and within about 14 days, color becomes faint yellow;Being transferred in new 3K culture medium by this culture, carry out successive transfer culture, condition of culture is the same, but transit time interval is shortened accordingly every time.Cultivate 10 days after first time switching, cultivate 7 days after second time switching, cultivate 5 days after third time switching.After successive transfer culture three times, accumulative incubation time has reached 864 hours, and microscopy observes the thalline finding there is the variform such as shaft-like, spherical.Through counting, microbe quantity reaches about 0.8 × 106cell/ml。
The composition of table 13K culture medium
(2) sulfuricum culture-medium cultivates (in Fig. 1 step 2)
Using sulfuricum culture-medium instead to cultivate, sulfuricum culture-medium formula and preparation method are in Table 2.
Table 2 sulfuricum culture-medium formula and preparation
Being inoculated in 100ml sulfuricum culture-medium by the cultivation bacterium solution that step (1) obtains, inoculum concentration is volume ratio 10%.The pH value regulating inoculation wild Oryza species with 10% dilute sulfuric acid and 10%NaOH solution is 4.0, is regulated by 10% dilute sulfuric acid and 10%NaOH solution and maintain solution ph 3.8~4.2 in incubation.Horizontal blank gas bath shaking table is cultivated, cultivation temperature 30 DEG C, rotating speed 150 revs/min.After cultivating 7 days, repeatedly transferring 3 times then through same culture medium, each transit time is spaced apart 7 days.After co-culturing 28 days, this leaching microbacteria quantity reaches about 1.0 × 108cell/ml.The sulfur oxidation rate of this leaching microbacteria is 69%.
(3) (in Fig. 1 step 3) is cultivated in resistance to arsenic performance screening domestication
The culture fluid that step (2) is obtained is transferred again, proceeds to 3K culture medium, and regulating initial pH value of medium with 10% dilute sulfuric acid is 1.8, is regulated by 10% dilute sulfuric acid and maintain solution ph 1.7~1.9 in incubation.Horizontal blank gas bath shaking table is cultivated, and rotating speed is 150 revs/min, and cultivation temperature is 30 DEG C.Adding the arsenic sulfide immobilization microcapsule prepared in advance in culture fluid, addition is 0.2g/L.The capsule material of this arsenic sulfide immobilization microcapsule is sodium alginate chitosan and carboxymethyl cellulose.This microcapsule can be slowly dissolve in 1.7~1.9 environment at pH value, discharges free arsenic ion, enters culture fluid system, and controls to dissociate arsenic ion concentration in culture fluid less than 0.2~1.0g/L.Horizontal blank gas bath shaking table is cultivated, and rotating speed is 150 revs/min, and cultivation temperature is 30 DEG C.Cultivating domestication every 5 days, add this microcapsule of 0.2g/L, cultivate with conditional operation, till microcapsule cumulative amount reaches 1.0g/L, after co-culturing 30 days, this leaching microbacteria quantity remains at 0.5 × 108cell/ml。
(4) screening and culturing (in Fig. 1 step 4)
The culture fluid that step (3) obtains is proceeded to screening culture medium carries out subculture switching, the pH value regulating inoculation wild Oryza species with 10% dilute sulfuric acid and 10%NaOH solution is 4.0, is regulated by 10% dilute sulfuric acid and 10%NaOH solution and maintain solution ph 3.8~4.2 in incubation.Horizontal blank gas bath shaking table is cultivated, and rotating speed is 150 revs/min, and cultivation temperature is 30 DEG C.Screening culture medium, with sulfuricum culture-medium for substrate, adds arsenic oxide 1.6g/L, incubation time 100 hours.
(5) flotation concentrate breeze cultivates (in Fig. 1 step 5)
The cultivation bacterium solution obtained to step (4) adds gold ore flotation concentrate breeze, breeze amount is culture gross weight the 5% of addition, and horizontal blank gas bath shaking table is cultivated, and rotating speed is 150 revs/min, and cultivation temperature is 30 DEG C.Monitoring culture fluid acidity and oxidation-reduction potential value at any time, is regulated by 10% dilute sulfuric acid in incubation and maintains solution ph 1.7~1.9.Incubation time 10 days.
(6) domestication (in Fig. 1 step 6)
Check separating by extraction and the sulfur oxidation rate of leaching microbacteria in the cultivation bacterium solution that step (5) obtains, if not up to preset standard, then repeat (3)~(5) step.Repeating altogether in this example 5 times, obtaining for this arsenic-bearing refractory gold ore mineral height arsenic ion toleration leaching microbacteria population micro organism quantity is 0.9 × 108Cell/ml, 15 days biological pre-oxidation separating by extraction are 62%, sulfur oxidation rate is 45%.
(7) biological pre-oxidation (in Fig. 2 step 1)
This gold ore flotation concentrate breeze adds the leaching microbacteria of the resistance to arsenic bacterium solution obtained through step (6), powder particle size is :-400 orders 90% (mass ratio), pre-oxidation system is supplemented 3K culture medium 20% (mass ratio), initial pulp density is 10wt%, and the volume ratio of the leaching microbacteria of resistance to arsenic bacterium solution and initial ore pulp is 15: 100.Pre oxidation controls within the scope of (30 ± 2) DEG C, and regulating pre-oxidation system original ph with 10% dilute sulfuric acid is 1.8, is regulated by 10% dilute sulfuric acid and maintain solution ph 1.7~1.9 in incubation.Preoxidation time 15 days.
(8) solid-liquid separation (in Fig. 2 step 2)
The pre-oxidation system that step (7) is obtained carries out solid-liquid separation operation, respectively obtains oxidation solution and oxidizing slag, and oxidation solution returns step (7), recycles leaching microbacteria therein and residual acid, and oxidizing slag enters cyanide gold-leaching operation.
(9) cyanide gold-leaching (in Fig. 2 step 3)
The oxidizing slag that step (8) is obtained carries out cyanide gold-leaching process, and cyaniding liquid-solid ratio is 2: 1, Calcium Oxide Dosage: 30kg/t calcium oxide processes 3 hours time, Cyanogran. consumption 10kg/t, 24 hours Cyanide Leaching time.After Cyanide Leaching, the leaching rate of gold reaches 85.5%.