Method for recycling vanadium through biological dump leaching by using fluorine-resistant acidophilic ore leaching bacteria

Abstract

The invention discloses a method for recycling vanadium through biological dump leaching by using fluorine-resistant acidophilic ore leaching bacteria. According to the technical scheme, an acidophilic ore leaching bacterium strain named as Acidithiobacillus ferrooxidans is adopted, a fluorine-resistant acidophilic ore leaching bacterium solution is obtained through domestication, and the F <->-resistant content of the fluorine-resistant acidophilic ore leaching bacterium solution reaches 0.36-2.7 g / L. The fluorine-resistant acidophilic mineral leaching bacteria liquid preserved at the ultralow temperature is subjected to expanding culture, and the fluorine-resistant acidophilic mineral leaching bacteria liquid subjected to expanding culture is obtained. And roasting the vanadium shale, building an ore heap, and intermittently spraying sulfuric acid to the ore heap. And then a fluorine-containing leaching aid is added into the fluorine-resistant acidophilic ore leaching bacterium liquid subjected to expanding culture to obtain a fluorine-containing acidophilic ore leaching bacterium liquid, the fluorine-containing acidophilic ore leaching bacterium liquid is intermittently dripped and sprayed to the ore heap subjected to sulfuric acid spraying for heap leaching, a leaching solution is obtained, and vanadium recovery is further achieved. The acidophilic ore leaching bacteria are subjected to fluorine-resistant domestication and enlarged culture, and are used for heap biological leaching of the low-grade vanadium shale, so that the leaching rate is high, and the treatment capacity is large.

Description

Technical Field

[0001] The present invention belongs to the technical fields of chemical engineering and bio-metallurgy. Specifically, it relates to a method for using fluoride-resistant acidophilic ore-leaching bacteria for bio-heap leaching to recover vanadium. Background Art

[0002] Vanadium is an important rare metal and has received extensive attention due to its wide industrial applications. Especially its applications in non-ferrous alloy production, catalysts, and batteries. As an important vanadium ore resource, vanadium shale has rich reserves, but the vanadium grade is generally low and the ore phase composition is complex. Moreover, most of the vanadium in it is hosted in the crystal lattice of (aluminum) silicate minerals, with a relatively stable structure and being difficult to leach. To meet the growing demand for vanadium resources, extracting vanadium from vanadium shale has become an urgent task, and various processes for extracting vanadium from vanadium shale have been reported. Currently, for the vanadium extraction process from vanadium shale, traditional chemical technologies include additive roasting - water leaching or low-acidity leaching, direct acid leaching method, and low-salt roasting - cyclic oxidation method. However, although these vanadium recovery methods are efficient and rapid, they still require a large amount of additives or acids and will cause serious environmental hazards.

[0003] Bioleaching technology uses microorganisms to recover precious metals and base metals from low-grade minerals and has developed into a successful and expanding field of biotechnology. It has been proven to be an effective, low-cost, and environmentally friendly method. Currently, this technology has been successfully applied to the industrial production of metals such as copper, gold, and uranium. As a kind of ore-leaching bacterium, Acidithiobacillus ferrooxidans can accelerate the electron transfer in the reaction process, produce high-valent oxidants, and a lower pH environment after participation, making the oxidation and decomposition process of minerals more rapid, so it is widely used in various metallurgical fields. In bioleaching of vanadium, vanadium hosted in minerals is released under the direct erosion of bacteria and the indirect action of bacterial growth metabolites, but the leaching rate of vanadium is generally low and difficult to meet industrial requirements.

[0004] Literature I (Fang Fang, Zhong Hong, Jiang Fangming, etc. Arsenic resistance domestication and ore-leaching ability of Acidithiobacillus ferrooxidans. Journal of Central South University, 2013) In order to improve the oxidation activity and arsenic resistance ability of Acidithiobacillus ferrooxidans during the leaching of arsenic gold concentrate, the continuous transfer domestication method was used to domesticate the isolated and purified A.f strain NSJ209 for arsenic resistance, and the tolerance of the original bacterium and the domesticated bacterium to As(Ⅲ) and As(Ⅴ) was investigated. This technology only aims to eliminate the influence of arsenic on bacteria, domesticate the bacteria for arsenic resistance, and the leaching object is arsenic gold concentrate.

[0005] Literature II (Wang Yongdong, Ding Dexin, Li Guangyue, etc. Continuous transfer domestication and co-domestication of Acidithiobacillus ferrooxidans resistant to uranium and fluoride ions. The Chinese Journal of Process Engineering, 2011) In order to improve the domestication efficiency of Acidithiobacillus ferrooxidans and obtain an A.f strain that can tolerate high concentrations of uranium and fluoride ions, the isolated and purified A.f strain SKS10 The uranium- and fluorine-resistant domestication methods were studied, and continuous transfer domestication and combined domestication methods were proposed. This technology only domesticates Acidithiobacillus ferrooxidans for uranium and fluorine resistance, without conducting leaching experiments. Its fluorine resistance ability is low, the influence of fluorine on Acidithiobacillus ferrooxidans is still large, the mineral treatment volume is small, and the leaching rate is low.

[0006] Literature III (Li Jiang, Rao Jun, Liu Yajie, etc. Industrial test on microbial heap leaching of high-fluorine uranium ore. Nonferrous Metals: Smelting Section, 2011) conducted an industrial test on microbial heap leaching of high-fluorine uranium ore based on previous tests. The ore piled up was 4315 t, the ore particle size was ~6 mm, the grade was 0.186%, the leaching rate calculated by slag was 92.63%, and the acid consumption was 3.14%. The used 05B bacterial community grew well in the tail liquid with a fluorine content of 2 - 3.98 g / L, and the leaching cycle was 112 d. The leaching object of this technology is high-fluorine uranium ore, which passive responds to the existence of fluorine, only reducing toxicity without utilizing the positive effect of fluorine.

[0007] The patented technology of "A method for biological heap leaching of low-sulfur ore" (CN 202211252334.9) mixes low-sulfur ore with reduced sulfur, inoculates acidophilic sulfur-oxidizing microorganisms and acidophilic iron-oxidizing microorganisms, and realizes the leaching of target metals through heap leaching. This invention does not domesticate the bacterial strain, heavy metal ions in the mineral are toxic to the bacterial strain, and the leaching rate is low; the leaching object is low-sulfur ore, and the leaching cycle is long.

[0008] The patented technology of "A method for bacterial leaching of high-fluorine uranium ore" (CN 117867275A) crushes high-fluorine uranium ore and loads it into columns or builds a heap to obtain an ore heap, sprays the ore heap with an acid-containing spraying liquid, conducts uranium adsorption treatment on the collected leaching liquid, and after defluorination treatment of the adsorbed tail liquid, recycles it to the spraying process; then implants bacteria into the ore heap; subsequently, sprays it with a spraying solution containing boric acid and acid for bacterial leaching, conducts uranium adsorption treatment on the collected bacterial leaching liquid, and recycles the adsorbed tail liquid to the bacterial leaching process. This technology is passive terminal treatment, does not improve the fluorine resistance of the bacterial strain, relies on defluorination pretreatment to eliminate inhibition, the toxic effect of fluorine on bacteria is large, and it affects the leaching rate.

[0009] The patented technology of "A fluorine-resistant ore-leaching bacterium and its high-efficiency leaching process applied to high-fluorine uranium ore" (CN 104745498A) adds aluminum sulfate to the acidifying solution. Since F - will form a complex ion with Fe 3+ in the solution, the content of free F - in the leaching solution is greatly reduced, reducing the toxic effect of F - on bacteria. This invention adds additional agents to avoid the toxic effect of fluorine, increasing agent consumption and high production costs. The leaching object is high-fluorine uranium ore.

[0010] In summary, in the prior art: only Acidithiobacillus ferrooxidans is domesticated to be uranium-resistant and fluorine-resistant, and the fluorine-resistant domestication only aims to avoid the influence of F - without utilizing the positive effect of F - to conduct leaching experiments. The fluorine resistance ability is low, the influence of fluorine on Acidithiobacillus ferrooxidans is still large, the leaching rate is low, and the treatment capacity is small; while the existing heap leaching method is only used for low-sulfur ores and high-fluorine uranium ores and is not used for vanadium shales. Summary of the Invention

[0011] The present invention aims to overcome the defects of the prior art and provides a fluorine-resistant acidophilic ore-leaching bacterial liquid for bioheap leaching of low-grade vanadium shales, with a high leaching rate and a large treatment capacity.

[0012] To achieve the above object, the specific steps of the technical solution adopted by the present invention are as follows:

[0013] Step 1: An acidophilic ore-leaching bacterium, named Acidithiobacillus ferrooxidans.

[0014] Primary domestication: Initially inoculate the Acidithiobacillus ferrooxidans strain into a liquid medium containing F - at a concentration of 0.045 - 0.36 g / L. When the lethality rate reaches 90 - 98%, transfer it to a solid medium and culture for 5 - 20 days, then screen to obtain the initially domesticated Acidithiobacillus ferrooxidans colonies; then inoculate the initially domesticated Acidithiobacillus ferrooxidans colonies into the liquid medium and culture until the logarithmic phase to obtain the initially domesticated fluorine-resistant acidophilic ore-leaching bacterial liquid.

[0015] Gradient domestication: Each time of domestication is to inoculate the fluorine-resistant acidophilic ore-leaching bacterial liquid obtained from the previous domestication into the liquid medium containing F - at the concentration for this time. The liquid medium containing F - at the concentration for this time is increased by a gradient of 0.045 - 0.13 g / L based on the liquid medium containing F - at the concentration for the previous time; repeat domestication 8 - 19 times to obtain a fluorine-resistant acidophilic ore-leaching bacterial liquid with an F - content of 0.36 - 2.7 g / L, and conduct ultra-low temperature preservation.

[0016] The specific process of the gradient domestication is as follows:

[0017] Second domestication: Inoculate the initially domesticated fluorine-resistant acidophilic ore-leaching bacterial liquid into a liquid medium containing F -In a liquid medium with a concentration of (0.045 - 0.36) g / L + (0.045 - 0.13) g / L, when the lethality rate reaches 90 - 98%, transfer it to the solid medium, culture for 5 - 20 days, screen, and obtain the Thiobacillus ferrooxidans colonies after the second domestication. Then inoculate the Thiobacillus ferrooxidans colonies after the second domestication into the liquid medium and culture until the logarithmic phase to obtain the liquid of the fluorine-tolerant acidophilic ore-leaching bacteria after the second domestication.

[0018] The third domestication: Inoculate the liquid of the fluorine-tolerant acidophilic ore-leaching bacteria after the second domestication into a liquid medium containing F - In a liquid medium with a concentration of (0.045 - 0.36) g / L + 2×(0.045 - 0.13) g / L, when the lethality rate reaches 90 - 98%, transfer it to the solid medium, culture for 5 - 20 days, screen, and obtain the Thiobacillus ferrooxidans colonies after the third domestication. Then inoculate the Thiobacillus ferrooxidans colonies after the third domestication into the liquid medium and culture until the logarithmic phase to obtain the liquid of the fluorine-tolerant acidophilic ore-leaching bacteria after the third domestication.

[0019] And so on.

[0020] The (n - 1)th domestication: Inoculate the liquid of the fluorine-tolerant acidophilic ore-leaching bacteria after the (n - 2)th domestication into the liquid medium containing F - In the liquid medium with a concentration of (0.045 - 0.36) g / L + (0.045 - 0.13)(n - 2) g / L, when the lethality rate reaches 90 - 98%, transfer it to the solid medium, culture for 5 - 20 days, screen, and obtain the Thiobacillus ferrooxidans colonies after the (n - 1)th domestication. Then inoculate the Thiobacillus ferrooxidans colonies after the (n - 1)th domestication into the liquid medium and culture until the logarithmic phase to obtain the liquid of the fluorine-tolerant acidophilic ore-leaching bacteria after the (n - 1)th domestication.

[0021] The nth domestication: Inoculate the liquid of the fluorine-tolerant acidophilic ore-leaching bacteria after the (n - 1)th domestication into the liquid medium containing F - In the liquid medium with a concentration of (0.045 - 0.36) g / L + (0.045 - 0.13)(n - 1) g / L, when the lethality rate reaches 90 - 98%, transfer it to the solid medium, culture for 5 - 20 days, screen, and obtain the Thiobacillus ferrooxidans colonies after the nth domestication. Then inoculate the Thiobacillus ferrooxidans colonies after the nth domestication into the liquid medium and culture until the logarithmic phase to obtain the liquid of the fluorine-tolerant acidophilic ore-leaching bacteria with a fluorine content of 0.36 - 2.7 g / L; Ultra-low temperature preserve the liquid of the fluorine-tolerant acidophilic ore-leaching bacteria. -

[0022] The n represents the number of domestication times, and n is a natural number from 8 to 19.

[0023] Step 2. At 15 - 40 °C and an aeration rate of 0.02 - 0.04 m3 Under the condition of / (L·h), the bacterial liquid of the fluorine-resistant acidophilic leaching bacteria stored at ultra-low temperature is expanded and cultured to a scale of 800 - 1200 L / d, and the bacterial liquid concentration is 10 9 ~10 12 cells / L to obtain the expanded bacterial liquid of the fluorine-resistant acidophilic leaching bacteria.

[0024] Step 3: Roast the vanadium shale with a particle size ≤ 6 mm at 600 - 800 °C for 30 - 60 min to build a ore heap with a height of 2 - 6 m, and the content of V2O5 in the vanadium shale is 0.5 - 1.7 wt%; then intermittently spray the ore heap with sulfuric acid with a concentration of 5 - 60 g / L until the pH of the effluent is stable at 0 - 0.1.

[0025] Step 4: According to the solid-liquid ratio of 0.36 - 2.7 g / L, add a fluorine-containing leaching aid to the expanded bacterial liquid of the fluorine-resistant acidophilic leaching bacteria to obtain a fluorine-containing acidophilic leaching bacteria liquid; then intermittently drip the fluorine-containing acidophilic leaching bacteria liquid onto the ore heap after sulfuric acid spraying for heap leaching to obtain a leaching solution.

[0026] The leaching solution is purified and enriched with vanadium, the lean organic phase is regenerated, vanadium is precipitated, and vanadium pentoxide is prepared to recover vanadium.

[0027] The preparation method of the liquid medium is: add ferrous sulfate heptahydrate to the 9K basic medium with a pH of 1.5 - 2.5 according to the solid-liquid ratio of 30 - 50 g / L to obtain the liquid medium.

[0028] The preparation method of the solid medium is to add agar powder to the 9K basic medium with a pH of 1.8 - 2.2 according to the solid-liquid ratio of 10 - 30 g / L, and sterilize it at 90 - 121 °C for 10 - 20 min to obtain the solid medium.

[0029] The 9K basic medium: ammonium sulfate is 2 - 4 g / L, dipotassium hydrogen phosphate is 0.4 - 0.6 g / L, potassium chloride is 0.05 - 0.15 g / L, magnesium sulfate heptahydrate is 0.4 - 0.6 g / L, and calcium nitrate is 0.005 - 0.015 g / L.

[0030] The inoculation amount of the Thiobacillus ferrooxidans colony inoculation is a single colony in the solid medium, and the diameter of the Thiobacillus ferrooxidans colony is 1 - 2 mm;

[0031] The inoculation amount of the inoculation of the bacterial liquid of the fluorine-resistant acidophilic leaching bacteria is 5 - 15 vol% of the liquid medium with the current F- concentration.

[0032] The ultra-low temperature preservation is carried out using a protective agent of 15% glycerol - liquid medium; the ultra-low temperature preservation temperature is -196 - -80 °C.

[0033] The spraying volume of the intermittent spraying is 10-30 L / (m 2 ·h), and the intermittent time of the intermittent spraying is 12 hours per day.

[0034] The fluorine-containing leaching aid is one of sodium fluoride, ammonium fluoride, and potassium fluoride dihydrate.

[0035] The vanadium concentration of the leaching solution is 0.7-1.2 g / L.

[0036] The spraying volume of the spray washing of ore is 10-30 L / (m 2 ·h). When the vanadium concentration of the washing water for spray washing of ore < 0.03 g / L or pH > 2.5, the spraying ends; the pH of the recycled washing water for spray washing of ore is 1.5-2.5.

[0037] Due to the adoption of the above technical solution, the present invention has the following positive effects compared with the prior art:

[0038] 1. The present invention uses an acidophilic ore-leaching bacterial strain named Acidithiobacillus ferrooxidans, and through domestication, a fluorine-resistant acidophilic ore-leaching bacterial solution is obtained, and the F - content reaches 0.36-2.7 g / L. Using the fluorine-resistant acidophilic ore-leaching bacterial solution to leach the vanadium shale system, under the dual action of the fluorine-containing leaching aid and the fluorine-resistant acidophilic ore-leaching bacteria, the vanadium shale ore heap after roasting and sulfuric acid spraying is subjected to bioheap leaching of vanadium shale, increasing the ore treatment volume, shortening the leaching cycle, reducing the economic cost, increasing the leaching rate of vanadium in vanadium shale, and significantly enhancing the microbial leaching effect.

[0039] 2. The present invention utilizes the function of fluoride in chemical leaching to destroy the mica lattice, and there is no need to perform defluorination treatment on it. A method of combining with chemical leaching to strengthen leaching is proposed. The fluorine-resistant domestication of acidophilic ore-leaching bacteria can effectively reduce or eliminate the influence of fluorine on the growth of acidophilic ore-leaching bacteria and shorten the leaching cycle.

[0040] 3. The present invention does not avoid the influence of F - . Utilizing the characteristics that F - participates in the coordination binding of the central atoms of the mica tetrahedron and octahedron structures and participates in the reaction synergistically with H + to achieve the destruction of the mica structure, through cultivating a fluorine-resistant acidophilic ore-leaching bacterial solution and performing bioheap leaching on vanadium shale, the production cost is low and the resource recovery rate is high.

[0041] Therefore, the acidophilic ore-leaching bacterial strain adopted by the present invention is subjected to fluorine-resistant domestication and enlarged cultivation, and is used for bioheap leaching of low-grade vanadium shale with a high leaching rate and a large treatment volume. Specific Embodiments

[0042] The present invention will be further described below in conjunction with specific embodiments, which is not a limitation on its protection scope.

[0043] A method for using fluorine-tolerant acidophilic leaching bacteria to recover vanadium by bioheap leaching. The method described in this specific embodiment is as follows:

[0044] Step 1: An acidophilic leaching bacterium, named Acidithiobacillus ferrooxidans.

[0045] Primary domestication: Inoculate the Acidithiobacillus ferrooxidans strain into a liquid medium with a F concentration of 0.045 - 0.36 g / L for the first time. When the lethality rate reaches 90 - 98%, transfer it to a solid medium and culture for 5 - 20 days, then screen to obtain the initially domesticated Acidithiobacillus ferrooxidans colonies. Then inoculate the initially domesticated Acidithiobacillus ferrooxidans colonies into the liquid medium and culture until the logarithmic phase to obtain the initially domesticated fluorine-tolerant acidophilic leaching bacteria liquid. - Gradient domestication: Each time of domestication is to inoculate the fluorine-tolerant acidophilic leaching bacteria liquid obtained from the previous domestication into a liquid medium with the F concentration for this time. The liquid medium with the F concentration for this time is increased by a gradient of 0.045 - 0.13 g / L based on the liquid medium with the F concentration of the previous time. Repeat domestication 8 - 19 times to obtain a fluorine-tolerant acidophilic leaching bacteria liquid with a F content of 0.36 - 2.7 g / L, and perform ultra-low temperature preservation.

[0046] The specific process of the gradient domestication is as follows: - The F concentration - The liquid medium with the F concentration of the previous time - The liquid medium with the F concentration of this time - The liquid medium with the F concentration of this time is increased by a gradient of 0.045 - 0.13 g / L based on the liquid medium with the F concentration of the previous time. Repeat domestication 8 - 19 times to obtain a fluorine-tolerant acidophilic leaching bacteria liquid with a F content of 0.36 - 2.7 g / L, and perform ultra-low temperature preservation.

[0047] The specific process of the gradient domestication is as follows:

[0048] Second domestication: Inoculate the initially domesticated fluorine-tolerant acidophilic leaching bacteria liquid into a liquid medium with a F concentration of (0.045 - 0.36) g / L + (0.045 - 0.13) g / L. When the lethality rate reaches 90 - 98%, transfer it to the solid medium and culture for 5 - 20 days, then screen to obtain the second-domesticated Acidithiobacillus ferrooxidans colonies. Then inoculate the second-domesticated Acidithiobacillus ferrooxidans colonies into the liquid medium and culture until the logarithmic phase to obtain the second-domesticated fluorine-tolerant acidophilic leaching bacteria liquid. - When the lethality rate reaches 90 - 98%, transfer it to the solid medium and culture for 5 - 20 days, then screen to obtain the second-domesticated Acidithiobacillus ferrooxidans colonies. Then inoculate the second-domesticated Acidithiobacillus ferrooxidans colonies into the liquid medium and culture until the logarithmic phase to obtain the second-domesticated fluorine-tolerant acidophilic leaching bacteria liquid.

[0049] Third domestication: Inoculate the second-domesticated fluorine-tolerant acidophilic leaching bacteria liquid into a liquid medium with a F concentration of -In a liquid medium with a concentration of (0.045 - 0.36) g / L + 2×(0.045 - 0.13) g / L, when the lethality rate reaches 90 - 98%, transfer it to the solid medium and culture for 5 - 20 days, then screen to obtain the Thiobacillus ferrooxidans colonies after the third domestication. Then inoculate the Thiobacillus ferrooxidans colonies after the third domestication into the liquid medium and culture until the logarithmic phase to obtain the acidophilic fluorine-tolerant ore-leaching bacteria solution after the third domestication.

[0050] And so on.

[0051] The (n - 1)th domestication: Inoculate the acidophilic fluorine-tolerant ore-leaching bacteria solution after the (n - 2)th domestication into the liquid medium containing F - with a concentration of (0.045 - 0.36) g / L + (0.045 - 0.13)(n - 2) g / L. When the lethality rate reaches 90 - 98%, transfer it to the solid medium and culture for 5 - 20 days, then screen to obtain the Thiobacillus ferrooxidans colonies after the (n - 1)th domestication. Then inoculate the Thiobacillus ferrooxidans colonies after the (n - 1)th domestication into the liquid medium and culture until the logarithmic phase to obtain the acidophilic fluorine-tolerant ore-leaching bacteria solution after the (n - 1)th domestication.

[0052] The nth domestication: Inoculate the acidophilic fluorine-tolerant ore-leaching bacteria solution after the (n - 1)th domestication into the liquid medium containing F - with a concentration of (0.045 - 0.36) g / L + (0.045 - 0.13)(n - 1) g / L. When the lethality rate reaches 90 - 98%, transfer it to the solid medium and culture for 5 - 20 days, then screen to obtain the Thiobacillus ferrooxidans colonies after the nth domestication. Then inoculate the Thiobacillus ferrooxidans colonies after the nth domestication into the liquid medium and culture until the logarithmic phase to obtain the acidophilic fluorine-tolerant ore-leaching bacteria solution with a fluorine content of 0.36 - 2.7 g / L; Ultra-low temperature preservation of the acidophilic fluorine-tolerant ore-leaching bacteria solution. - The n represents the number of domestication times, and n is a natural number from 8 to 19.

[0053] Step 2. Under the conditions of 15 - 40 °C and an aeration rate of 0.02 - 0.04 m

[0054] / (L·h), expand and culture the ultra-low temperature-preserved acidophilic fluorine-tolerant ore-leaching bacteria solution to a scale of 800 - 1200 L / d, and the bacteria solution concentration is 10 3 - 10 9 - 10 12 cells / L to obtain the expanded acidophilic fluorine-tolerant ore-leaching bacteria solution.

[0055] Step 3: Roast the vanadium shale with a particle size ≤ 6 mm at 600 - 800 °C for 30 - 60 min to build a ore heap with a height of 2 - 6 m, where the V2O5 content of the vanadium shale is 0.5 - 1.7 wt%; then intermittently spray the ore heap with sulfuric acid at a concentration of 5 - 60 g / L until the pH of the effluent stabilizes at 0 - 0.1.

[0056] Step 4: According to the solid-liquid ratio of 0.36 - 2.7 g / L, add a fluorine-containing leaching aid to the expanded culture of the fluorine-tolerant acidophilic leaching bacteria to obtain a fluorine-tolerant acidophilic leaching bacteria solution; then intermittently drip the fluorine-tolerant acidophilic leaching bacteria solution onto the ore heap after sulfuric acid spraying for heap leaching to obtain a leaching solution.

[0057] The preparation method of the liquid medium is: according to the solid-liquid ratio of 30 - 50 g / L, add ferrous sulfate heptahydrate to the 9K basal medium with a pH of 1.5 - 2.5 to obtain the liquid medium.

[0058] The preparation method of the solid medium is: according to the solid-liquid ratio of 10 - 30 g / L, add agar powder to the 9K basal medium with a pH of 1.8 - 2.2, and sterilize at 90 - 121 °C for 10 - 20 min to obtain the solid medium.

[0059] The 9K basal medium: ammonium sulfate is 2 - 4 g / L, dipotassium hydrogen phosphate is 0.4 - 0.6 g / L, potassium chloride is 0.05 - 0.15 g / L, magnesium sulfate heptahydrate is 0.4 - 0.6 g / L, and calcium nitrate is 0.005 - 0.015 g / L.

[0060] The inoculation amount of the Thiobacillus ferrooxidans colony inoculation is a single colony in the solid medium, and the diameter of the Thiobacillus ferrooxidans colony is 1 - 2 mm.

[0061] The inoculation amount of the fluorine-tolerant acidophilic leaching bacteria solution inoculation is 5 - 15 vol% of the liquid medium with the current F- concentration.

[0062] The ultra-low temperature preservation is carried out using a protective agent of 15% glycerol - liquid medium; the ultra-low temperature preservation temperature is -196 to -80 °C.

[0063] The spraying amount of the intermittent spraying is 10 - 30 L / (m 2 ·h), and the intermittent time of the intermittent spraying is 12 hours per day.

[0064] The fluorine-containing leaching aid is one of sodium fluoride, ammonium fluoride, and potassium fluoride dihydrate.

[0065] The vanadium concentration of the leaching solution is 0.7 - 1.2 g / L.

[0066] The spraying amount of the spray washing of the ore is 10 - 30 L / (m2 ·h) When the vanadium concentration of the ore washing water for spray ore washing < 0.03 g / L or pH > 2.5, the spray is ended; the pH of the recycled ore washing water for spray ore washing is 1.5 - 2.5.

[0067] In this specific embodiment:

[0068] The leaching solution is used to recover vanadium through processes of purifying and enriching vanadium, regenerating the lean organic phase, precipitating vanadium, and preparing vanadium pentoxide.

[0069] Details are not repeated in the examples.

[0070] Example 1

[0071] A method for using a fluorine - resistant acidophilic ore - leaching bacterium to recover vanadium by bio - heap leaching. The method in this example is as follows:

[0072] Step 1: An acidophilic ore - leaching bacterium, named Acidithiobacillus ferrooxidans.

[0073] Primary domestication: The Acidithiobacillus ferrooxidans strain is initially inoculated into a liquid medium containing F - at a concentration of 0.045 g / L. When the lethality rate reaches 90%, it is transferred to a solid medium, cultured for 5 days, screened, and the initially domesticated Acidithiobacillus ferrooxidans colonies are obtained; then the initially domesticated Acidithiobacillus ferrooxidans colonies are inoculated into the liquid medium and cultured to the logarithmic phase to obtain the initially domesticated fluorine - resistant acidophilic ore - leaching bacterium liquid.

[0074] Gradient domestication: Each time of domestication is to inoculate the fluorine - resistant acidophilic ore - leaching bacterium liquid obtained from the previous domestication into a liquid medium containing F - at the concentration of this time. The liquid medium containing F - at the concentration of this time is increased by a gradient of 0.045 g / L based on the liquid medium containing F - at the concentration of the previous time; The domestication is repeated 8 times to obtain a fluorine - resistant acidophilic ore - leaching bacterium liquid with an F - content of 0.36 g / L, and it is cryopreserved at ultra - low temperature.

[0075] The specific process of the gradient domestication is as follows:

[0076] Second domestication: The initially domesticated fluorine - resistant acidophilic ore - leaching bacterium liquid is inoculated into a liquid medium containing F - at a concentration of 0.045 g / L + 0.045 g / L. When the lethality rate reaches 90%, it is transferred to the solid medium, cultured for 5 days, screened, and the second - domesticated Acidithiobacillus ferrooxidans colonies are obtained; then the second - domesticated Acidithiobacillus ferrooxidans colonies are inoculated into the liquid medium and cultured to the logarithmic phase to obtain the second - domesticated fluorine - resistant acidophilic ore - leaching bacterium liquid.

[0077] Third domestication: Inoculate the acidophilic fluorine-resistant leaching bacteria solution after the second domestication into the liquid medium containing F - at a concentration of 0.045 g / L + 2 × 0.045 g / L. When the lethality rate reaches 90%, transfer it to the solid medium and culture for 5 days. After screening, obtain the Thiobacillus ferrooxidans colonies after the third domestication. Then inoculate the Thiobacillus ferrooxidans colonies after the third domestication into the liquid medium and culture until the logarithmic phase to obtain the acidophilic fluorine-resistant leaching bacteria solution after the third domestication.

[0078] And so on.

[0079] The 7th domestication: Inoculate the acidophilic fluorine-resistant leaching bacteria solution after the 6th domestication into the liquid medium containing F - at a concentration of 0.045 g / L + 6 × 0.045 g / L. When the lethality rate reaches 90%, transfer it to the solid medium and culture for 5 days. After screening, obtain the Thiobacillus ferrooxidans colonies after the 7th domestication. Then inoculate the Thiobacillus ferrooxidans colonies after the 7th domestication into the liquid medium and culture until the logarithmic phase to obtain the acidophilic fluorine-resistant leaching bacteria solution after the 7th domestication.

[0080] The 8th domestication: Inoculate the acidophilic fluorine-resistant leaching bacteria solution after the 7th domestication into the liquid medium containing F - at a concentration of 0.045 g / L + 7 × 0.045 g / L. When the lethality rate reaches 90%, transfer it to the solid medium and culture for 5 days. After screening, obtain the Thiobacillus ferrooxidans colonies after the 8th domestication. Then inoculate the Thiobacillus ferrooxidans colonies after the 8th domestication into the liquid medium and culture until the logarithmic phase to obtain the acidophilic fluorine-resistant leaching bacteria solution with an F - content of 0.36 g / L; Ultra-low temperature preservation of the acidophilic fluorine-resistant leaching bacteria solution.

[0081] Step 2: Under the conditions of 15 °C and an aeration rate of 0.02 m 3 / (L·h), expand and culture the ultra-low temperature-preserved acidophilic fluorine-resistant leaching bacteria solution to a scale of 1200 L / d, with a bacterial solution concentration of 10 9 cells / L to obtain the expanded acidophilic fluorine-resistant leaching bacteria solution.

[0082] Step 3: Roast the vanadium shale with a particle size ≤ 6 mm at 600 °C for 30 min to build a ore pile with a height of 5 m. The content of V2O5 in the vanadium shale is 0.5 wt%; Then intermittently spray the ore pile with sulfuric acid with a concentration of 5 g / L until the pH of the effluent stabilizes at 0.

[0083] Step 4: According to a solid-liquid ratio of 0.36 g / L, add a fluorine-containing leaching aid to the expanded fluorine-tolerant acidophilic ore-leaching bacterial solution to obtain a fluorine-containing acidophilic ore-leaching bacterial solution; then intermittently drip the fluorine-containing acidophilic ore-leaching bacterial solution onto the ore heap after sulfuric acid spraying for heap leaching to obtain a leaching solution.

[0084] The preparation method of the liquid medium is: according to a solid-liquid ratio of 30 g / L, add ferrous sulfate heptahydrate to the 9K basic medium with a pH of 1.5 to obtain the liquid medium.

[0085] The preparation method of the solid medium is: according to a solid-liquid ratio of 10 g / L, add agar powder to the 9K basic medium with a pH of 1.8, and sterilize at 90 °C for 10 min to obtain the solid medium.

[0086] The 9K basic medium: ammonium sulfate is 2 g / L, dipotassium hydrogen phosphate is 0.45 g / L, potassium chloride is 0.05 g / L, magnesium sulfate heptahydrate is 0.6 g / L, and calcium nitrate is 0.005 g / L.

[0087] The inoculation amount of the Thiobacillus ferrooxidans colony inoculation is a single colony in the solid medium, and the diameter of the Thiobacillus ferrooxidans colony is 1 mm.

[0088] The inoculation amount of the fluorine-tolerant acidophilic ore-leaching bacterial solution inoculation is 5 vol% of the liquid medium with the current F- concentration.

[0089] The ultra-low temperature preservation is carried out using a protective agent of 15% glycerol - liquid medium; the ultra-low temperature preservation temperature is -196 °C.

[0090] The spraying amount of the intermittent spraying is 30 L / (m 2 ·h), and the intermittent time of the intermittent spraying is 12 hours per day.

[0091] The fluorine-containing leaching aid is sodium fluoride.

[0092] The vanadium concentration of the leaching solution is 0.7 g / L.

[0093] The spraying amount of the spray washing of the ore is 30 L / (m 2 ·h), and when the vanadium concentration of the washing water for spray washing the ore < 0.03 g / L or pH > 2.5, the spraying ends; the pH of the recycled spray washing water is 1.5.

[0094] Example 2

[0095] A method for bioheap leaching of vanadium using a fluorine-tolerant acidophilic ore-leaching bacterium. The method in this example is:

[0096] Step 1: An acidophilic mineral leaching bacterium, named Acidithiobacillus ferrooxidans, was obtained.

[0097] Primary domestication: The Acidithiobacillus ferrooxidans strain was initially inoculated into a liquid medium containing F - at a concentration of 0.124 g / L. When the lethality rate reached 92%, it was transferred to a solid medium and cultured for 20 days. After screening, the initially domesticated Acidithiobacillus ferrooxidans colonies were obtained. Then, the initially domesticated Acidithiobacillus ferrooxidans colonies were inoculated into the above liquid medium and cultured until the logarithmic phase to obtain the initially domesticated fluorine-tolerant acidophilic mineral leaching bacterium liquid.

[0098] Gradient domestication: Each time of domestication was to inoculate the fluorine-tolerant acidophilic mineral leaching bacterium liquid obtained from the previous domestication into a liquid medium containing F - at a concentration for this time. The liquid medium containing F - at a concentration for this time was increased by a gradient of 0.066 g / L based on the liquid medium containing F - at a concentration for the previous time. The domestication was repeated 10 times to obtain a fluorine-tolerant acidophilic mineral leaching bacterium liquid with a fluorine content of 0.718 g / L, which was cryopreserved at ultra-low temperature. - The specific process of the gradient domestication is as follows:

[0099] The specific process of the gradient domestication is as follows:

[0100] Second domestication: The initially domesticated fluorine-tolerant acidophilic mineral leaching bacterium liquid was inoculated into a liquid medium containing F - at a concentration of 0.124 g / L + 0.066 g / L. When the lethality rate reached 92%, it was transferred to the above solid medium and cultured for 20 days. After screening, the second-domesticated Acidithiobacillus ferrooxidans colonies were obtained. Then, the second-domesticated Acidithiobacillus ferrooxidans colonies were inoculated into the above liquid medium and cultured until the logarithmic phase to obtain the second-domesticated fluorine-tolerant acidophilic mineral leaching bacterium liquid.

[0101] Third domestication: The second-domesticated fluorine-tolerant acidophilic mineral leaching bacterium liquid was inoculated into a liquid medium containing F - at a concentration of 0.124 g / L + 2×0.066 g / L. When the lethality rate reached 92%, it was transferred to the above solid medium and cultured for 20 days. After screening, the third-domesticated Acidithiobacillus ferrooxidans colonies were obtained. Then, the third-domesticated Acidithiobacillus ferrooxidans colonies were inoculated into the above liquid medium and cultured until the logarithmic phase to obtain the third-domesticated fluorine-tolerant acidophilic mineral leaching bacterium liquid.

[0102] And so on.

[0103] The 9th domestication: The fluorine-tolerant acidophilic mineral leaching bacterium liquid obtained from the 8th domestication was inoculated into a liquid medium containing F -In the liquid medium with a concentration of 0.124 g / L + 0.066×8 g / L, when the lethality rate reaches 92%, transfer it to the solid medium, culture for 20 days, screen to obtain the Thiobacillus ferrooxidans colony after the 9th domestication, and then inoculate the Thiobacillus ferrooxidans colony after the 9th domestication into the liquid medium and culture it to the logarithmic phase to obtain the fluorine-tolerant acidophilic mineral leaching bacteria solution after the 9th domestication.

[0104] The 10th domestication: Inoculate the fluorine-tolerant acidophilic mineral leaching bacteria solution after the 9th domestication into the liquid medium containing F - with a concentration of 0.124 g / L + 0.066×9 g / L. When the lethality rate reaches 92%, transfer it to the solid medium, culture for 20 days, screen to obtain the Thiobacillus ferrooxidans colony after the 10th domestication, and then inoculate the Thiobacillus ferrooxidans colony after the 10th domestication into the liquid medium and culture it to the logarithmic phase to obtain the fluorine-tolerant acidophilic mineral leaching bacteria solution with an F - content of 0.718 g / L; perform ultra-low temperature preservation on the fluorine-tolerant acidophilic mineral leaching bacteria solution.

[0105] Step 2: Under the conditions of 40 °C and an aeration rate of 0.04 m 3 / (L·h), expand the ultra-low temperature preserved fluorine-tolerant acidophilic mineral leaching bacteria solution to a scale of 1000 L / d, and the bacteria solution concentration is 9×10 9 cells / L to obtain the expanded fluorine-tolerant acidophilic mineral leaching bacteria solution.

[0106] Step 3: Roast the vanadium shale with a particle size ≤ 6 mm at 700 °C for 52 min to build a ore heap with a height of 4 m, and the V2O5 content of the vanadium shale is 0.8 wt%; then intermittently spray the ore heap with sulfuric acid with a concentration of 18 g / L until the pH of the effluent stabilizes at 0.03.

[0107] Step 4: According to the solid-liquid ratio of 0.718 g / L, add a fluorine-containing leaching aid to the expanded fluorine-tolerant acidophilic mineral leaching bacteria solution to obtain a fluorine-containing acidophilic mineral leaching bacteria solution; then intermittently drip the fluorine-containing acidophilic mineral leaching bacteria solution onto the ore heap after sulfuric acid spraying for heap leaching to obtain a leaching solution.

[0108] The preparation method of the liquid medium is: According to the solid-liquid ratio of 50 g / L, add ferrous sulfate heptahydrate to the 9K basic medium with a pH of 1.8 to obtain the liquid medium.

[0109] The preparation method of the solid medium is to add agar powder to the 9K basic medium with a pH of 1.9 according to the solid-liquid ratio of 30 g / L, and sterilize it at 100 °C for 12 min to obtain the solid medium.

[0110] The 9K basal medium: ammonium sulfate is 4 g / L, dipotassium hydrogen phosphate is 0.6 g / L, potassium chloride is 0.07 g / L, magnesium sulfate heptahydrate is 0.45 g / L, and calcium nitrate is 0.007 g / L.

[0111] The inoculation amount of the Acidithiobacillus ferrooxidans colony inoculation is a single colony in the solid medium, and the diameter of the Acidithiobacillus ferrooxidans colony is 2 mm.

[0112] The inoculation amount of the Acidiphilium multivorum bacterium solution inoculation is 12 vol% of the liquid medium with the current F- concentration.

[0113] The ultra-low temperature preservation is carried out using a cryoprotectant of 15% glycerol - liquid medium; the ultra-low temperature preservation temperature is -169 °C.

[0114] The spraying amount of the intermittent spraying is 15 L / (m 2 ·h), and the intermittent time of the intermittent spraying is 12 hours per day.

[0115] The fluorine-containing leaching aid is ammonium fluoride.

[0116] The vanadium concentration of the leaching solution is 1.2 g / L.

[0117] The spraying amount of the spray washing of the ore is 15 L / (m 2 ·h), and when the vanadium concentration of the washing water for spray washing the ore < 0.03 g / L or pH > 2.5, the spraying ends; the pH of the recycled spray washing water is 1.7.

[0118] Example 3

[0119] A method for bioheap leaching of vanadium using Acidiphilium multivorum. The method in this example is as follows:

[0120] Step 1, An acidophilic ore leaching bacterium, named Acidithiobacillus ferrooxidans.

[0121] Primary domestication: The Acidithiobacillus ferrooxidans strain is initially inoculated into a liquid medium with an F - concentration of 0.203 g / L. When the lethality rate reaches 94%, it is transferred to a solid medium and cultured for 16 days, and then screened to obtain the initially domesticated Acidithiobacillus ferrooxidans colony; then the initially domesticated Acidithiobacillus ferrooxidans colony is inoculated into the liquid medium and cultured to the logarithmic phase to obtain the initially domesticated Acidiphilium multivorum bacterium solution.

[0122] Gradient domestication: Each domestication is to inoculate the Acidiphilium multivorum bacterium solution obtained from the previous domestication into the liquid medium with the current F - concentration, and the current F -The liquid medium with a certain concentration is increased in gradient of 0.088 g / L based on the liquid medium with the previous F - concentration; the acclimation is repeated 13 times to obtain the fluorine-resistant acidophilic iron-oxidizing bacteria liquid with an F - content of 1.259 g / L, and it is cryopreserved at ultra-low temperature.

[0123] The specific process of the gradient acclimation is as follows:

[0124] Second acclimation: Inoculate the fluorine-resistant acidophilic iron-oxidizing bacteria liquid after the first acclimation into the liquid medium with an F - concentration of 0.203 g / L + 0.088 g / L. When the lethality rate reaches 94%, transfer it to the solid medium and culture for 16 days. After screening, obtain the Thiobacillus ferrooxidans colonies after the second acclimation. Then inoculate the Thiobacillus ferrooxidans colonies after the second acclimation into the liquid medium and culture until the logarithmic phase to obtain the fluorine-resistant acidophilic iron-oxidizing bacteria liquid after the second acclimation.

[0125] Third acclimation: Inoculate the fluorine-resistant acidophilic iron-oxidizing bacteria liquid after the second acclimation into the liquid medium with an F - concentration of 0.203 g / L + 2×0.088 g / L. When the lethality rate reaches 94%, transfer it to the solid medium and culture for 16 days. After screening, obtain the Thiobacillus ferrooxidans colonies after the third acclimation. Then inoculate the Thiobacillus ferrooxidans colonies after the third acclimation into the liquid medium and culture until the logarithmic phase to obtain the fluorine-resistant acidophilic iron-oxidizing bacteria liquid after the third acclimation.

[0126] And so on.

[0127] Twelfth acclimation: Inoculate the fluorine-resistant acidophilic iron-oxidizing bacteria liquid after the eleventh acclimation into the above-mentioned liquid medium with an F - concentration of 0.203 g / L + 11×0.088 g / L. When the lethality rate reaches 94%, transfer it to the solid medium and culture for 16 days. After screening, obtain the Thiobacillus ferrooxidans colonies after the twelfth acclimation. Then inoculate the Thiobacillus ferrooxidans colonies after the twelfth acclimation into the liquid medium and culture until the logarithmic phase to obtain the fluorine-resistant acidophilic iron-oxidizing bacteria liquid after the twelfth acclimation.

[0128] Thirteenth acclimation: Inoculate the fluorine-resistant acidophilic iron-oxidizing bacteria liquid after the twelfth acclimation into the above-mentioned liquid medium with an F - concentration of 0.203 g / L + 12×0.088 g / L. When the lethality rate reaches 94%, transfer it to the solid medium and culture for 16 days. After screening, obtain the Thiobacillus ferrooxidans colonies after the thirteenth acclimation. Then inoculate the Thiobacillus ferrooxidans colonies after the thirteenth acclimation into the liquid medium and culture until the logarithmic phase to obtain the fluorine-resistant -The acidophilic fluorine-tolerant ore leaching bacteria solution with a content of 1.259 g / L; the acidophilic fluorine-tolerant ore leaching bacteria solution is cryopreserved.

[0129] Step 2: Under the conditions of 28 °C and an aeration rate of 0.035 m 3 / (L·h), the cryopreserved acidophilic fluorine-tolerant ore leaching bacteria solution is expanded to a scale of 800 L / d, and the bacteria solution concentration is 6×10 10 per liter, obtaining the expanded acidophilic fluorine-tolerant ore leaching bacteria solution.

[0130] Step 3: Roast the vanadium shale with a particle size ≤ 6 mm at 650 °C for 45 min to build a ore heap with a height of 2 m, and the content of V2O5 in the vanadium shale is 1.7 wt%; then intermittently spray the ore heap with sulfuric acid with a concentration of 60 g / L until the pH of the effluent stabilizes at 0.1.

[0131] Step 4: According to a solid-liquid ratio of 1.259 g / L, add a fluorine-containing leaching aid to the expanded acidophilic fluorine-tolerant ore leaching bacteria solution to obtain an acidophilic fluorine-containing ore leaching bacteria solution; then intermittently drip the acidophilic fluorine-containing ore leaching bacteria solution onto the ore heap after sulfuric acid spraying for heap leaching to obtain a leaching solution.

[0132] The preparation method of the liquid medium is: according to a solid-liquid ratio of 40 g / L, add ferrous sulfate heptahydrate to the 9K basic medium with a pH of 2.0, and then the liquid medium is obtained.

[0133] The preparation method of the solid medium is: according to a solid-liquid ratio of 20 g / L, add agar powder to the 9K basic medium with a pH of 2.0, and sterilize at 105 °C for 15 min, then the solid medium is obtained.

[0134] The 9K basic medium: ammonium sulfate is 3 g / L, dipotassium hydrogen phosphate is 0.5 g / L, potassium chloride is 0.1 g / L, magnesium sulfate heptahydrate is 0.5 g / L, and calcium nitrate is 0.01 g / L.

[0135] The inoculation amount of the Thiobacillus ferrooxidans colony inoculation is a single colony in the solid medium, and the diameter of the Thiobacillus ferrooxidans colony is 1.5 mm.

[0136] The inoculation amount of the acidophilic fluorine-tolerant ore leaching bacteria solution inoculation is 7 vol% of the liquid medium with the current F- concentration.

[0137] The cryopreservation is carried out using a protective agent of 15% glycerol - liquid medium; the cryopreservation temperature is -136 °C.

[0138] The spraying amount of the intermittent spraying is 25 L / (m 2 ·h), and the intermittent time of the intermittent spraying is 12 hours per day.

[0139] The fluorine-containing leaching aid is potassium fluoride dihydrate.

[0140] The vanadium concentration of the leaching solution is 0.8 g / L.

[0141] The spraying volume of the spray washing of the ore is 25 L / (m 2 ·h). When the vanadium concentration of the washing water for spray washing the ore is < 0.03 g / L or the pH > 2.5, the spraying ends; the pH of the recycled washing water for spray washing the ore is 2.5.

[0142] Example 4

[0143] A method for using a fluorine-resistant acidophilic leaching bacterium to recover vanadium by bioheap leaching. The method described in this example is as follows:

[0144] Step 1: An acidophilic leaching bacterium, named Acidithiobacillus ferrooxidans.

[0145] Primary domestication: The Acidithiobacillus ferrooxidans strain is initially inoculated into a liquid medium containing F - at a concentration of 0.281 g / L. When the lethality rate reaches 96%, it is transferred to a solid medium and cultured for 12 days, followed by screening to obtain the initially domesticated Acidithiobacillus ferrooxidans colonies. Then, the initially domesticated Acidithiobacillus ferrooxidans colonies are inoculated into the liquid medium and cultured until the logarithmic phase to obtain the initially domesticated fluorine-resistant acidophilic leaching bacterium liquid.

[0146] Gradient domestication: Each time of domestication is to inoculate the fluorine-resistant acidophilic leaching bacterium liquid obtained from the previous domestication into a liquid medium with the F - concentration for this time. The liquid medium with the F - concentration for this time is increased by a gradient of 0.109 g / L based on the liquid medium with the F - concentration of the previous time; the domestication is repeated 16 times to obtain a fluorine-resistant acidophilic leaching bacterium liquid with an F - content of 1.916 g / L, which is stored at ultra-low temperature.

[0147] The specific process of the gradient domestication is as follows:

[0148] Second domestication: The initially domesticated fluorine-resistant acidophilic leaching bacterium liquid is inoculated into a liquid medium containing F - at a concentration of 0.281 g / L + 0.109 g / L. When the lethality rate reaches 96%, it is transferred to the solid medium and cultured for 12 days, followed by screening to obtain the second-domesticated Acidithiobacillus ferrooxidans colonies. Then, the second-domesticated Acidithiobacillus ferrooxidans colonies are inoculated into the liquid medium and cultured until the logarithmic phase to obtain the second-domesticated fluorine-resistant acidophilic leaching bacterium liquid.

[0149] Third domestication: Inoculate the acidophilic fluoride-resistant mineral leaching bacteria solution after the second domestication into a liquid medium containing F - with a concentration of 0.281 g / L + 2×0.109 g / L. When the lethality rate reaches 96%, transfer it to the solid medium and culture for 12 days. After screening, obtain the Acidithiobacillus ferrooxidans colonies after the third domestication. Then inoculate the Acidithiobacillus ferrooxidans colonies after the third domestication into the liquid medium and culture until the logarithmic phase to obtain the acidophilic fluoride-resistant mineral leaching bacteria solution after the third domestication.

[0150] And so on.

[0151] 15th domestication: Inoculate the acidophilic fluoride-resistant mineral leaching bacteria solution after the 14th domestication into the liquid medium containing F - with a concentration of 0.281 g / L + 14×0.109 g / L. When the lethality rate reaches 96%, transfer it to the solid medium and culture for 12 days. After screening, obtain the Acidithiobacillus ferrooxidans colonies after the 15th domestication. Then inoculate the Acidithiobacillus ferrooxidans colonies after the 15th domestication into the liquid medium and culture until the logarithmic phase to obtain the acidophilic fluoride-resistant mineral leaching bacteria solution after the 15th domestication.

[0152] 16th domestication: Inoculate the acidophilic fluoride-resistant mineral leaching bacteria solution after the 15th domestication into the liquid medium containing F - with a concentration of 0.281 g / L + 15×0.109 g / L. When the lethality rate reaches 96%, transfer it to the solid medium and culture for 12 days. After screening, obtain the Acidithiobacillus ferrooxidans colonies after the 16th domestication. Then inoculate the Acidithiobacillus ferrooxidans colonies after the 16th domestication into the liquid medium and culture until the logarithmic phase to obtain the acidophilic fluoride-resistant mineral leaching bacteria solution with an F - content of 1.916 g / L; Ultra-low temperature preservation of the acidophilic fluoride-resistant mineral leaching bacteria solution.

[0153] Step 2: Under the conditions of 20 °C and an aeration rate of 0.025 m 3 / (L·h), expand and culture the ultra-low temperature-preserved acidophilic fluoride-resistant mineral leaching bacteria solution to a scale of 1100 L / d, with a bacterial solution concentration of 5×10 11 cells / L to obtain the expanded acidophilic fluoride-resistant mineral leaching bacteria solution.

[0154] Step 3: Roast the vanadium shale with a particle size ≤ 6 mm at 750 °C for 38 min to build a ore heap with a height of 6 m. The vanadium shale contains 1.4 wt% of V2O5; Then intermittently spray the ore heap with sulfuric acid with a concentration of 35 g / L until the pH of the discharged liquid stabilizes at 0.05.

[0155] Step 4: According to the solid-liquid ratio of 1.916 g / L, add a fluorine-containing leaching aid to the expanded culture of the fluorine-tolerant acidophilic mineral leaching bacteria to obtain a fluorine-containing acidophilic mineral leaching bacteria solution; then intermittently drip the fluorine-containing acidophilic mineral leaching bacteria solution onto the ore heap after sulfuric acid spraying for heap leaching to obtain a leachate.

[0156] The preparation method of the liquid medium is as follows: According to the solid-liquid ratio of 45 g / L, add ferrous sulfate heptahydrate to the 9K basic medium with a pH of 2.3 to obtain the liquid medium.

[0157] The preparation method of the solid medium is as follows: According to the solid-liquid ratio of 25 g / L, add agar powder to the 9K basic medium with a pH of 2.1, and sterilize at 115 °C for 18 min to obtain the solid medium.

[0158] The 9K basic medium: ammonium sulfate is 3.5 g / L, dipotassium hydrogen phosphate is 0.55 g / L, potassium chloride is 0.12 g / L, magnesium sulfate heptahydrate is 0.55 g / L, and calcium nitrate is 0.012 g / L.

[0159] The inoculation amount of the Thiobacillus ferrooxidans colony inoculation is a single colony in the solid medium, and the diameter of the Thiobacillus ferrooxidans colony is 1.3 mm.

[0160] The inoculation amount of the fluorine-tolerant acidophilic mineral leaching bacteria solution inoculation is 10 vol% of the liquid medium with the current F- concentration.

[0161] The ultra-low temperature preservation is carried out using a protective agent of 15% glycerol - liquid medium; the ultra-low temperature preservation temperature is -105 °C.

[0162] The spraying amount of the intermittent spraying is 20 L / (m 2 ·h), and the intermittent time of the intermittent spraying is 12 hours per day.

[0163] The fluorine-containing leaching aid is sodium fluoride.

[0164] The vanadium concentration of the leachate is 1.1 g / L.

[0165] The spraying amount of the spray washing of the ore is 20 L / (m 2 ·h), and when the vanadium concentration of the washing water for spray washing the ore < 0.03 g / L or pH > 2.5, the spraying ends; the pH of the recycled washing water for spray washing the ore is 2.0.

[0166] Example 5

[0167] A method for bioheap leaching of vanadium using fluorine-tolerant acidophilic mineral leaching bacteria. The method in this example is as follows:

[0168] Step 1: An acidophilic mineral leaching bacterium, named Acidithiobacillus ferrooxidans, is used.

[0169] Primary domestication: The Acidithiobacillus ferrooxidans strain is initially inoculated into a liquid medium containing F - at a concentration of 0.36 g / L. When the lethality rate reaches 98%, it is transferred to a solid medium and cultured for 18 days. After screening, the initially domesticated Acidithiobacillus ferrooxidans colonies are obtained. Then, the initially domesticated Acidithiobacillus ferrooxidans colonies are inoculated into the liquid medium and cultured until the logarithmic phase to obtain the initially domesticated fluorine-tolerant acidophilic mineral leaching bacterium liquid.

[0170] Gradient domestication: Each time of domestication is to inoculate the fluorine-tolerant acidophilic mineral leaching bacterium liquid obtained from the previous domestication into a liquid medium containing F - at a concentration, and the liquid medium containing F - at a concentration is based on the liquid medium containing F - at a concentration and increased by a gradient of 0.13 g / L; the domestication is repeated 19 times to obtain a fluorine-tolerant acidophilic mineral leaching bacterium liquid with a fluorine content of 2.7 g / L, and it is cryopreserved at ultra-low temperature. - The specific process of the gradient domestication is as follows:

[0171] The second domestication: The initially domesticated fluorine-tolerant acidophilic mineral leaching bacterium liquid is inoculated into a liquid medium containing F

[0172] at a concentration of 0.36 g / L + 0.13 g / L. When the lethality rate reaches 98%, it is transferred to the solid medium and cultured for 18 days. After screening, the second-domesticated Acidithiobacillus ferrooxidans colonies are obtained. Then, the second-domesticated Acidithiobacillus ferrooxidans colonies are inoculated into the liquid medium and cultured until the logarithmic phase to obtain the second-domesticated fluorine-tolerant acidophilic mineral leaching bacterium liquid. - The third domestication: The second-domesticated fluorine-tolerant acidophilic mineral leaching bacterium liquid is inoculated into a liquid medium containing F

[0173] at a concentration of 0.36 g / L + 2×0.13 g / L. When the lethality rate reaches 98%, it is transferred to the solid medium and cultured for 18 days. After screening, the third-domesticated Acidithiobacillus ferrooxidans colonies are obtained. Then, the third-domesticated Acidithiobacillus ferrooxidans colonies are inoculated into the liquid medium and cultured until the logarithmic phase to obtain the third-domesticated fluorine-tolerant acidophilic mineral leaching bacterium liquid. - And so on.

[0174] The 18th domestication: The 17th-domesticated fluorine-tolerant acidophilic mineral leaching bacterium liquid is inoculated into a liquid medium containing F

[0175] at a concentration of 0.36 g / L + 17×0.13 g / L. When the lethality rate reaches 98%, it is transferred to the solid medium and cultured for 18 days. After screening, the 18th-domesticated Acidithiobacillus ferrooxidans colonies are obtained. Then, the 18th-domesticated Acidithiobacillus ferrooxidans colonies are inoculated into the liquid medium and cultured until the logarithmic phase to obtain the 18th-domesticated fluorine-tolerant acidophilic mineral leaching bacterium liquid. -In the liquid medium with a concentration of 0.36 g / L + 17×0.13 g / L, when the lethality rate reaches 98%, it is transferred to the solid medium and cultured for 18 days, then screened to obtain the Thiobacillus ferrooxidans colonies after the 18th domestication. Then, the Thiobacillus ferrooxidans colonies after the 18th domestication are inoculated into the liquid medium and cultured until the logarithmic phase to obtain the acidophilic fluorine-tolerant ore-leaching bacterial liquid after the 18th domestication.

[0176] The 19th domestication: Inoculate the acidophilic fluorine-tolerant ore-leaching bacterial liquid after the 18th domestication into the liquid medium containing F - with a concentration of 0.36 g / L + 18×0.13 g / L. When the lethality rate reaches 98%, it is transferred to the solid medium and cultured for 18 days, then screened to obtain the Thiobacillus ferrooxidans colonies after the 19th domestication. Then, the Thiobacillus ferrooxidans colonies after the 19th domestication are inoculated into the liquid medium and cultured until the logarithmic phase to obtain the acidophilic fluorine-tolerant ore-leaching bacterial liquid with an F - content of 2.7 g / L; the acidophilic fluorine-tolerant ore-leaching bacterial liquid is cryopreserved at ultra-low temperature.

[0177] Step 2: Under the conditions of 35 °C and an aeration rate of 0.03 m 3 / (L·h), expand and culture the acidophilic fluorine-tolerant ore-leaching bacterial liquid cryopreserved at ultra-low temperature to a scale of 900 L / d, and the bacterial liquid concentration is 10 12 cells / L to obtain the expanded acidophilic fluorine-tolerant ore-leaching bacterial liquid.

[0178] Step 3: Roast the vanadium shale with a particle size ≤ 6 mm at 800 °C for 60 min to build an ore heap with a height of 3 m. The V2O5 content of the vanadium shale is 1.1 wt%; then intermittently spray the ore heap with sulfuric acid with a concentration of 50 g / L until the pH of the effluent stabilizes at 0.07.

[0179] Step 4: According to a solid-liquid ratio of 2.7 g / L, add a fluorine-containing leaching aid to the expanded acidophilic fluorine-tolerant ore-leaching bacterial liquid to obtain an acidophilic fluorine-tolerant ore-leaching bacterial liquid; then intermittently drip the acidophilic fluorine-tolerant ore-leaching bacterial liquid onto the ore heap after sulfuric acid spraying for heap leaching to obtain a leachate.

[0180] The preparation method of the liquid medium is: Add ferrous sulfate heptahydrate to the 9K basal medium with a pH of 2.5 according to a solid-liquid ratio of 35 g / L to obtain the liquid medium.

[0181] The preparation method of the solid medium is to add agar powder to the 9K basal medium with a pH of 2.2 according to a solid-liquid ratio of 15 g / L, and sterilize it at 121 °C for 20 min to obtain the solid medium.

[0182] The 9K basal medium: ammonium sulfate is 2.5 g / L, dipotassium hydrogen phosphate is 0.4 g / L, potassium chloride is 0.15 g / L, magnesium sulfate heptahydrate is 0.4 g / L, and calcium nitrate is 0.015 g / L.

[0183] The inoculation amount of the inoculated Acidithiobacillus ferrooxidans colonies is a single colony in the solid medium, and the diameter of the Acidithiobacillus ferrooxidans colonies is 1.8 mm.

[0184] The inoculation amount of the inoculated Acidiphilium multivorum bacteria solution is 15 vol% of the liquid medium with the current F- concentration.

[0185] The ultra-low temperature preservation is carried out using a protective agent of 15% glycerol - liquid medium; the ultra-low temperature preservation temperature is -80 °C.

[0186] The spraying amount of the intermittent spraying is 10 L / (m 2 ·h), and the intermittent time of the intermittent spraying is 12 hours per day.

[0187] The fluorine-containing leaching aid is potassium fluoride dihydrate.

[0188] The vanadium concentration of the leachate is 1.0 g / L.

[0189] The spraying amount of the spray washing of the ore is 10 L / (m 2 ·h), and when the vanadium concentration of the washing water for the spray washing of the ore < 0.03 g / L or pH > 2.5, the spraying ends; the pH of the recycled washing water for the spray washing of the ore is 2.2.

[0190] The present specific embodiment has the following positive effects compared with the prior art:

[0191] 1. The present specific embodiment uses an acidophilic ore-leaching bacterial strain named Acidithiobacillus ferrooxidans, and obtains an Acidiphilium multivorum bacteria solution through domestication. The F - content reaches 0.36 - 2.7 g / L. Using the Acidiphilium multivorum bacteria solution to leach the vanadium shale system, under the dual action of the fluorine-containing leaching aid and the Acidiphilium multivorum, the vanadium shale ore heap after roasting and sulfuric acid spraying is subjected to biological heap leaching of the vanadium shale, increasing the ore treatment volume, shortening the leaching cycle, reducing the economic cost, increasing the leaching rate of vanadium in the vanadium shale, and significantly enhancing the microbial leaching effect.

[0192] 2. The present specific embodiment utilizes the effect of fluoride in chemical leaching to destroy the mica lattice, and there is no need to perform defluorination treatment on it. A method of combining with chemical leaching to enhance leaching is proposed. The fluoride tolerance domestication of the acidophilic ore-leaching bacteria can effectively reduce or eliminate the influence of fluorine on the growth of acidophilic ore-leaching bacteria, and shorten the leaching cycle.

[0193] 3. This specific implementation does not avoid the influence of F - . By taking advantage of the fact that F - participates in the coordination and binding of the central atoms in the mica tetrahedron and octahedron structures, and cooperates with H + to participate in the reaction synergistically to achieve the destruction of the mica structure, a fluorine-tolerant and acidophilic bioleaching bacterial solution is cultivated, and the vanadium shale is subjected to biological heap leaching, with low production costs and high resource recovery rates.

[0194] Therefore, the acidophilic bioleaching bacterial solution used in this specific implementation is fluorine-tolerant domesticated and enlarged cultured, and is used for the biological heap leaching of low-grade vanadium shale with high leaching rates and large treatment capacities.

Claims

1. A method for bioheap leaching of vanadium recovery using fluorine-tolerant acidophilic leaching bacteria, characterized in that The steps of the method are as follows: Step 1: An acidophilic mineral leaching bacterium, named Acidithiobacillus ferrooxidans; Primary domestication: Initially inoculate the Thiobacillus ferrooxidans strain into a liquid medium with an F - concentration of 0.045 - 0.36 g / L. When the lethality rate reaches 90 - 98%, transfer it to a solid medium and culture for 5 - 20 days, then screen to obtain the initially domesticated Thiobacillus ferrooxidans colonies. Then inoculate the initially domesticated Thiobacillus ferrooxidans colonies into the above liquid medium and culture until the logarithmic phase to obtain the initially domesticated fluorine-tolerant acidophilic bioleaching bacteria liquid; Gradient domestication: For each domestication, the acidophilic fluorine-tolerant bioleaching bacteria solution obtained from the previous domestication was inoculated into the liquid medium containing F in this time. - The concentration of the liquid medium containing F in this time - was increased by a gradient of 0.045 - 0.13 g / L based on the liquid medium containing F in the previous time. - The domestication was repeated 8 - 19 times to obtain an acidophilic fluorine-tolerant bioleaching bacteria solution with an F content of 0.36 - 2.7 g / L, and then cryopreserved. - ​ Step 2. Under the conditions of 15-40 °C and an aeration rate of 0.02-0.04 m 3 / (L·h), expand the ultra-low temperature preserved fluorine-tolerant acidophilic leaching bacteria liquid to a scale of 800-1200 L / d, and the concentration of the bacteria liquid is 10 9 ~10 12 cells / L to obtain the expanded fluorine-tolerant acidophilic leaching bacteria liquid; Step 3: Roast the vanadium shale with a particle size of ≤6 mm at 600 - 800 °C for 30 - 60 min to build a ore heap with a height of 2 - 6 m. The content of V2O5 in the vanadium shale is 0.5 - 1.7 wt%. Then intermittently spray the ore heap with sulfuric acid with a concentration of 5 - 60 g / L until the pH of the effluent stabilizes at 0 - 0.1; Step 4: According to the solid-liquid ratio of 0.36 - 2.7 g / L, add a fluorine-containing leaching aid to the expanded culture of the fluorine-tolerant acidophilic mineral leaching bacterium solution to obtain a fluorine-tolerant acidophilic mineral leaching bacterium solution. Then intermittently drip the fluorine-tolerant acidophilic mineral leaching bacterium solution onto the ore heap after sulfuric acid spraying for heap leaching to obtain a leaching solution; The leaching solution is purified and enriched with vanadium, the lean organic phase is regenerated, vanadium is precipitated, and vanadium pentoxide is prepared to recover vanadium.

2. The method for using the fluorine-resistant acidophilic leaching bacterium according to claim 1 for bioheap leaching to recover vanadium, characterized in that, The preparation method of the liquid medium is: Add ferrous sulfate heptahydrate to the 9K basal medium with a pH of 1.5 - 2.5 according to the solid-liquid ratio of 30 - 50 g / L to obtain the liquid medium.

3. The method for bioheap leaching to recover vanadium using the fluorine-resistant acidophilic mineral leaching bacterium according to claim 1, wherein The preparation method of the solid medium is: Add agar powder to the 9K basal medium with a pH of 1.8 - 2.2 according to the solid-liquid ratio of 10 - 30 g / L, and sterilize it at 90 - 121 °C for 10 - 20 min to obtain the solid medium.

4. The method for bioheap leaching to recover vanadium using the fluorine-tolerant acidophilic leaching bacterium according to claim 2 or claim 3, characterized in that, The 9K basal medium: ammonium sulfate is 2 - 4 g / L, dipotassium hydrogen phosphate is 0.4 - 0.6 g / L, potassium chloride is 0.05 - 0.15 g / L, magnesium sulfate heptahydrate is 0.4 - 0.6 g / L, and calcium nitrate is 0.005 - 0.015 g / L.

5. The method for bioheap leaching of vanadium using the fluorine-tolerant acidophilic mineral leaching bacterium according to claim 1, characterized in that The inoculation amount of the Acidithiobacillus ferrooxidans colony inoculation is a single colony in the solid medium, and the diameter of the Acidithiobacillus ferrooxidans colony is 1 - 2 mm; The inoculation amount of the fluorine-tolerant acidophilic mineral leaching bacterium solution inoculation is 5 - 15 vol% of the liquid medium with the current F- concentration.

6. The method for bioheap leaching of vanadium recovery using the fluorine-tolerant acidophilic leaching bacterium according to claim 1, characterized in that, The ultra-low temperature preservation is carried out using a protective agent of 15% glycerol - liquid medium; the ultra-low temperature preservation temperature is -196 - -80 °C.

7. The method for bioheap leaching to recover vanadium using the fluorine-resistant acidophilic mineral leaching bacteria according to claim 1, wherein The spray volume of the intermittent spraying is 10 to 30 L / (m 2 ·h), and the intermittent time of the intermittent spraying is 12 hours per day.

8. The method for bioheap leaching to recover vanadium using the fluorine-resistant acidophilic leaching bacterium according to claim 1, wherein The fluorine-containing leaching aid is one of sodium fluoride, ammonium fluoride, and potassium fluoride dihydrate.

9. The method for bioheap leaching of vanadium recovery using the fluorine-tolerant acidophilic leaching bacterium according to claim 1, wherein The vanadium concentration of the leaching solution is 0.7 - 1.2 g / L.

10. The method for bioheap leaching of vanadium recovery using the fluorine-resistant acidophilic leaching bacterium according to claim 1, wherein The spraying volume of the spray washing of ore is 10-30 L / (m 2 ·h). When the vanadium concentration of the washing water for spray washing of ore < 0.03 g / L or pH > 2.5, the spraying ends; the pH of the recycled washing water for spray washing of ore is 1.5-2.5.