CN113897483A - Application of acidithiobacillus psychrophilus in oxidative leaching of pyrite and low-grade uranium ore, system and method - Google Patents

Application of acidithiobacillus psychrophilus in oxidative leaching of pyrite and low-grade uranium ore, system and method Download PDF

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CN113897483A
CN113897483A CN202111154270.4A CN202111154270A CN113897483A CN 113897483 A CN113897483 A CN 113897483A CN 202111154270 A CN202111154270 A CN 202111154270A CN 113897483 A CN113897483 A CN 113897483A
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pyrite
leaching
acidithiobacillus
oxidation
ferrivorans
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王清良
邓瑶
王红强
胡鄂明
雷治武
吕俊文
魏小辉
张锐
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University of South China
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/18Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
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    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12NMICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N1/00Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
    • C12N1/20Bacteria; Culture media therefor
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B60/00Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
    • C22B60/02Obtaining thorium, uranium, or other actinides
    • C22B60/0204Obtaining thorium, uranium, or other actinides obtaining uranium
    • C22B60/0217Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
    • C22B60/0221Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching
    • C22B60/0226Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching using acidic solutions or liquors

Abstract

The invention provides an application, a system and a method of cold-resistant acidophilic thiobacillus in oxidative leaching of pyrite and low-grade uranium ore, and relates to the technical field of microbial metallurgy. The invention adopts pyrite series test results to show that when the pH of the solution is 2, Fe2+And Fe3+Under the existing condition, the acidithiobacillus psychrophilus can rapidly oxidize pyrite, and the oxidation rate respectively reaches 98.05% and 87.30%. Acidithiobacillus psychrophilus oxidizing UO2The results of a series of condition tests show that when the pH value of the solution is 2, the Acidithiobacillus caldus + Fe is resistant2+System pair UO2The leaching rate is highest, and is respectively 94.69 percent and 99.94 percent after 1g/L of pyrite is added; durableAcidithiobacillus caldus + Fe3+System pair UO2The leaching rate is 49.77 percent, and the leaching rate is 61.55 percent when a small amount of pyrite is added. The invention also constructs a model of the cold resistant acidovorax thiobacillus oxidation leaching stage, and can better explain the leaching UO2And (5) regularity.

Description

Application of acidithiobacillus psychrophilus in oxidative leaching of pyrite and low-grade uranium ore, system and method
Technical Field
The invention belongs to the technical field of microbial metallurgy, and particularly relates to application of cold-resistant Acidithiobacillus caldus in oxidative leaching of pyrite and low-grade uranium ore, a system and a method.
Background
Uranium (U) is a strategic element and essential for use as a fuel in nuclear power plants and nuclear weapons. The rapid development of scientific technology enables uranium to be used as important strategic material and nuclear energy fuel, and to be rapidly applied in the fields of scientific research, medical treatment, aviation and the like, so that the global demand for uranium resources is greatly increased. The microbial metallurgy, also called microbial leaching technology, is widely used due to the advantages of environmental protection, economy, simple flow and the like, shows strong advantages in the exploitation of low-grade and difficultly-treated lean mineral resources, and can greatly improve the leaching rate of metals. In China, the dump leaching research experiment of the ore outside the surface is carried out by acid and bacteria in the mine of the institute of microbiology of Chinese academy of sciences and the former five places of nuclear industry between 1965 and 1971. In the early 90 s of the last century, the nuclear industry uranium ore mining research institute performs indoor bacterial column leaching tests on domestic low-grade uranium ores, and a good effect is achieved. In 2005, the semi-industrial test (2200t) of treating low-grade ore of uranium toshiba ore by a bacterial heap leaching method in Beijing chemical institute of health of nuclear industry succeeded. Up to now, the microorganism mineral leaching technology has made great progress and is widely applied in the field of leaching of various metals such as copper, gold, zinc and uranium.
As early as the 70 s in the 19 th century, the famous scholars silvernen proposed two main mechanisms of bacterial leaching, namely direct action and indirect action, which is the initial hypothesis of the bacterial leaching mechanism; later, bacterial leaching is applied to industrial practice in a large number, the related process technology is continuously improved, people have different discoveries in the process, and the complex combined action of biological oxidation, chemical oxidation and electrochemical oxidation integrated is provided; according to Crundwell, the previous researches are summarized and concluded, and different action mechanisms exist between bacteria and different minerals, which are mainly divided into three mechanisms of direct action, indirect action and combined action. The microorganisms used for leaching ores are chemoautotrophic bacteria generally, and besides, some heterotrophic bacteria, fungi and other microorganisms play a vital role in the microbial leaching process. In contrast, chemoautotrophic bacteria are most common in industrial leaching applications, including three types: mesophilic bacteria, moderate thermophilic bacteria and extreme thermophilic bacteria, the main classification standard is mainly based on the environmental temperature to which the bacteria can adapt. The low-temperature bacteria are generally applied to the fields of sewage treatment, environmental remediation, high-efficiency degradation and the like, and are rare in the aspect of microbial metallurgy.
Disclosure of Invention
In view of the above, the invention aims to provide an application, a system and a method of the psychrophilic acid-tolerant thiobacillus in the oxidative leaching of pyrite and low-grade uranium ore, search the oxidation law of a.ferrivorans, design pyrite as an experimental raw material, and obtain the optimal oxidation condition of pyrite through analysis; constructing an A.ferrivorans oxidized pyrite stage model; simultaneously, the catalyst is subjected to UO according to the optimal oxidation conditions2As an experimental object, the leaching rule of uranium under the optimal condition is obtained.
In order to achieve the above object, the present invention provides the following technical solutions:
use of Acidithiobacillus caldus (Acidithiobacillus ferrorans) for the oxidative leaching of pyrites and low-grade uranium ores.
The invention provides a system for oxidizing and leaching pyrite, wherein the pH value of the system is 2.0, the system comprises a bacterial liquid of Acidithiobacillus acidophilus, a culture medium and pyrite, and the culture medium contains 1g/L-5g/L Fe2+Or Fe3+
Preferably, the volume ratio of the bacterial liquid to the culture medium is 1: 9.
preferably, the composition of the medium comprises: (NH)4)2SO43g/L、K2HPO40.5g/L、KCl 0.1g/L、MgSO40.5g/L、Ca(NO3)20.01g/L and Fe2+(1g/L-5g/L)。
Preferably, the mass volume ratio of the pyrite in the system to the system is 0.1 g: 100 mL.
The invention also provides a method for oxidizing and leaching pyrite, which comprises the step of preparing the system and culturing at the temperature of 30 ℃ and the rotating speed of 170 r/min.
The invention also provides a system for oxidizing and leaching the low-grade uranium ore, the pH value of the system is 2.0, the system comprises a bacterial liquid of Acidithiobacillus acidophilus, a culture medium and the low-grade uranium ore, and the culture medium contains 1g/L-5g/L Fe2+Or Fe3+
Preferably, the volume ratio of the bacterial liquid to the culture medium in the system is 1: 9, the mass volume ratio of the low-grade uranium ore to the system is 0.1 g: 100 mL.
Preferably, 0.1g of pyrite is also included per 100mL of the system.
The invention also provides a method for oxidizing and leaching low-grade uranium ore, which comprises the steps of preparing the system and culturing at the temperature of 30 ℃ and the rotating speed of 170 r/min.
Has the advantages that: the invention selects cold-resistant acidithiobacillus psychrophilus with uranium resistance as an oxidant, pyrite and UO2Is a subject of study; research on the oxidation leaching performance of bacteria in energy bases with different iron ion valence states on uranium is carried out. It was found that in Fe2+Under the condition, the oxidation rate of the A.ferrivorans system to pyrite is 98.05 percent, and in the Fe condition3+Under the condition, the oxidation rate of the pyrite is 87.30 percent. In the presence of Fe2+Ferrivorans system pair UO2The oxidative leaching rate of (2) was 94.70%, and the leaching rate was increased to 99.96% after the addition of 1g/L pyrite. The invention constructs an A.ferrivorans oxidation model and discloses UO2The oxidation leaching mechanism of isThe bacterial uranium leaching provides a new theoretical basis.
Drawings
Fig. 1 is a graph of the change in pH, Eh, Σ Fe of a. ferrivorans oxidized pyrite;
FIG. 2 is an XRD pattern of slag under different energy sources (A)0Bacteria + pyrite; a. the1:Fe2++ bacteria + pyrite; a. the2:Fe3++ pyrite; a. the3:Fe3++ bacteria + pyrite; origin: pyrite raw ore samples);
FIG. 3 is an SEM image of a pyrite raw ore sample;
FIG. 4 is an SEM image of pyrite slag under the energy base of iron ions of different valence states (A)0Bacteria + pyrite; a. the1:Fe2++ bacteria + pyrite; a. the2:Fe3++ pyrite; a. the3:Fe3++ bacteria + pyrite);
FIG. 5 is an FTIR spectrum of jarosite produced in two different systems;
FIG. 6 is an XRD spectrum of a secondary mineral;
FIG. 7 is an XPS spectrum of a secondary mineral;
FIG. 8 is a change curve of uranium concentration (a) and uranium leaching rate (b);
figure 9 is a ferrivorans oxidized pyrite leach UO2And (4) phase model.
Detailed Description
The invention provides application of Acidithiobacillus psychrophilus (Acidithiobacillus. ferrivorans) in oxidative leaching of pyrite and low-grade uranium ore.
The Acidithiobacillus psychrophilus (A. ferrivorans for short), aerobic gram-negative bacteria and Thiobacillus are inorganic autotrophic microorganisms with strong tolerance and energy conversion, and the strain can grow by taking ferrous iron, sulfur, thiosulfate and pyrite as energy sources. Ferivorans can grow under the condition of 5-35 ℃ and oxidize Fe under the low-temperature environment (5-25℃)2+The higher the rate. Ferrivorans obtains energy by oxidizing ferrous ions or reduced sulfides, and has a specific oxidation-reduction potential as various cytochromes in an electron transport chainWith Fe3+The oxidation in the culture solution is increased. The strain can grow by using ferrous iron, sulfur, thiosulfate and pyrite as energy sources, and oxidize Fe2+Is Fe3+To obtain energy, Fe produced3+Can oxidize the target metal in the mineral and oxidize the element sulfur in the mineral to generate sulfuric acid to further erode the mineral. Analysis of a. ferrivorans whole genome sequence revealed its potential for extreme environmental adaptation.
The invention provides a system for oxidizing and leaching pyrite, wherein the pH value of the system is 2.0, the system comprises a bacterial liquid of Acidithiobacillus acidophilus, a culture medium and pyrite, and the culture medium contains 1g/L-5g/L Fe2+Or Fe3+
The volume ratio of the bacterial liquid to the culture medium is preferably 1: 9. the preferable method for obtaining the bacterial liquid comprises the following steps: taking out the strain from the freezing condition of 4 ℃, inoculating 10mL of bacterial liquid into a 250mL conical flask according to the volume ratio of 10 percent, adding 90mL of culture medium liquid, and shaking under the optimal culture condition (the temperature is 30 ℃, the initial pH is 2.0, and the rotation speed of a shaking table is 170 r/min); activating for about two days under the optimal culture condition every time, taking out 10mL of bacterial liquid from a first generation conical flask, and repeating the steps; repeating for more than three generations to obtain active strain, wherein Fe in the strain liquid2+The oxidation rate is more than 95%. The continuous activation operation of the strains is uninterrupted, and the activity of the bacteria is maintained for later use.
Inoculating 10% of activated bacteria at 30 deg.C, initial pH of 2.0, and rotating table at 170 r/min. The stock solution of bacteria is preferably inoculated when it is blood red or dark red, and the composition of the culture medium of the invention preferably comprises: (NH)4)2SO43g/L、K2HPO40.5g/L、KCl 0.1g/L、MgSO40.5g/L and Ca (NO)3)20.01 g/L. In the present invention, the Fe2 +From FeSO4·7H2O is provided in a specific concentration range of 1g/L to 5 g/L.
The mass volume ratio of the pyrite to the system in the system is preferably 0.1 g: 100mL, and in the present invention, the pyrite is preferably ground and sieved through a 200-mesh sieve to obtain powdered pyrite.
The invention also provides a method for oxidizing and leaching pyrite, which comprises the step of preparing the system and culturing at the temperature of 30 ℃ and the rotating speed of 170 r/min.
In the present invention, Fe in pyrite serves as an energy source of a. ferrivorans, and iron in pyrite can be more rapidly oxidized into solution under the action of a. ferrivorans. With Fe2+When existing, the oxidation rate of pyrite reaches 98.05%, and Fe exists3+When the method exists, the leaching rate of the pyrite reaches 87.30%, and the oxidation effect is good.
The invention also provides a system for oxidizing and leaching the low-grade uranium ore, the pH value of the system is 2.0, the system comprises a bacterial liquid of Acidithiobacillus acidophilus, a culture medium and the low-grade uranium ore, and the culture medium contains 1g/L-5g/L Fe2+Or Fe3+
The compositions of the bacterial liquid and the culture medium are preferably the same as those described above, and are not described in detail herein. The volume ratio of the bacterial liquid to the culture medium in the system is preferably 1: and 9, the mass volume ratio of the low-grade uranium ore to the system is preferably 0.1 g: 100 mL. In the present invention, 0.1g of pyrite is preferably further included per 100mL of the system. In the system, A. ferrivorans and Fe are present2+The leaching rate of uranium can be greatly improved by two factors, namely, when the activity of A.ferrivorans is stronger, Fe is oxidized2+In the process, the leaching rate of uranium can be greatly increased. And the addition of 1g/L pyrite has a trace gain effect on leaching of uranium.
In the present invention, A. ferrivorans oxidizes UO2The results of the series of conditional tests show that when the solution pH is 2, a. ferrivorans + Fe2+System pair UO2The leaching rate is highest, and is improved after 1g/L pyrite (100mL system) is added, and is respectively 94.69 percent and 99.94 percent; ferrivorans + Fe3+System pair UO2The leaching rate is 49.77 percent, and the leaching rate is 61.55 percent when a small amount of pyrite is added.
The invention also provides a method for oxidizing and leaching low-grade uranium ore, which comprises the steps of preparing the system and culturing at the temperature of 30 ℃ and the rotating speed of 170 r/min.
The time for the cultivation according to the invention is preferably two days.
The following examples are provided to illustrate the application, system and method of the psychrophilic acid resistant thiobacillus in the oxidative leaching of pyrite and low grade uranium ore, but they should not be construed as limiting the scope of the invention.
Example 1
1 test part
1.1 starting materials
The pyrite is purchased from mining company Limited in big Baoshan, Guangdong province, and is ground and sieved by a 200-mesh sieve to obtain powdery pyrite. The XRF chemical composition analysis of the pyrite as received is shown in Table 1, and the analysis result shows that the main component of the pyrite is FeS2And the purity is higher, so the method is an ideal experimental raw material.
TABLE 1 analysis of mineral composition of pyrite
Figure BDA0003288039390000051
Figure BDA0003288039390000061
1.2A. ferrivorans oxidation test method
1.2.1 oxidized pyrite test method
Weighing four parts of pyrite, wherein each part is 0.1g, adding the four parts of pyrite into a 250mL conical flask, sequentially adding cultured active bacterial liquid into each test sample, and inoculating the active bacterial liquid into each test sample to obtain 100mL of pyrite, and adjusting the pH value to 2.0 by using dilute sulfuric acid. Biological oxidation test conditions of pyrite: the temperature is 30 ℃ and the rotating speed is 170 r/min. Samples were taken every 24 hours to measure pH, Eh and sigma Fe concentrations. The specific addition amounts are shown in table 2 below.
Table 2 influence of iron ion valency on a. ferrivorans oxidation
Figure BDA0003288039390000062
1.2.2 oxidative leaching of UO2Test method
Through the analysis of the group A test, the UO is weighed2Five parts, each 0.1g, are added into a 250mL conical flask, then the cultured active bacterial liquid is sequentially added into each test sample, the total amount is 100mL, and the pH is adjusted to 2.0 by dilute sulfuric acid. UO2Bioleaching test conditions of (1): the temperature is 30 ℃ and the rotating speed is 170 r/min. Samples were taken every 24 hours to measure pH, Eh and sigma Fe concentrations. The specific addition amounts are shown in table 3 below.
TABLE 3A Ferivorans Oxidation Leaching UO2Design of experiments
Figure BDA0003288039390000063
Figure BDA0003288039390000071
2 test results and analysis
The changes of the solution pH, Eh and E Fe concentrations are important parameters reflecting the oxidation process, and FIG. 1 shows the related parameter change trends in two experimental processes.
2.1Fe2+、Fe3+Effects on A.Ferivorans oxidized pyrite
The parameters related to the change of the valence state of the iron ions to the oxidized pyrite of the a. ferrivorans are shown in (a) to (c) of fig. 1. Analysis of pyrite and Fe by analysis of pH Change law3+The reaction is as in formula (2.1), and leaching is divided into three stages: 0-2 d, the main reaction is A. ferrivorans oxidizing Fe2+H + will be consumed resulting in an increase in pH, as in formula (2.3); 2 to 4d, A. ferrivorans oxidizing Fe2+The main reaction still exists, but the A. ferrivorans are mostly adsorbed to the surface of the pyrite at this time, and the FeS oxidation starts2And produce H +, alleviate H+So that the pH still rises, but the rate of rise slows; after 4 days, Fe in solution2+Depletion, at which point a. ferrivorans predominatesTo obtain energy from oxidized pyrite, as in formula (2.4), Fe3+Reacts with pyrite, as in formula (2.2), while jarosite starts to form and precipitates, as in formula (2.5). Wherein A is0Only bacteria, which react predominantly according to the formula (2.4), A2Only Fe3+
Factor, which mainly occurs in the reaction of formula (2.2), A3There are two former factors, and the reaction takes place according to formula (2.4) and formula (2.2).
FeS2+Fe2(SO4)3→3FeSO4+2S (2.1)
FeS2+7Fe2(SO4)3+8H2O→15FeSO4+8H2SO4 (2.2)
Figure BDA0003288039390000072
Figure BDA0003288039390000081
K++3Fe3++2SO4 2-+6H2O→KFe3(SO4)2(OH)6+6H+ (2.5)
Eh size may reflect Fe3+/Fe2+Ratio of Fe in microbial leaching system2+And Fe3+A cyclic conversion process exists in the whole system, and the leaching rate of the system is mainly composed of Fe2+Conversion to Fe3+Is determined by the rate of the signal. Leaching for 0-2 d to obtain Fe in the solution3+Increase of Fe2+Ions are reduced, so that the Eh value is increased quickly; after 3d of leaching, the bacterial activity is reduced and even the bacteria die, and Fe3+Hydrolysis to generate jarosite and Fe3+And the Eh value is reduced, so that the rise of the Eh value is slowed down and even reduced.
The concentration of sigma Fe in the four leaching systems is different, wherein A1,A3Slightly decreased, and analysis shows that in the initial stage of leaching,A1,A3Iron ions in the system, with the help of A. ferrivorans, FeS2、Fe3+And Fe2+The three can well complete the mutual conversion, so the concentration of sigma Fe can quickly rise; in the later stages of leaching, the precipitate produced in leaching accumulates to cover the mineral surface, preventing further leaching of the metal, so that the concentration of ∑ Fe remains unchanged and even decreases as a result of co-precipitation.
The above studies show that Fe in pyrite acts as an energy source for a. ferrivorans, and iron in pyrite can be oxidized into solution more rapidly by a. ferrivorans. A. the0,A2The system has no obvious oxidation effect on the pyrite, does not generate precipitate in the oxidation process, and has low oxidation rate; a. the1,A3In both systems, the oxidation effect of pyrite is obvious, A1The oxidation rate of pyrite reaches 98.05 percent, A3The leaching rate of pyrite reaches 87.30%, and the oxidation effect is better.
2.2 Secondary mineral characterization analysis
2.2.1 XRD comparative analysis of slag
After the reaction is finished, taking the pyrite under different energy bases after the reaction for XRD analysis and test, wherein the spectrum is shown in figure 2.
And (4) carrying out retrieval qualitative analysis on the XRD (X-ray diffraction) spectrums of the original pyrite and the leaching residue. Observation A1And A3And comparing with pyrite raw ore, finding A1And A3Several peaks are added in the positions of the three frame lines of 1, 2 and 3, other several miscellaneous peaks are removed, Jade 6.0 analysis is adopted, and comparison with related documents proves that the raised peaks are mainly jarosite. Jarosite and schlerite are hydrolytic precipitates generated in the ore leaching process, can be attached to the surface of pyrite, and prevent the leaching from continuing. A. the0And A2The presence of jarosite was not detected in the slag, which also corresponds to the apparent description during the leaching process.
By analysis of their characterization, A1System and A3The system can finally generate a secondary mineral jarosite; a. the0Or A2No precipitation is produced during the oxidation of the system, i.e. A0Or A2The system is not oxidized as much as A1Or A3And (4) preparing the system.
2.2.2 SEM comparative analysis of slag
In the presence of A. ferrivorans + Fe3+Or A. ferrivorans + Fe2+In the process, the oxidation leaching of the pyrite is very obvious. After the experiment, SEM analysis was performed on the pyrite slag to analyze the changes in the surface structure of the pyrite before and after the leaching. See fig. 3 and 4 for pyrite as received and for slag SEM images.
As can be seen from FIG. 3, the surface of the original ore sample of pyrite is relatively flat, but a lot of white crystalline substances are attached, and combined with XRF and XRD analysis of the sample, the main component of the crystalline substances is considered to be quartz (SiO)2) While the black wall is FeS which is the main substance of pyrite2. As can be seen from fig. 4(a0), the surface of the pyrite in the a.ferrivorans + pyrite system is smoother and more compact than the original ore sample, and the analysis suggests that the a.ferrivorans does not directly act on the pyrite, and the smoother surface of the slag is a physical action factor because the slag is soaked and shaken for a long time in an acidic environment, so that the edges and corners of the surface are ground flat. A. the2Due to the presence of Fe in the system3+The surface of the pyrite shows roughness and roughness under the chemical oxidation action of the pyrite, and Fe3+Not enough to destroy the metal sulfide lattice. (A)1) And (A)3) Respectively bacteria + Fe2++ pyrite system and bacteria + Fe3+The SEM image of the slag in the pyrite system is very intuitive, and a plurality of sunken cavities appear on the surface of the leached ore particles, so that a layered gully structure is presented, and corrosion traces are very obvious. At the same time, comparison (A)1) And (A)3) It is found that (A)1) Such a mark of the gully is more obvious. The combined analysis suggests that a. ferrivorans is comparable to Fe, compared to either a single iron ion or a. ferrivorans factor3+Or Fe2+Combined and coacted on pyrite, Fe2+The oxidation leaching effect is more obvious.
2.2.3 FTIR analysis of Secondary minerals
Are respectively to A1And A3System ofThe resulting secondary mineral was analyzed by FTIR and the results are shown in fig. 5.
As shown in FIG. 5, A1And A3The system generates jarosite FTIR spectrum which shows basically the same characteristic peak. 3391cm-1Is the telescopic vibration characteristic peak of-OH, 1638cm-1Characteristic peak of HOH deformation stretching vibration generated by water molecule deformation, 1043cm-1The peak is the-OH deformation stretching vibration characteristic peak. 1401cm-1For CH belonging to protein secondary structure2It is shown that while jarosite is produced, the bacteria self-propagate and synthesize a large amount of proteins and sugars. SO on jarosite4 2-The molecular stretching vibration characteristic peak mainly comprises two parts: located at 1196cm-1And 1091cm-1Is v3 (SO)4) Characteristic peak at 615cm-1And 634cm-1Has a shoulder peak of v4 (SO)4) Characteristic peak. 522cm-1The characteristic peak corresponds to FeO6An octahedral structure. The FTIR characteristic peaks of jarosite generated in this study were essentially the same as the standard jarosite characteristic peaks. Shows A1,A3In the system, jarosite precipitates are generated in the later oxidation stage, the generation of the precipitates is further promoted by the participation of bacteria, and jarosite and S-related oxides can be gathered and covered on the surface of minerals to prevent further leaching of metals. So A1System and A3The concentration of sigma Fe is kept constant at the later stage of leaching of the system and even the concentration is reduced because of the occurrence of coprecipitation.
2.2.4 XRD analysis of Secondary minerals
And filtering the A1 system with the best oxidation leaching effect to obtain the generated secondary mineral, drying the secondary mineral to obtain a yellow powdery substance, and carrying out XRD diffraction analysis on the yellow powdery substance, wherein the map is shown in figure 6.
The XRD pattern of the generated secondary mineral has typical characteristic peaks of standard jarosite and elemental sulfur, and the yellow powder is a mixture of jarosite and elemental sulfur. Analysis of the oxidation paths of Fe and S shows that the oxidation of Fe only occurs with a single process of electron transfer, while the oxidation of S is more complex than that of Fe. S except SO4 2-And S2 2-Two basic valence states, also present as S0、Sn 2-、SO3 2-And S2O3 2-And the intermediate valence state is equal. In the primary reaction stage, S element on the surface of the pyrite is firstly dissolved by Fe in the solution3+And O2Oxidation to form S0And Sn 2-As shown in formulas (2.6) - (2.7).
Figure BDA0003288039390000101
Sn 2-→S0 (2.7)
Elemental S is oxidized to form SO under the action of a. ferrivorans3 2-And S2O3 2-As shown in formulas (2.8) - (2.9).
Fe3++3O2+2S2 2-+e-→2S2O3 2-+Fe2+ (2.8)
S0-4e-+3H2O→SO3 2-+6H+ (2.9)
SO3 2-And S2O3 2-Is an extremely unstable thiosulfate which is easily oxidized by bacteria in a low pH environment to finally form SO4 2-As shown in formulas (2.10) - (2.11). Finally, SO formed4 2-With Fe in the liquid phase3+And K+Form jarosite precipitate as shown in formula (2.5).
Figure BDA0003288039390000111
Figure BDA0003288039390000112
2.2.5 XPS analysis of Secondary minerals
To further investigate the existence of elements in the transformation process of secondary minerals under the action of A.ferrivoransA with the formula and valence changed and the best oxidation effect1The binding energy of Fe2p, C1 s and O1s of the photoelectron spectroscopy pairs is adopted to measure the secondary mineral solid sample generated by the reaction, and the XPS PEAK 41 software is used to perform seal fitting on the obtained XPS spectrogram, which is shown in figure 7.
Fe 2p3/2And Fe2p1/2The binding energies of (A) and (B) are 711.7eV and 722.5eV (FIG. 7 (b)), which are both higher than 710eV, indicating that the iron in the secondary mineral exists in the form of Fe (III), demonstrating that Fe in the system is oxidized by A.ferrivorans2+Is substantially totally oxidized into Fe3+. For Fe2p3/2Performing seal-separating fitting analysis to obtain Fe (III) and Fe (III) -SO4And Fe (OH) O characteristic peaks corresponding to electron binding energies of 715.8eV, 713.5eV, and 711.6eV, respectively; fe2p1/2The two satellite peak binding energies of (a) are 727.1eV and 725.2eV, respectively.
From the XPS spectrum of O1s ((d) in FIG. 7), it can be seen that there are Fe (OH) O and Fe2O3Characteristic peak of (2). The C1 s peak results (FIG. 7 (C)) show the presence of three carbon bonds, C-O, C-OH and C-C, respectively, indicating that the jarosite surface has traces of microbial presence, resulting in carbon-based organics.
2.3A. ferrivorans oxidative leach UO2Effects influence
UO2The changes of the addition amount to the pH and Eh of the a. ferrivorans oxidation leaching and the iron ion concentration in the solution are shown in (d) to (f) of fig. 1. In the bacterial immersion system, Eh reacts Fe3+/Fe2+The larger the ratio, the larger the Eh value is, the Fe in the system is shown3+The higher the concentration, the positive effect on leaching. In the system with uranium, the Eh value is determined by Fe3+/Fe2+And U6+/U4+Both of them are determined together, and the pH value and the Eh change have a certain correlation at 0-2 d, because of Fe3+For UO2Chemical oxidation of, Fe3+Is reduced to Fe2+And further make Fe3+/Fe2+The ratio is reduced, Eh shows a downward trend, and the relevant reaction equation is shown as the formula (2.12).
UO2+Fe2(SO4)3→2FeSO4+UO2SO4 (2.12)
By comparing the concentration of the sigma Fe with the group A, the general trend of the group C conforms to the constructed model, and the good corresponding relation exists, so that the leaching of the iron C can be seen3>C4>C1>C2>C0In agreement with the previous study rules.
Solid UO as leaching test continued2The uranium leaching rate in different systems changes along with time as shown in figure 8.
It can be seen that C is compared to other leaching systems1System and C3The uranium leaching rate of the system is relatively high and is 94.69 percent and 99.94 percent. Meanwhile, the rising curves of the uranium leaching rates of the two are basically consistent and are in a step shape, which correspond to the first three periods of an A.ferrivorans growth curve, namely 1-3 d corresponds to a slow period, 3-6 d corresponds to a logarithmic period, and 7-8 d corresponds to a stable period. C2System and C4System pair UO2Leaching was relatively low, 49.77% and 61.55%, respectively.
The change analysis in the two groups of experiments of A, C and the uranium leaching process is combined to obtain that A.ferrivorans and Fe exist in the system2+The leaching rate of uranium can be greatly improved by two factors, namely, when the activity of A.ferrivorans is stronger, Fe is oxidized2+In the process, the leaching rate of uranium can be greatly increased. And the addition of 1g/L pyrite has a trace gain effect on leaching of uranium.
2.4A. construction of ferrivorans Oxidation phase model
And comprehensively analyzing the A and C groups of tests, and combining the characterization analysis of the slag and the secondary minerals, wherein the iron ions and the S element are considered to play a vital role in the whole microbial oxidation process. Analyzing and summarizing the oxidation law of A.ferrivorans and establishing that Fe exists in an initial environment system under an acidic condition3+And Fe2+Ferrivorans oxidized pyrite stage model, as in fig. 9.
The first stage is mainly a microbial oxidation stage. Inoculation of ferrivorans into a new environmental system will preferentially utilize Fe in the liquid phase2+Free Fe in liquid phase2+Is consumed rapidly. In the same period, the inorganic chemical oxidation is carried out simultaneously, Fe2+A large amount of Fe is generated while oxidizing3+,Fe3+Further oxidize FeS on the surface of the pyrite2Forming elemental S or an intermediate oxide of S, and the iron element is replaced from the pyrite. The microbial oxidation proceeds at a much greater rate than inorganic chemical oxidation at this stage, and the liquid phase pH shows a tendency to rise.
The second stage is mainly the formation of a pyrite surface sulfidization film and the surface oxidation of pyrite. Simultaneous UO2In Fe3+Under the action of the catalyst, UO is generated2 2+Ferrivorans adsorbs to the surface of pyrite in large quantities due to the adhesive properties of EPS. The S simple substance generated by the first stage oxidation can generate a series of S intermediate oxides under the oxidation action of A.ferrivorans, and the S intermediate oxides are finally oxidized to SO4 2-The final state of (1). The series of S intermediates and a. ferrivorans polymerize simultaneously on the surface of pyrite, forming a sulfide film layer. At the same time, Fe3+Can continuously oxidize pyrite and UO2Ferrivorans may also produce direct oxidation of pyrite, which continues to erode the surface of the pyrite and uranium dioxide, changing the morphology. Also due to the presence of a. ferrivorans EPS, a significant amount of free iron ions in the liquid phase may be adsorbed, possibly resulting in a reduction of iron ions in the liquid phase.
The third stage is mainly manifested by strengthening of the vulcanized film and decay of a. ferrivorans. The reaction proceeds to this stage, where a. ferrivorans has been propagated in large areas and distributed throughout the environmental system. UO2Substantially completely oxidized in solution as UO2 2+The ionic state exists and at the same time, Fe exists in the liquid phase2+After the iron source is basically consumed, the iron source which is oxidized and supplemented from the pyrite is rapidly consumed, so that the A.ferrivorans which are adsorbed to the surface of the pyrite and erode the pit are supplemented by the old iron source, certain biological activity is kept, the sulfide film is continuously strengthened, and the inside and the outside of the pyrite are separated due to the existence of the sulfide film; and a large amount of A.ferrivorans outside the pyrite, without the supplement of iron source, the life activity is lost,beginning large-area decline; this process is accompanied by jarosite formation, simultaneous microbial oxidation and inorganic chemical oxidation, which causes inward depression of the pyrite surface, the encapsulation of a.ferrivorans in the film and the loss of a.ferrivorans in the outer layer of the film due to this "jail" layer, oxygen is isolated and no energy is supplied, and essentially all die. Meanwhile, the vulcanized film continues to generate oxidation reaction, and more SO is generated4 2-With addition of Fe3+Is absorbed to the vulcanization film layer, and the vulcanization film layer is converted into an jarosite layer. By this time, microbial oxidation and inorganic chemical oxidation have been carried out on pyrite and UO2The action of (c) is totally stopped.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. Use of Acidithiobacillus caldus (Acidithiobacillus ferrorans) for the oxidative leaching of pyrites and low-grade uranium ores.
2. The system for oxidizing and leaching pyrite is characterized in that the pH value of the system is 2.0, the system comprises a bacterial liquid of Acidithiobacillus acidophilus, a culture medium and pyrite, and the culture medium contains 1g/L-5g/L of Fe2+Or Fe3+
3. The system of claim 2, wherein the volume ratio of the bacterial liquid to the culture medium is 1: 9.
4. the system of claim 2 or 3, wherein the composition of the culture medium comprises: (NH)4)2SO4 3g/L、K2HPO4 0.5g/L、KCl 0.1g/L、MgSO4 0.5g/L、Ca(NO3)20.01g/L and Fe2+(1g/L-5g/L)。
5. The system according to claim 2, wherein the mass-to-volume ratio of pyrite to the system in the system is 0.1 g: 100 mL.
6. A method for oxidative leaching of pyrite, characterized in that the system according to any one of claims 2 to 5 is formulated and cultured at a temperature of 30 ℃ and a rotation speed of 170 r/min.
7. The system for oxidizing and leaching low-grade uranium ore is characterized in that the pH value of the system is 2.0, the system comprises a bacterial liquid of Acidithiobacillus psychrophilus (Acidithiobacillus. ferrivorans), a culture medium and the low-grade uranium ore, and the culture medium contains 1g/L of Fe2+Or Fe3+
8. The system of claim 7, wherein the volume ratio of the bacteria liquid to the culture medium in the system is 1: 9, the mass volume ratio of the low-grade uranium ore to the system is 0.1 g: 100 mL.
9. The system according to claim 7 or 8, characterized in that 0.1g of pyrite is further included per 100mL of the system.
10. A method for oxidative leaching of low-grade uranium ore, characterized in that a system according to any one of claims 7 to 9 is prepared and cultured at a temperature of 30 ℃ and a rotation speed of 170 r/min.
CN202111154270.4A 2021-09-29 2021-09-29 Application of acidithiobacillus psychrophilus in oxidative leaching of pyrite and low-grade uranium ore, system and method Pending CN113897483A (en)

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