Method for bioleaching semiconductor sulfide minerals by using jarosite to enhance photocatalysis
Technical Field
The invention belongs to the technical field of biological metallurgy, and particularly relates to a method for bioleaching semiconductor sulfide minerals by using jarosite to enhance photocatalysis.
Background
At present, the copper is extracted mainly by adopting a pyrometallurgy method, and the method can generate a large amount of pollution and has high cost. The bioleaching technology has the advantages of simple operation, mild reaction conditions, environmental friendliness, low cost and the like, and can treat low-grade complex minerals which are difficult to treat, so that the bioleaching technology is widely concerned. At present, 20-25% of copper all over the world is obtained by bioleaching, so that bioleaching has good application prospect in the field of mineral resource processing. However, sulfide mineral bioleaching has the defects of long leaching period, low leaching rate and the like, and further wide application of the sulfide mineral bioleaching is limited. There is therefore a need to find a viable method to increase the bioleaching efficiency of sulphide minerals. In recent years, a large number of researchers have improved leaching of sulfide mineral bacteria by means of adjusting the pH value and oxidation-reduction potential of the system, adding a catalyst, mixing flora at high temperature during use, and the like. They have met with some success, but they have ignored the semiconducting properties of sulfide mineral bioleaching processes.
The photo-generated electrons excited when the visible light irradiates the semiconductor sulfide minerals can be converted into chemical energy utilized by acidophilic iron sulfur oxidizing bacteria to promote the growth of the bacteria, so that the biological leaching of the sulfide minerals can be promoted by utilizing the photocatalytic performance of the sulfide minerals. But more jarosite is generated in the process of bioleaching the sulfide minerals under the illumination condition, the jarosite can passivate the surfaces of the sulfide minerals, the transfer rate of photoproduction electrons can be inhibited, the recombination of the photoproduction electrons and photoproduction holes is increased, and the efficiency of bioleaching the photocatalytic sulfide minerals is reduced. Therefore, the inhibition of the formation of jarosite on the surface of the sulfide minerals has important significance for improving the bacterial leaching efficiency of the photocatalytic sulfide minerals. The added jarosite can be used as a seed crystal to promote the formation of jarosite on the surface of the seed crystal in a leaching system, so that the formation of passivation jarosite on the surface of a sulfide mineral can be reduced, and the biological leaching efficiency of the sulfide mineral is remarkably improved. The method remarkably increases the biological leaching efficiency of the photocatalytic semiconductor sulfide minerals by additionally biologically synthesizing the jarosite.
Disclosure of Invention
The invention aims to improve the biological leaching efficiency of photocatalytic semiconductor sulfide minerals, and provides a method for strengthening the biological leaching of photocatalytic semiconductor sulfide minerals by jarosite.
The purpose of the invention is realized by the following modes:
a method for leaching jarosite from semiconductor sulfide minerals by using photocatalysis is characterized in that jarosite is added in the process of leaching the semiconductor sulfide minerals by using photocatalysis.
According to the method for the jarosite-enhanced photocatalytic biological leaching of semiconductor sulfide minerals, the concentration of the jarosite in a photocatalytic biological leaching system of semiconductor sulfide minerals is 0.1-6 g/L; further preferably, the concentration is 0.5 to 2 g/L.
The jarosite is used for strengthening the photocatalytic biological leaching of semiconductor sulfide minerals, and the jarosite is biosynthesized.
The jarosite-enhanced photocatalytic semiconductor sulfide mineral bioleaching method comprises the following steps: according to 108-109cells/mL inoculum size acidophilic ferrooxidans were inoculated into 250mL containing 0.08-0.32M FeSO4·7H2O and 13.33-53.30mM K2SO4pH 2.0-3.0 in aqueous solution, and FeSO4·7H2O and K2SO4The molar ratio of (1: 6), culturing at 20-50 deg.C with the rotation speed of shaker of 100-. The yellow precipitate is collected, preferably with 0.1M H2SO4And repeatedly washing with deionized water for 3-5 times, and vacuum drying at 50 deg.C for 12 hr.
The method for strengthening the photo-catalytic biological leaching of the semiconductor sulfide minerals by the jarosite has the advantages that the illumination intensity in a photo-catalytic biological leaching system of the semiconductor sulfide minerals is 4000-12000lux, and is preferably 8000-12000 lux.
The method for the jarosite-enhanced photocatalytic biological leaching of semiconductor sulfide minerals is characterized in that 1-5% of semiconductor sulfide minerals with pulp concentration are added into a photocatalytic semiconductor sulfide mineral biological leaching system.
The biological leaching of the jarosite-enhanced photocatalytic semiconductor sulfide mineral is carried out by utilizing acidophilic iron-sulfur oxidizing bacteria, preferably domesticating the acidophilic iron-sulfur oxidizing bacteria.
The acidophilic iron-sulfur oxidizing bacteria include: acidithiobacillus ferrooxidans (Acidithiobacillus ferrooxidans), Acidithiobacillus mesophilic (Ferrithrixthermotolerans) or leptospirillum ferrooxidans (Leptospirillum ferrooxidans). All belong to conventional commercially available mineral leaching bacteria.
The method for leaching the semiconductor sulfide minerals by using jarosite to enhance photocatalysis comprises the following steps of inoculating the semiconductor sulfide minerals by using an inoculation amount of 1 multiplied by 107-9×107cells/ml acidophilic iron sulfur oxidizing bacteria are inoculated into a leaching system.
The method for the jarosite-enhanced photocatalytic semiconductor sulfide mineral bioleaching comprises the steps that the pH value of a leaching system is 1.5-3.0, the rotating speed of a shaking table is 100-200rpm, and the temperature is 20-50 ℃.
The jarosite-enhanced photocatalytic bioleaching method for semiconductor sulfide minerals comprises the following steps: one or more of chalcopyrite, covellite, bornite, chalcocite and pyrite, preferably the semiconductor sulphide mineral is crushed and sieved to a particle size below 74 μm, and stored in a nitrogen atmosphere for later use before use.
A method of biosynthesizing jarosite enhanced photocatalytic bioleaching of semiconductor sulphide minerals, preferably comprising the steps of:
(1) firstly, inoculating 5-10ml of acidophilic iron-sulfur oxidizing bacteria bacterial liquid into 100ml of 9K culture medium containing semiconductor sulfide ore with 1% ore pulp concentration, and repeatedly performing acclimatization culture until the bacterial concentration can reach 108cells/ml, finishing the first domestication, collecting bacteria, repeating the steps, and sequentially domesticating in the semiconductor sulfide ore pulp with the ore pulp concentration of 2%, 3%, 4% and 5% until the acidophilic iron-sulfur oxidizing bacteria can adapt to the semiconductor sulfide ore pulp concentration of 1-5% of the ore pulp concentration.
(2) According to 108-109cells/mL inoculum size acidophilic ferrooxidans were inoculated into 250mL containing 0.08-0.32M FeSO4·7H2O and 13.33-53.30mM K2SO4pH 2.0-3.0 in aqueous solution, and FeSO4·7H2O and K2SO4The molar ratio of (1 to 6) is 100-200rpm at 20-50 deg.C, collecting yellow precipitate after 3-7 days, and adding 0.1M H2SO4Repeatedly washing with deionized water for 3-5 times, and vacuum drying at 50 deg.C for 12 hrSo as to obtain the biosynthetic jarosite.
(3) Inoculating acidophilic iron-sulfur oxidizing bacteria with inoculum size of 3 × 107-9×107cells/ml are inoculated into a 9K culture medium containing semiconductor sulfide minerals with the concentration of 1-5% of ore pulp for amplification culture, and the conditions of amplification culture are that the initial pH is 1.5-3.0 and the temperature is 20-50 ℃.
(4) Centrifugally collecting the acidophilic iron-sulfur oxidizing bacteria cultured to the middle logarithmic phase in the step (3), wherein the inoculation amount of the acidophilic iron-sulfur oxidizing bacteria is 1 × 107-9×107cells/ml is inoculated into a 9k culture medium containing 0.1-6.0g/L biosynthetic jarosite and 1-5% pulp concentration semiconductor sulfide mineral, pH is 1.5-3.0, and leaching is carried out under the conditions that the illumination intensity is 4000-12000lux, the rotating speed of a shaking table is 100-200rpm and the temperature is 20-50 ℃.
(5) Respectively measuring pH and oxidation reduction potential in the solution of the bacterial leaching system by using a pH meter and a portable potential measuring instrument every 3 days, and measuring Fe in the solution by using an ICP emission spectrometer2+Total iron ions and Cu2+And (4) concentration.
(6) And after bioleaching is finished, filtering and collecting slag by using filter paper to analyze the surface appearance and the phase and element composition.
The 9K culture medium of the invention has the following formula: (NH)4)2SO43.0g/L、KC1 0.1g/L、K2HPO40.5g/L、MgSO4·7H2O0.5g/L、Ca(NO3)20.01g/L, with 0.01mol/L H2SO4Adjusting the pH value to 1.5-3.0.
The added biosynthetic jarosite can be used as a seed crystal to promote the jarosite in a leaching system to be mainly formed on the surface of the seed crystal, so that the formation of the jarosite on the surface of a semiconductor sulfide mineral is reduced. Surface morphology analysis, phase and element composition analysis show that jarosite can reduce passivation substances (jarosite and S)n 2-/S0) are formed on the surface of the sulphide minerals (as shown in fig. 6 and 7), so that the added biosynthetic jarosite promotes bioleaching of the sulphide minerals. Moreover, the invention unexpectedly finds that the effect of the biological synthesized jarosite is better than that of the chemical synthesized jarosite.
The method obviously improves the bacterial leaching efficiency of the photocatalytic semiconductor sulfide mineral by adding the biosynthetic jarosite, has simple required equipment, mild reaction condition, low cost and environmental protection, and thus provides possibility for wide application of the photocatalytic semiconductor sulfide mineral bioleaching. The invention is mainly suitable for semiconductor sulfide minerals.
Drawings
FIG. 1 is a graph showing the trend of copper ion concentration in a solution of the leaching system of example 1;
FIG. 2 is a graph showing the trend of the copper ion concentration in the solution of the leaching system of example 2;
FIG. 3 is a graph showing the trend of the copper ion concentration in the solution of the leaching system of example 3;
FIG. 4 is a graph showing the trend of the copper ion concentration in the solution of the leaching system of example 4;
FIG. 5 is a graph showing the trend of the copper ion concentration in the solution of the leaching system of example 5;
FIG. 6 is a scanning electron microscope image of surface topography;
dark 0.0g/L means no light and no addition of biosynthetic jarosite,
dark 1.0g/L indicates no light and 1.0g/L biosynthetic jarosite is added to the leaching system,
illumination of 0.0g/L indicates illumination without addition of biosynthetic jarosite,
illumination 1.0g/L indicates illumination and 1.0g/L of biosynthetic jarosite was added to the leaching system.
FIG. 7 is an elemental composition analysis X-ray photoelectron spectroscopy analysis chart;
dark 0.0g/L means no light and no addition of biosynthetic jarosite,
dark 1.0g/L indicates no light and 1.0g/L biosynthetic jarosite is added to the leaching system,
illumination of 0.0g/L indicates illumination without addition of biosynthetic jarosite,
illumination 1.0g/L indicates illumination and 1.0g/L of biosynthetic jarosite was added to the leaching system.
Detailed Description
The following specific examples or embodiments are intended to further illustrate the invention, but are not intended to limit the invention.
Example 1
The method of the embodiment is mainly carried out according to the following steps:
(1) according to 4X 108cells/mL inoculum size Cochlospira ferrooxidans was inoculated to 250mL of a solution containing 0.16MFeSO4·7H2O and 26.65mM K2SO4The culture was carried out at 40 ℃ with a shaker rotation speed of 170rpm in an aqueous solution of pH2.0, and after 3 days, the yellow precipitate was collected by filtration through filter paper and 0.1M of H was used2SO4Repeatedly cleaning with deionized water for 3-5 times, and vacuum drying at 50 deg.C for 12 hr to obtain jarosite material;
(2) crushing and screening a chalcopyrite ore sample until the particle size is below 74 mu m, storing the chalcopyrite ore sample for later use in a nitrogen atmosphere, detecting by synchronous radiation XRD before an experiment to find that the main phase composition of the chalcopyrite ore is chalcopyrite, and a small amount of silicon dioxide and pyrite exist, and analyzing mineral elements by XRF to be Cu, 33.21%, S, 31.59%, Fe, 28.21%, O, 4.88% and other elements to be 2.11%;
(3) pre-domesticated leptospirillum ferrixide with the inoculum size of 3.2 multiplied by 107Inoculating cells/ml into a 9K culture medium containing chalcopyrite with the pulp concentration of 2 percent for amplification culture, wherein the conditions of the amplification culture are that the initial pH is 2.0 and the temperature is 40 ℃;
(4) centrifugally collecting leptospira ferrooxidans cultured to the middle logarithmic phase in the step (3), wherein the inoculation amount of leptospira ferrooxidans is 3.2 multiplied by 107cells/ml are inoculated into 9k culture medium containing 0.5g/L biosynthetic jarosite and 2% pulp concentration chalcopyrite, pH2.0, and leached for 28 days under the conditions of illumination intensity of 12000lux, shaking table rotation speed of 170rpm and temperature of 40 ℃.
(5) Measuring Cu in the solution by adopting an ICP emission spectrometer every 3 days2+Concentration (shown in fig. 1).
And (4) conclusion: as shown in FIG. 1, the leaching rate of chalcopyrite under the combined action of 12000Lux visible light with light intensity and 0.5g/L biosynthetic jarosite is improved by 34 percent compared with the leaching rate of a control group without adding the biosynthetic jarosite under dark conditions, and is improved by 6.9 percent compared with the leaching rate of the chalcopyrite without adding the biosynthetic jarosite with light intensity of 12000 Lux. When no illumination is added and the jarosite is biosynthesized, the chalcopyrite is seriously passivated on the 16 th day, the concentration of copper ions is not increased any more, and the illumination or the biosynthesized jarosite copper ions can be continuously increased until the higher acceleration is achieved in 28 days.
Example 2
The method of the embodiment is mainly carried out according to the following steps:
(1) according to 5X 108Inoculation amount of cells/mL Acidithiobacillus ferrooxidans was inoculated into 250mL of a culture medium containing 0.16MFeSO4·7H2O and 26.65mM K2SO4The culture was carried out at 30 ℃ with a shaker rotation speed of 170rpm in an aqueous solution of pH2.0, and after 3 days, the yellow precipitate was collected by filtration through filter paper and 0.1M of H was used2SO4Repeatedly cleaning with deionized water for 3-5 times, and vacuum drying at 50 deg.C for 12 hr to obtain jarosite material;
(2) crushing and screening a chalcopyrite ore sample until the particle size is below 74 mu m, storing the chalcopyrite ore sample for later use in a nitrogen atmosphere, detecting by synchronous radiation XRD before an experiment to find that the main phase composition of the chalcopyrite ore is chalcopyrite, and a small amount of silicon dioxide and pyrite exist, and analyzing mineral elements by XRF to be Cu, 33.21%, S, 31.59%, Fe, 28.21%, O, 4.88% and other elements to be 2.11%;
(3) inoculating Acidithiobacillus ferrooxidans domesticated in advance to 3.2 × 107Inoculating cells/ml into a 9K culture medium containing chalcopyrite with the pulp concentration of 2 percent for amplification culture, wherein the conditions of the amplification culture are that the initial pH is 2.0 and the temperature is 30 ℃;
(4) centrifugally collecting the acidithiobacillus ferrooxidans cultured to the middle logarithmic phase in the step (3), wherein the inoculation amount of the acidithiobacillus ferrooxidans is 3.2 multiplied by 107cells/ml are inoculated into 9k culture medium containing 1.0g/L biosynthetic jarosite and 2% pulp concentration chalcopyrite, pH2.0, and leached for 28 days under the conditions of illumination intensity of 12000lux, shaking table rotation speed of 170rpm and temperature of 30 ℃.
(5) Every 3 days, the ICP emission spectrometer is used for measuring Cu in the solution2+Concentration (shown in fig. 2).
And (4) conclusion: as shown in FIG. 2, the leaching rate of chalcopyrite under the combined action of 12000Lux visible light with light intensity and 1.0g/L biosynthetic jarosite is increased by 35.7 percent compared with the leaching rate of a control group without adding the biosynthetic jarosite under dark conditions, and is increased by 8.2 percent compared with the leaching rate of the light intensity of 12000Lux biosynthetic jarosite without adding the biosynthetic jarosite. When no illumination is added and the jarosite is biosynthesized, the chalcopyrite is seriously passivated on the 16 th day, the concentration of copper ions is not increased any more, and the illumination or the biosynthesized jarosite copper ions can be continuously increased until the higher acceleration is achieved in 28 days.
Example 3
The method of the embodiment is mainly carried out according to the following steps:
(1) according to 4X 108Inoculation amount of cells/mL Acidithiobacillus ferrooxidans was inoculated into 250mL of a culture medium containing 0.16MFeSO4·7H2O and 26.65mM K2SO4The culture was carried out at 30 ℃ with a shaker rotation speed of 170rpm in an aqueous solution of pH2.0, and after 3 days, the yellow precipitate was collected by filtration through filter paper and 0.1M of H was used2SO4Repeatedly cleaning with deionized water for 3-5 times, and vacuum drying at 50 deg.C for 12 hr to obtain jarosite material;
(2) crushing and screening a chalcopyrite ore sample until the particle size is below 74 mu m, storing the chalcopyrite ore sample for later use in a nitrogen atmosphere, detecting by synchronous radiation XRD before an experiment to find that the main phase composition of the chalcopyrite ore is chalcopyrite, and a small amount of silicon dioxide and pyrite exist, and analyzing mineral elements by XRF to be Cu, 33.21%, S, 31.59%, Fe, 28.21%, O, 4.88% and other elements to be 2.11%;
(3) inoculating Acidithiobacillus ferrooxidans domesticated in advance to 3.2 × 107Inoculating cells/ml into a 9K culture medium containing chalcopyrite with the pulp concentration of 2 percent for amplification culture, wherein the conditions of the amplification culture are that the initial pH is 2.0 and the temperature is 30 ℃;
(4) centrifugally collecting the acidithiobacillus ferrooxidans cultured to the middle logarithmic phase in the step (3), wherein the inoculation amount of the acidithiobacillus ferrooxidans is 3.2 multiplied by 107cells/ml are inoculated into 2g/L biosynthetic jarosite and 2% pulp concentrationLeaching chalcopyrite with a concentration of 9k in a culture medium with a pH value of 2.0 for 28 days under the conditions that the illumination intensity is 12000lux, the rotating speed of a shaking table is 170rpm and the temperature is 30 ℃;
(5) every 3 days, the ICP emission spectrometer is used for measuring Cu in the solution2+Concentration (shown in fig. 3).
And (4) conclusion: as shown in FIG. 3, the leaching rate of chalcopyrite under the combined action of 12000Lux visible light with 2g/L biosynthetic jarosite is improved by 34.6 percent compared with the leaching rate of a control group without adding the biosynthetic jarosite under dark conditions, and is improved by 7.3 percent compared with the leaching rate of the chalcopyrite without adding the biosynthetic jarosite under 12000Lux visible light. When no illumination is added and the jarosite is biosynthesized, the chalcopyrite is seriously passivated on the 16 th day, the concentration of copper ions is not increased any more, and the illumination or the biosynthesized jarosite copper ions can be continuously increased until the higher acceleration is achieved in 28 days.
Example 4
The method of the embodiment is mainly carried out according to the following steps:
(1) according to 4X 108Inoculation amount of cells/mL Acidithiobacillus ferrooxidans was inoculated into 250mL of a culture medium containing 0.16MFeSO4·7H2O and 26.65mM K2SO4The culture was carried out at 30 ℃ with a shaker rotation speed of 170rpm in an aqueous solution of pH2.0, and after 3 days, the yellow precipitate was collected by filtration through filter paper and 0.1M of H was used2SO4Repeatedly cleaning with deionized water for 3-5 times, and vacuum drying at 50 deg.C for 12 hr to obtain jarosite material;
(2) crushing and screening a chalcopyrite ore sample until the particle size is below 74 mu m, storing the chalcopyrite ore sample for later use in a nitrogen atmosphere, detecting by synchronous radiation XRD before an experiment to find that the main phase composition of the chalcopyrite ore is chalcopyrite, and a small amount of silicon dioxide and pyrite exist, and analyzing mineral elements by XRF to be Cu, 33.21%, S, 31.59%, Fe, 28.21%, O, 4.88% and other elements to be 2.11%;
(3) inoculating Acidithiobacillus ferrooxidans domesticated in advance to 3.2 × 107Inoculating cells/ml into a 9K culture medium containing chalcopyrite with the pulp concentration of 2 percent for amplification culture, wherein the conditions of the amplification culture are that the initial pH is 2.0 and the temperature is 30 ℃;
(4) centrifugally collecting the acidithiobacillus ferrooxidans cultured to the middle logarithmic phase in the step (3), wherein the inoculation amount of the acidithiobacillus ferrooxidans is 3.2 multiplied by 107cells/ml are inoculated into 9k culture medium containing 4g/L of biosynthetic jarosite and 2% of chalcopyrite with pulp concentration and pH2.0, and are leached for 28 days under the conditions that the illumination intensity is 12000lux, the rotating speed of a shaking table is 170rpm and the temperature is 30 ℃;
(5) every 3 days, the ICP emission spectrometer is used for measuring Cu in the solution2+Concentration (shown in fig. 4).
And (4) conclusion: as shown in FIG. 4, the leaching rate of chalcopyrite under the combined action of 12000Lux visible light with 4g/L biosynthetic jarosite is improved by 33.5 percent compared with the leaching rate of a control group without adding the biosynthetic jarosite under dark conditions, and is improved by 6.5 percent compared with the leaching rate of the chalcopyrite without adding the biosynthetic jarosite under 12000Lux visible light with 4g/L biosynthetic jarosite. When no illumination is added and the jarosite is biosynthesized, the chalcopyrite is seriously passivated on the 16 th day, the concentration of copper ions is not increased any more, and the illumination or the biosynthesized jarosite copper ions can be continuously increased until the higher acceleration is achieved in 28 days.
Example 5
The procedure of this example is the same as example 2, but the jarosite used is chemically synthesized, not biosynthesized, and the jarosite chemical synthesis procedure is: 0.2g of KNO3And 1.18g of Fe2(SO4)3Adding into 100ml 0.1M sulfuric acid solution, magnetically stirring at 80 deg.C for 12 hr, filtering to collect yellow precipitate, and adding 0.1M H2SO4Repeatedly washing with deionized water for 3-5 times, and vacuum drying at 50 deg.C for 12 hr to obtain jarosite material.
The results show that: the leaching rate of chalcopyrite under the combined action of the visible light with the light intensity of 12000Lux and the chemically synthesized jarosite with the light intensity of 1g/L is improved by 26.8 percent compared with the leaching rate of a control group without adding the jarosite under the dark condition, and is increased by 1.1 percent compared with the leaching rate of the jarosite without adding the biologically synthesized jarosite with the light intensity of 12000Lux (as shown in figure 5). The promoting effect of the chemically synthesized jarosite is obviously weaker than that of the biologically synthesized jarosite.