CN1351180A - Microbe-catalytic oxidization-reduction compling process for extracting valuable metals from manganese oxide ore - Google Patents
Microbe-catalytic oxidization-reduction compling process for extracting valuable metals from manganese oxide ore Download PDFInfo
- Publication number
- CN1351180A CN1351180A CN 00130238 CN00130238A CN1351180A CN 1351180 A CN1351180 A CN 1351180A CN 00130238 CN00130238 CN 00130238 CN 00130238 A CN00130238 A CN 00130238A CN 1351180 A CN1351180 A CN 1351180A
- Authority
- CN
- China
- Prior art keywords
- pyrite
- leaching
- culture medium
- strain
- domestication
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
A mocrobe-catalytic oxidization-reduction process for extracting valuable metals from manganese oxide ore features that the sulfur ferrous oxide bacillus is used as bacterial strain, the leathen culture medium is used, pyrite is used as reducer, and the bacterial infusion of pyrite is used to regulate pH value. After said bacterial strain is nuturalized, it is used for catalytic oxidaization-reduction reaction of said manganese oxide ore in acidic environment to directly extract valuable metals. Its advantages include simple process, less investment, low cost and environment protection.
Description
The invention relates to the technical field of microbial metallurgy, in particular to a microbial catalytic oxidation-reduction coupling leaching method for valuable metals in manganese oxide ore in deep sea and land.
Oxidized ore and reduced ore are the most important mineral resources, oxidation-reduction reaction is difficult to occur between solid phases due to the complex structure of the ore, and valuable metal extraction process is complex and generally needs to be roasted under high temperature and high pressure by adding corresponding oxidant or reducing agent. But can catalyze oxidation-reduction reaction under normal temperature and normal pressure in the presence of microorganisms.
Various processes are researched and applied at home and abroad for the wet treatment of manganese oxide ores, wherein the traditional reduction roasting-dilute sulfuric acid leaching method is the most mature and reliable method and the most common method is also applied. But the process has a high-temperature reduction roasting operation, namely, high-valence manganese oxide ore is heated to 700-800 ℃, reduced into bivalent manganese oxide by a reducing agent and leached by dilute sulfuric acid solution. The process consumes a large amount of heat energy and has poor working conditions, so people adopt experimental research of directly adding a reducing agent into ore pulp and leaching manganese oxide ores under the condition of heating or normal temperature, namely manganese is leached out while the manganese oxide ores are reduced;
the manganese industry of China (Vol.13 No. 61995) discloses a manganese test by low-temperature leaching of manganese oxide ore reduced by aniline, and the manganese oxide ore used for the test is an acidic manganese oxide ore with low phosphorus and high iron, and the chemical components of the manganese oxide ore are as follows: MnO233.58％、Fe11.98％、CaO 0.55％、MgO 0.26％、SiO 7.56％、Al2O39.16%, P0.068% and S0.89%, 30g of manganese oxide ore for experiments, and the particle size is as follows: -0.074mm of 70% and a leaching agent of 15% dilute sulphuric acid solution, operating at room temperature, aniline and MnO in the ore2The weight ratio of the ore pulp to the water is 1: 1, the solid-liquid ratio of the ore pulp is 1: 5, the leaching time is 6 hours, and the leaching rate is 90 percent. Therefore, the process is effective in using aniline as a reducing agent to leach manganese from manganese oxide ore at low temperature. But the production cost of the aniline is higher at present, and the aniline is not suitable for industrial production;
the manganese industry of China (Vol.13 No. 41995) discloses research on reduction leaching of manganese oxide ore, the manganese content of a manganese oxide raw ore is 26.45%, manganese concentrate obtained by crushing and magnetic separation contains 35.9% of manganese, a reducing agent is pyrite, the leaching temperature is 95 ℃, the manganese yield is 66%, and thus the method also has the problems of energy consumption, poor operating conditions and the like;
the deep sea manganese oxide ore is a composite oxide ore taking iron and manganese high-valence oxides as main ore phases. Valuable metals with industrial extraction value comprise Cu, Co, Ni, Mn and the like, wherein Ni, Co and Cu are embedded in the crystal lattices of iron, manganese-oxygen-iron and manganese oxide in an adsorption or ion substitution mode, basically, no possibility of mechanical sorting enrichment exists, and the crystal lattices of the manganese oxide must be firstly damaged for extracting the elements. The manganese dioxide does not react with acid and alkali at normal temperature and normal pressure, so that the processing process is complicated.
Since sixty years, a great deal of research work is carried out on the processing treatment of the deep-sea manganese oxide ore, dozens of schemes are proposed, wherein the research is deeper, and the following five methods are mainly used through the expansion test and inspection: a reduction roasting ammonia leaching method, a cuprous ion ammonia leaching method, a high-temperature high-pressure sulfuric acid leaching method, a hydrogen chloride reduction roasting leaching method and a smelting-vulcanization-leaching method.
Of the five methods mentioned above, the first two are ammonia leaching methods, which have the advantages of no leaching of iron and manganese, strong selectivity, less reagent corrosion, less consumption and easy recovery. The disadvantages are low leaching recovery, especially low cobalt recovery, and difficulty in recovering manganese. The high-temperature high-pressure sulfuric acid leaching method has the advantages of strong selectivity, no need of drying ores, direct leaching, reliable process, low cobalt yield, incapability of recovering manganese, high requirement on equipment materials and high investment. The hydrogen chloride reduction roasting leaching method has high metal recovery rate (particularly cobalt), can comprehensively recover four metals of manganese, cobalt, nickel and copper, but has large reagent consumption and strong corrosivity, and the process for recovering manganese is not only complex, but also has high energy consumption. The advantages of smelting-sulfurizing-leaching method are high recovery rate of metal, recovery of Mn, less consumption of reagent in process, but high energy consumption.
The invention patent application with application number 00102747.6 of the applicant discloses a microbial leaching method of heavy metals in deep sea polymetallic nodules, which uses thiobacillus ferrooxidans, thiobacillus thiooxidans or mixed strains thereof as strains, a mixture of Leathen culture medium and textile dye sewage as a culture medium, pyrite, ferrous sulfate and sulfur elements as reducing agents, a bacterial raw pyrite leaching agent is used for adjusting the pH value, the strains are domesticated, the polymetallic nodules do not need to be dried and ground, and the heavy metals in the deep sea polymetallic nodules are directly leached in normal temperature and acidic environment.
The specific leaching steps include:
eliminating the induction period of the strain on pyrite:
the strain adopts Thiobacillus ferrooxidans T.f, Thiobacillus thiooxidans T.t or a mixed strain of Thiobacillus ferrooxidans and Thiobacillus thiooxidans;
the culture medium is a mixed culture medium and is prepared by mixing a Leathen culture medium and textile dye sewage in a weight ratio of 20: 1-3: 1, and the pH value is 1.5-2.5;
2 or 3 times of domesticating strains:
(1) 1, domestication: putting the crushed pyrite into a culture medium, wherein the weight ratio of the pyrite to the culture medium is 1: 50-1: 40, adding a strain liquid of a mixed bacterium of Thiobacillus ferrooxidans (Thiobacillus ferrooxidans T.f.), Thiobacillus thiooxidans (Thiobacillus thiooxidans T.t.) or Thiobacillus ferrooxidans and Thiobacillus thiooxidans, wherein the volume ratio of the strain liquid to the culture medium is 1: 20-1: 15, and carrying out 1 st acclimation for 6-10 days;
(2) and 2, domestication: placing the crushed pyrite into a culture medium, wherein the weight ratio of the pyrite to the culture medium is 1: 40-1: 20, taking a leaching solution obtained after 1 st acclimation as a strain solution, wherein the volume ratio of the strain solution to the culture medium is 1: 15-1: 10, and then carrying out 2 nd acclimation for 6-10 days;
(3) and 3, domestication: placing the crushed pyrite into a culture medium, wherein the weight ratio of the pyrite to the culture medium is 1: 20-1: 10, taking a leaching solution obtained after the 2 nd acclimation as a strain solution, and carrying out 3 rd acclimation for 6-10 days, wherein the volume ratio of the strain solution to the culture medium is 1: 10-1: 5;
(II) preparing a bacterial pyrite leaching agent:
(1) seed expansion: crushing pyrite, adding the crushed pyrite into a culture medium, wherein the weight ratio of the pyrite to the culture medium is 1: 20-3: 20, taking the pyrite leaching solution obtained in the step (I) (2) or the step (I) (3) as a seed solution, carrying out seed expansion, wherein the volume ratio of the seed solution to the culture medium is 1: 10-1: 5, and culturing for 3-5 days on a shaking table at the temperature of 25-38 ℃;
(2) inoculation: crushing pyrite, adding the crushed pyrite into a culture medium, wherein the weight ratio of the pyrite to the culture medium is 1: 20-3: 20, taking the steep liquor after seed expansion as a seed liquor, and inoculating, wherein the volume ratio of the seed liquor to the culture medium is 1: 10-1: 5;
(3) preparing a bacterial pyrite leaching agent: after inoculation, leaching in a reactor at normal temperature, preferably 25-38 ℃, and filtering and centrifuging when the pH value of the leaching solution is less than 1 to obtain the bacterial pyrite leaching agent liquid.
And (5) repeating the steps (two) (1) to (3) by using the prepared bacterial pyrite leaching agent liquid, and adjusting the pH value by using the bacterial pyrite leaching agent liquid to control the pH value to be between 1.5 and 2.5 to obtain the bacterial pyrite leaching agent.
(III) eliminating the induction period of the strain to the polymetallic tuberculosis:
the strain adopts Thiobacillus ferrooxidans T.f, Thiobacillus thiooxidans T.t or a mixed strain of Thiobacillus ferrooxidans and Thiobacillus thiooxidans;
the culture medium is prepared by mixing a Leathen culture medium and textile dye sewage in a weight ratio of 20: 1-3: 1, and the pH value is 1.5-2.5;
2 or 3 times of domesticating strains:
(1) 1, domestication: putting the crushed deep-sea polymetallic tuberculosis into a culture medium for domesticating strains, wherein the weight ratio of the polymetallic tuberculosis to the culture medium is 1: 50-1: 40, adding Thiobacillus ferrooxidans (Thiobacillus ferrooxidans T.f.), Thiobacillus thiooxidans (Thiobacillus thiooxidans T.t) or mixed strain liquid of the Thiobacillus ferrooxidans and the Thiobacillus thiooxidans, wherein the volume ratio of the strain liquid to the culture medium is 1: 20-1: 15, carrying out 1 st domestication for 6-10 days, adding the bacterial pyrite leaching agent prepared in the step (II) in the domestication process, and controlling the pH value to be 1.5-2.5;
(2) and 2, domestication: putting the crushed domesticated strain polymetallic tuberculosis into a culture medium, wherein the weight ratio of the domesticated strain polymetallic tuberculosis to the culture medium is 1: 40-1: 20, taking a leaching solution obtained after the 1 st domestication as a strain solution, wherein the volume ratio of the strain solution to the culture medium is 1: 15-1: 10, then carrying out 2 nd domestication for 6-10 days, adding the bacterium pyrite leaching agent prepared in the step (two) in the domestication process, and controlling the pH value to be 1.5-2.5;
(3) and 3, domestication: putting the crushed domesticated strain polymetallic tuberculosis into a culture medium, wherein the weight ratio of the domesticated strain polymetallic tuberculosis to the culture medium is 1: 20-1: 10, taking a leaching solution obtained after 2 nd domestication as a strain solution, the volume ratio of the strain solution to the culture medium is 1: 10-1: 5, carrying out 3 rd domestication for 6-10 days, adding the bacterium pyrite leaching agent prepared in the step (two) in the domestication process, and controlling the pH value to be 1.5-2.5;
(IV) seed expansion: adding the crushed pyrite, ferrous sulfate or elemental sulfur as a reducing agent into a culture medium, wherein the weight ratio of the reducing agent to the culture medium is 1: 100-3: 20, using the mineral leaching liquid obtained in the step (III) (2) or the step (III) (3) as a seed liquid, wherein the volume ratio of the seed liquid to the culture medium is 1: 10-1: 5, culturing for 3-5 days on a shaking table, controlling the temperature at 25-38 ℃, adding the bacterial pyrite leaching agent prepared in the step (II) and controlling the pH value at 1.5-2.5;
(V) inoculation: adding a reducing agent and polymetallic nodules into a culture medium, wherein the weight ratio of the culture medium to the polymetallic nodules is 100: 1-5: 1, the weight ratio of the polymetallic nodules to the reducing agent is 20: 1-1: 1, adding the expanded extract as a seed solution, inoculating, wherein the volume ratio of the seed solution to the culture medium is 1: 20-7: 10, and adding or not adding a bacterial pyrite leaching agent in the inoculation process; adjusting the initial pH value to 1-6 preferably by adding a bacterial pyrite leaching agent, and adjusting the initial pH value to 1-3 preferably;
(VI) leaching: after inoculation, column leaching, heap leaching, tank leaching and leaching by using a conical flask on a shaking table or an airlift reactor, wherein in the leaching process, air can be introduced or not introduced, the temperature is normal temperature, the temperature is controlled to be between 25 and 38 ℃, the leaching effect is good, and the air flow in the air introduction process is 0 to 10L/min; during the leaching process, adding or not adding a bacterium-producing pyrite leaching agent, finishing the leaching when the color of the leaching solution is changed from black or black brown to brown or tan and the pH value of the leaching solution is constant, so as to obtain the leaching solution containing Mn, Fe, Co, Ni and Cu; the pH value is controlled to be between 1 and 6 by adding the bacterial pyrite leaching agent, the effect is better, and the pH value is controlled to be between 1 and 3 by adding the bacterial pyrite leaching agent, so that the effect is optimal.
Said invention is characterized by that its leaching process is implemented under the aerobic condition, and air must be introduced, and in the whole leaching process, Mn is added4+And O2 are electron donors, which are in a competitive relationship when being reduced, and the reaction speed of mineral leaching is slow. Meanwhile, the mass transfer rate of oxygen is often the control step of the leaching process, and the process design of industrial production is complicated due to the strengthened mass transfer of oxygen, so that the exploration of the process of reducing the oxidized ore under the anaerobic condition has important application value.
The invention aims to: the microbial catalytic oxidation-reduction coupled leaching method of valuable metals in manganese oxide ore is provided, wherein the 'preparation bacteria pyrite leaching agent' in the steps of the method is basically the same as the 'preparation bacteria pyrite leaching agent' in the invention patent application with the application number of 00102747.6 (the difference is that the strain adopts thiobacillus ferrooxidans, and the culture medium is Leathen culture medium), and the difference is that: the method disclosed by the invention utilizes the anaerobic property of Thiobacillus ferrooxidans T.f, and under the catalysis of the anaerobic property, manganese oxide ore and a reducer pyrite are coupled to generate an oxidation-reduction reaction, so that valuable metals in minerals are directly leached.
The embodiments of the present invention are as follows:
the invention provides a microbial oxidation-reduction coupling leaching method of valuable metals in manganese oxide ore, which comprises the following leaching steps:
preparing a bacterial pyrite leaching agent:
(1) eliminating the induction period of the strain on the pyrite:
the strain is as follows: thiobacillus ferrooxidans T.f
The culture medium adopts Leathen culture medium, and the pH value is 1.5-2.5;
2 or 3 times of domesticating strains:
a. 1, domestication: putting the crushed pyrite into a culture medium, wherein the weight ratio of the pyrite to the culture medium is 1: 50-1: 40, adding a strain liquid of Thiobacillus ferrooxidans T.f, wherein the volume ratio of the strain liquid to the culture medium is 1: 20-1: 15, and carrying out 1 st acclimation for 6-10 days;
b. and 2, domestication: placing the crushed pyrite into a culture medium, wherein the weight ratio of the pyrite to the culture medium is 1: 40-1: 20, taking a leaching solution obtained after the 1 st acclimation as a strain solution, and carrying out the 2 nd acclimation for 6-10 days, wherein the volume ratio of the strain solution to the culture medium is 1: 15-1: 10;
c. and 3, domestication: placing the crushed pyrite into a culture medium, wherein the weight ratio of the pyrite to the culture medium is 1: 20-1: 10, taking a leaching solution obtained after the 2 nd acclimation as a strain solution, and carrying out 3 rd acclimation for 6-10 days, wherein the volume ratio of the strain solution to the culture medium is 1: 10-1: 5;
(2) preparing a bacterial pyrite leaching agent:
a. seed expansion: crushing pyrite, adding the crushed pyrite into a culture medium, wherein the weight ratio of the pyrite to the culture medium is 1: 20-3: 20, taking the pyrite leaching solution obtained in the step (1) b or the step (1) c as a seed solution, carrying out seed expansion, wherein the volume ratio of the seed solution to the culture medium is 1: 10-1: 5, and culturing for 3-5 days on a shaking table at the temperature of 25-38 ℃;
b. inoculation: crushing pyrite, adding the crushed pyrite into a culture medium, wherein the weight ratio of the pyrite to the culture medium is 1: 20-3: 20, taking the steep liquor after seed expansion as a seed liquor, and inoculating, wherein the volume ratio of the seed liquor to the culture medium is 1: 10-1: 5;
c. preparing a bacterial pyrite leaching agent: after inoculation, leaching by using a column leaching reactor or a gas lift reactor or a conical flask in a shaking table at normal temperature, preferably at 25-38 ℃, and filtering and centrifuging when the pH value of the leaching solution is less than 1 to obtain a bacterial pyrite leaching agent solution;
repeating the steps (2) a-c by using the prepared strain pyrite leaching agent liquid, adjusting the pH value by using the strain pyrite leaching agent liquid, and controlling the pH value to be between 1.5 and 2.5 to obtain a strain pyrite leaching agent;
it is characterized in that the leaching step also comprises:
(II) eliminating the induction period of the strain on manganese oxide ore:
the strain adopts Thiobacillus ferrooxidans T.f;
the culture medium adopts Leathen culture medium, and the pH value is 1.5-2.5;
2 or 3 times of domesticating strains:
(1) 1, domestication: putting crushed manganese oxide ore and pyrite into a culture medium, wherein the weight ratio of the manganese oxide ore to the culture medium is 1: 60-1: 40, adding Thiobacillus ferrooxidans (Thiobacillus ferrooxidans T.f.), the volume ratio of a strain liquid to the culture medium is 1: 15-1: 10, the weight ratio of the manganese oxide ore to the pyrite is 1: 4-1: 2, carrying out 1 st domestication for 6-10 days, adding the bacterial pyrite leaching agent prepared in the step (1) in the domestication process, and controlling the pH value to be 1.5-2.5;
(2) and 2, domestication: putting crushed manganese oxide ore and pyrite into a culture medium, wherein the weight ratio of the manganese oxide ore to the culture medium is 1: 40-1: 20, taking a leaching solution obtained after 1 st domestication as a strain solution, the volume ratio of the strain solution to the culture medium is 1: 10-1: 5, the weight ratio of the manganese oxide ore to the pyrite is 1: 2-4: 3, and then carrying out 2 nd domestication for 6-10 days, wherein in the domestication process, the bacterial pyrite leaching agent prepared in the step (1) is added, and the pH value is controlled to be 1.5-2.5;
(3) and 3, domestication: putting the crushed manganese oxide ore and pyrite into a culture medium, taking a leachate obtained after 2 nd domestication as a strain liquid, taking the volume ratio of the strain liquid to the culture medium as 1: 20-1: 15, taking the leachate as a strain liquid, taking the weight ratio of the strain liquid to the pyrite as 4: 3-2: 1, carrying out 3 rd domestication for 6-10 days, adding the bacterial raw pyrite leaching agent prepared in the step (1) in the domestication process, and controlling the pH value to be 1.5-2.5;
(III) inoculation: adding reducing agents pyrite and manganese oxide ore into a culture medium, wherein the weight ratio of the manganese oxide ore to the culture medium is 1: 60-1: 15, the weight ratio of the manganese oxide ore to the pyrite is 1: 4-2: 1, adding an immersion liquid of (II) (2) or (II) (3) as a seed liquid, inoculating, wherein the volume ratio of the seed liquid to the culture medium is 1: 15-1: 2, adding a bacterium-producing pyrite immersion agent, and adjusting the initial pH value to 1-6, preferably 1-3;
(IV) leaching: after inoculation, heap leaching, tank leaching and leaching by using a conical flask on a shaking table or a circulating reactor are selected, and in the leaching process, aeration and anaerobic reaction are not carried out. The temperature is normal temperature, the temperature is controlled between 25 ℃ and 38 ℃, the leaching effect is good, during the leaching process, a bacterium-producing pyrite leaching agent can be added or not added, the pH value of the leaching solution continuously drops, and the leaching solution does not rise any more, so that the leaching is finished; the pH value is controlled to be between 1 and 6 by adding the bacterial pyrite leaching agent, the effect is better, and the pH value is controlled to be between 1 and 3 by adding the bacterial pyrite leaching agent, so that the effect is optimal.
The microbial oxidation-reduction coupling leaching method of valuable metals in manganese oxide ore provided by the invention has the following advantages:
1. coupling manganese oxide ore and reduced ore pyrite by utilizing the catalytic action of T.f. microorganisms under the anaerobic condition to generate oxidation-reduction reaction;
2. the anaerobic property of the T.f. facultative bacteria is fully utilized, and the leaching process and equipment are simplified;
3. the leaching effect of manganese oxide ore by using the bacterial pyrite leaching agent is remarkable, the agent is saved, and the cost is reduced;
4. the method has loose leaching conditions, high leaching rate and high leaching rate;
5. the method has the advantages of simple process, low energy consumption, small environmental pollution and high resource utilization rate.
The invention provides a microbial oxidation-reduction coupling leaching method of valuable metals in manganese oxide ore, which has the leaching mechanism as follows:
thiobacillus ferrooxidans is a facultative acidophilicThe chemoautotrophic bacteria can catalyze and oxidize and reduce the ore under aerobic condition, and can catalyze and reduce the oxidized ore under aerobic or anaerobic condition in the presence of a reducing agent. T.f. bacteria leach manganese oxide ore by using pyrite as a reducing agent under an anaerobic condition, the activity is stronger than that under an aerobic condition, the leaching speed is high, and Fe in the reaction is leached2+S-is an electron donor, Mn4+Is an electron acceptor (Mn under aerobic conditions)4+、O2Both electron acceptors). Under anaerobic conditions, the electron flow is along the cell wall rather than across it, and the reaction is as follows:
FeS2+8H2bacteria of Fe2++2SO4 2-+16H++14e-
With reduction of manganese dioxide, i.e. Mn4+Reduction to Mn2+The mineral lattice is destroyed; meanwhile, under the catalytic action of the strains, other valuable metals attached to the crystal lattices are leached out;
thiobacillus ferrooxidans T.f. under anaerobic conditions, electrons generated by oxidizing sulfur compounds enter the transfer chain at the Flavoprotein (FP) or cytochrome b level, indicating that two sites can generate ATP for each pair of transferred electrons, with the high valence metal of manganese oxide ore as the final electron acceptor. Under aerobic conditions, electrons generated by oxidation of sulfur compounds enter the transport chain at the level of cytochrome C, with O2For the final electron acceptor, only one site is coupled to ATP synthesis for each pair of transferred electrons.
During microbial metabolism, oxygen acts in the cytoplasmic membrane at a local pH of about 7, at which the reduction potential is 0.816V due to Fe3+Reduction to Fe2+Has a standard potential of 0.77V, so Fe3+ is less oxidizing than oxygen and is also milder than oxygen; mn4+Reduction to Mn2+Has a standard potential of 1.208V; in the whole reaction bodyWherein, pH is 1-3, Fe3+/Fe2+Potential ratio Mn4+/Mn2+Low, weak oxidizing agents. In addition, higher concentration of Mn4+The presence of the catalyst is beneficial to increasing the E value of a leaching system, namely maintaining a higher oxidation-reduction potential of the system. Since the potential is also a measure of culture activity, a larger potential value indicates that mineral dissolution can be promoted more rapidly. On the contrary, if no microorganism is involved in the system, Fe2+Is oxidized into Fe3+The speed of (a) is remarkably reduced, and the E in the system is reduced, which is not beneficial to the dissolution of minerals and the exposure of valuable metals in the leaching process. Manganese oxide ore directly participates in redox reaction as an electron acceptor, so that the mineral actively accelerates the biological process. That is, the oxidized ore and the reducing agent are coupled under the catalytic action of the microorganism and the enzyme.
In the experiment, most of the bacterial ores are attached to the surface of the tuberculosis, and the bacteria are adsorbed to the surface of the mineral, which is the requirement for taking nutrient substances and is also an energy requirement; substances required for bacterial survival, e.g. Fe2+、S1-Iso-enrichment at the solid-liquid interface; thin and thinThe adsorption of bacteria to the surface of free mineral can reduce the free energy of the system. The close contact, adsorption, of bacteria and minerals is the condition for the bacteria to be attacked and leached by their enzymes.
The invention is further described with reference to the following examples:
example 1: the microorganism oxidation-reduction coupling leaching method for valuable metals in manganese oxide ore provided by the invention is used for leaching and extracting valuable metal manganese in manganese oxide ore, and the specific leaching steps are as follows:
preparing a bacterial pyrite leaching agent:
1. eliminating the induction period of the strain on the pyrite:
the strain adopts Thiobacillus ferrooxidans T.f;
the culture medium adopts Leathen culture medium, the pH value is 1.5, and the components of the culture medium are shown in the table 3;
TABLE 3 composition of Leathen medium
| Composition of | Content (g/L) |
| (NH4)2SO4 | 0.5 |
| KCl | 0.05 |
| K2HPO4 | 0.05 |
| MgSO4·7H2O | 0.5 |
| Ca(NO3)2·2H2O | 0.01 |
| FeSO4·7H2O | 7.2 |
| PH | 2.0 |
This example was divided into 3 acclimated strains:
a. 1, domestication: putting pyrite with the particle size of-200 meshes into a culture medium, wherein the weight ratio of the pyrite (which is collected from Shanxi city of Cross and the components of which are shown in Table 5) to the culture medium is 1: 50, adding a strain liquid of thiobacillus ferrooxidans (Thiobacillus ferrooxidans T.f.), wherein the volume ratio of the strain liquid to the culture medium is 1: 20, and carrying out 1 st acclimation for 6 days;
b. and 2, domestication: putting pyrite with the particle size of-200 meshes into a culture medium, wherein the weight ratio of the pyrite to the culture medium is 1: 30, taking a leaching solution obtained after the 1 st acclimation as a strain solution (10 milliliters), wherein the volume ratio of the strain solution to the culture medium is 1: 15, and then carrying out 2 nd acclimation for 6 days;
c. and 3, domestication: putting pyrite with the particle size of-200 meshes into a culture medium, wherein the weight ratio of the pyrite to the culture medium is 1: 20 or 1: 10, taking a leaching solution obtained after the 2 nd domestication as a strain solution, and carrying out 3 rd domestication for 6 days, wherein the volume ratio of the strain solution to the culture medium is 1: 10;
2. preparing a bacterial pyrite leaching agent:
a. seed expansion: adding pyrite with the particle size of-200 meshes into a culture medium, wherein the weight ratio of the pyrite to the culture medium is 1: 20, taking 20 ml of the pyrite leaching solution obtained in the step (1) c as a seed solution, carrying out seed expansion, wherein the volume ratio of the seed solution to the culture medium is 1: 10, and carrying out shake cultivation and seed expansion for 3 days at the temperature of 25 ℃;
b. inoculation: adding pyrite with the particle size of-200 meshes into a culture medium, wherein the weight ratio of the pyrite to the culture medium is 1: 20, taking 20 ml of the expanded extract as a seed solution, and inoculating, wherein the volume ratio of the seed solution to the culture medium is 1: 10;
c. preparing a bacterial pyrite leaching agent: and culturing the inoculated mixed solution on a shaking table at the rotating speed of 180r/min and the temperature of 25 ℃, filtering and centrifuging when the pH value of the leaching solution is less than 1 to obtain the bacterial pyrite leaching agent liquid.
Repeating the steps (2) a-c by using the prepared strain pyrite leaching agent liquid, adjusting the pH value by using the strain pyrite leaching agent liquid, and controlling the pH value to be 1.5 to obtain a strain pyrite leaching agent for later use;
eliminating the induction period of the strain to the pyrolusite:
the strain is of Thiobacillus ferrooxidans T.f;
adopting Leathen culture medium, pH 1.5;
domesticating strains for 3 times:
1. 1, domestication: putting 6 g of manganese ore (purchased from a Chinese geological museum and containing 51.8% of manganese) and 2 g of pyrite (purchased from the Chinese geological museum and containing 36.7% of iron and 37.93% of sulfur) with the particle size of-200 meshes into a culture medium, wherein the weight ratio of the manganese ore to the pyrite is 3: 1, the weight ratio of the manganese ore to the culture medium is 1: 50, adding 25 ml of ferrous oxide thiobacillus liquid, the volume ratio of the liquid to the culture medium is 1: 12, adjusting the pH value by using a bacterial pyrite leaching agent in the domestication process, controlling the pH value to be 1.5, carrying out 1 st domestication for 10 days,
2. and 2, domestication: putting 8 g of manganese ore and 6 g of pyrite with the particle size of-200 meshes into a culture medium, wherein the weight ratio of the manganese ore to the pyrite is 4: 3, the weight ratio of the manganese ore to the culture medium is 1: 30, taking 30 ml of leachate obtained after 1 st domestication as a strain liquid, the volume ratio of the strain liquid to the culture medium is 1: 8, adding a bacterial pyrite leaching agent to adjust the pH value in the domestication process, controlling the pH value to be 1.5, and carrying out 2 nd domestication for 10 days;
3. and 3, domestication: putting 10 g of manganite and 15 g of pyrite with the particle size of-200 meshes into a culture medium, wherein the weight ratio of the manganite to the pyrite is 2: 3, the weight ratio of the manganite to the culture medium is 1: 18, taking 60 ml or 45 ml of leachate obtained after 2 nd domestication as a strain liquid, the volume ratio of the strain liquid to the culture medium is 1: 3 or 1: 4, adding a bacterium-producing pyrite leaching agent to adjust the pH value in the domestication process, controlling the pH value to be 1.5, and carrying out 3 rd domestication for 10 days;
(III) inoculation: adding 4 g of-200 meshes of pyrolusite into a culture medium, wherein the weight ratio of the culture medium to the deep-sea manganese oxide ore is 50: 1, the weight ratio of the pyrolusite to the pyrite is 4: 3, then taking 1.(2) or 1.(3) extract as a seed solution (50 ml), the volume ratio of the seed solution to the culture medium is 1: 4, and adding a bacterial pyrite leaching agent to adjust the pH value to 1.5;
(IV) leaching: leaching the inoculated leachate by using a shaking table on a conical flask, controlling the temperature at 25 ℃ and the rotation speed of the shaking table at 180r/min in the leaching process, adding a bacterial pyrite leaching agent in the leaching process, controlling the pH value to be 1.5, and finishing leaching when the pH value of the leaching solution continuously drops, wherein the obtained result is that the content of Mn in the leachate is measured by using an atomic absorption method; measuring the pH value by using a domestic 302pH meter; the strain was observed with a domestic XSX-2 microscope and directly counted on a hemocytometer.
The leaching time is 9 days, and the leaching rate of manganese is 99.9 percent.
Example 2: the microorganism oxidation-reduction coupling leaching method of valuable metals in manganese oxide ore provided by the invention is used for extracting the valuable metals manganese in pyrolusite, and the specific leaching steps are as follows:
preparing a bacterial pyrite leaching agent:
1. eliminating the induction period of the strain on the pyrite:
the culture medium was Leathen medium, pH 2.5, the composition of which is the same as in Table 3 of example 1;
domesticating strains for 2 times:
a. 1, domestication: putting 4 g of pyrite with the particle size of-26 meshes into a culture medium, wherein the weight ratio of the pyrite to the culture medium is 1: 40, adding a strain liquid of Thiobacillus ferrooxidans (Thiobacillus ferrooxidans T.f.), wherein the volume ratio of the strain liquid to the culture medium is 1: 15, and carrying out 1 st acclimation for 8 days;
b. and 2, domestication: 10 g of pyrite with the particle size of-5 mm is placed in a culture medium, the weight ratio of the pyrite to the culture medium is 1: 20, 20 ml of leachate obtained after 1 st domestication is used as a strain liquid, the volume ratio of the strain liquid to the culture medium is 1: 10, and then 2 nd domestication is carried out for 8 days;
2. preparing a bacterial pyrite leaching agent:
a. seed expansion: crushing 30g of pyrite with the particle size of-10 mm, adding the crushed pyrite into a culture medium, wherein the weight ratio of the pyrite to the culture medium is 3: 20, taking 40 ml of the pyrite mineral leaching solution obtained in the step (1) b as a seed solution, performing seed expansion, wherein the volume ratio of the seed solution to the culture medium is 1: 5, and culturing for 5 days on a shaking table at the temperature of 38 ℃;
b. inoculation: adding 300 g of pyrite with the particle size of-10 mm into a culture medium, wherein the weight ratio of the pyrite to the culture medium is 3: 20, inoculating 400 ml of the expanded extract serving as a seed solution, wherein the volume ratio of the seed solution to the culture medium is 1: 5;
c. preparing a bacterial pyrite leaching agent: and leaching the inoculated mixed solution by using a column leaching method, wherein the leaching temperature is 38 ℃, and when the pH value of the leaching solution is less than 1, filtering and centrifuging to obtain the bacterial pyrite leaching agent liquid.
Repeating the steps (2) a-c by using the prepared bacterial pyrite leaching agent liquid, adjusting the pH value by using the bacterial pyrite leaching agent liquid, and controlling the pH value to be 2.5 to obtain a bacterial pyrite leaching agent for later use;
(II) eliminating the induction period of the strain to the pyrolusite:
the strain adopts ferrous sulfate iron ore bacillus (T.f.) strain; adopting Leathen culture medium, pH is 2.5;
domesticating strains for 3 times:
1. 1, domestication: putting 4 g of pyrolusite (purchased from a Chinese geological museum and containing 45.84% of manganese) with the particle size of-150 meshes and 3 g of pyrite into a culture medium, wherein the weight ratio of the pyrolusite to the pyrite is 4: 3, the weight ratio of the pyrolusite to the culture medium is 1: 50, adding 25 ml of a strain liquid of thiobacillus ferrooxidans, the volume ratio of the strain liquid to the culture medium is 1: 8, carrying out 1 st domestication for 8 days, and adding a bacterial pyrite leaching agent to control the pH to be 2.5 in the domestication process;
2. and 2, domestication: putting 6 g of pyrolusite and 2 g of pyrite with the particle size of-150 meshes into a culture medium, wherein the weight ratio of the pyrolusite to the pyrite is 3: 1, the weight ratio of the pyrolusite to the culture medium is 1: 30, taking 15 ml of leachate obtained after 1 st domestication as a strain liquid, the volume ratio of the strain liquid to the culture medium is 1: 12, and then carrying out 2 nd domestication for 8 days, wherein in the domestication process, a bacterium-producing pyrite leaching agent is added to control the pH value to be 2.5;
3. and 3, domestication: putting 8 g of pyrolusite and 12 g of pyrite with the particle size of-150 meshes into a culture medium, wherein the weight ratio of the pyrolusite to the pyrite is 2: 3, the weight ratio of the pyrolusite to the culture medium is 1: 16 or 1: 18, taking 32 ml or 36 ml of leachate obtained after 2 nd domestication as a strain liquid, the volume ratio of the strain liquid to the culture medium is 1: 4, carrying out 3 rd domestication for 8 days, and adding a bacterial pyrite leaching agent to control the pH value to be 2.0 or 2.5 in the domestication process;
(III) inoculation: adding 30g of pyrite and 20 g of pyrolusite serving as reducing agents into a culture medium, wherein the weight ratio of the culture medium to the pyrolusite is 30: 1, the weight ratio of the pyrolusite to the reducing agents is 2: 3, the volume ratio of a seed solution to the culture medium is 1: 6, and adding a bacterial pyrite leaching agent to adjust the initial pH to 2.5;
(IV) leaching: and (3) leaching by tank leaching after inoculation, wherein in the leaching process, the temperature is controlled at 38 ℃, a bacterium-added raw pyrite leaching agent is added, the pH value is controlled at 2.5, and the pH value is continuously reduced and does not rise any more, so that the leaching is finished. Measuring the leaching amount of Mn by an atomic absorption method; measuring the PH by using a domestic 302PH meter; the strain was observed with a domestic XSX-2 microscope and directly counted on a hemocytometer.
Leaching time: the leaching rate of manganese is 99.8 percent in 8 days.
Example 3: the method for extracting the valuable metal manganese in the deep sea manganese oxide ore by using the microorganism oxidation-reduction coupling leaching method of the valuable metal in the manganese oxide ore provided by the invention comprises the following specific leaching steps:
preparing a bacterial pyrite leaching agent:
1. eliminating the induction period of the strain on the pyrite:
the strain adopts Thiobacillus ferrooxidans T.f; the culture medium was Leathen medium, pH 2.0, and the composition of the Leathen medium is the same as that in Table 3 of example 1;
domesticating strains for 3 times:
a. 1, domestication: putting 4 g of pyrite with the granularity of-26 meshes into a culture medium, wherein the weight ratio of the pyrite to the culture medium is 1: 45, adding a strain liquid of Thiobacillus ferrooxidans (Thiobacillus ferrooxidans T.f.), wherein the volume ratio of the strain liquid to the culture medium is 1: 18, and carrying out 1 st acclimation for 10 days;
b. and 2, domestication: putting pyrite with the particle size of-2 mm into a culture medium, wherein the weight ratio of the pyrite to the culture medium is 1: 40, taking 20 ml of leachate obtained after 1 st domestication as a strain liquid, wherein the volume ratio of the strain liquid to the culture medium is 1: 12, and then carrying out 2 nd domestication for 10 days;
c. and 3, domestication: 10 g of pyrite with the particle size of-5 mm is placed in a culture medium, the weight ratio of the pyrite to the culture medium is 1: 15, 30 ml of leachate obtained after the 2 nd acclimation is used as a strain liquid, the volume ratio of the strain liquid to the culture medium is 1: 6 or 1: 5, and the 3 rd acclimation is carried out for 10 days;
2. preparing a bacterial pyrite leaching agent:
a. seed expansion: crushing 50 g of pyrite with the particle size of-5 mm, adding the crushed pyrite into a culture medium, wherein the weight ratio of the pyrite to the culture medium is 1: 10, taking 62.5 ml of the pyrite mineral leaching solution obtained in the step (1) c as a seed solution, carrying out seed expansion, wherein the volume ratio of the seed solution to the culture medium is 1: 8, and carrying out shake cultivation for 4 days at the temperature of 30 ℃;
b. inoculation: adding 200 g of pyrite with the particle size of-5 mm into a culture medium, wherein the weight ratio of the pyrite to the culture medium is 1: 10, taking 250 ml of the expanded extract as a seed solution, and inoculating, wherein the volume ratio of the seed solution to the culture medium is 1: 8;
c.preparing a bacterial pyrite leaching agent: after inoculation, leaching by using an air-lift reactor, wherein the leaching temperature is 30 ℃, and when the pH value of the leaching solution is less than 1, filtering and centrifuging to obtain the bacterial pyrite leaching agent liquid.
Repeating the steps (2) a-c by using the prepared strain pyrite leaching agent liquid, adjusting the pH value by using the strain pyrite leaching agent liquid, and controlling the pH value to be 2 to obtain a strain pyrite leaching agent for later use;
eliminating the induction period of the strain on the deep-sea manganese oxide ore:
adopting a Leathen culture medium with the pH value of 2.0;
domesticating strains for 2 times:
1. 1, domestication: putting 6 g of deep sea manganese nodule (obtained from the east Pacific ocean and having the grade shown in table 1) with the particle size of-100 meshes and 2 g of pyrite into a culture medium, wherein the weight ratio of the manganese nodule to the pyrite is 3: 1, the weight ratio of the manganese nodule to the culture medium is 1: 45, adding 22.5 ml of a strain liquid of thiobacillus ferrooxidans, the volume ratio of the strain liquid to the culture medium is 1: 12, carrying out 1 st domestication for 6 days, and adding a bacterial pyrite leaching agent to control the pH value to be 2.0 in the domestication process;
the following table shows the components (%) of the deep sea manganese oxide ore:
2. and 2, domestication: putting 6 g of manganese nodule with the particle size of-100 meshes and 8 g of pyrite into a culture medium, wherein the weight ratio of the manganese nodule to the pyrite is 3: 4, the weight ratio of the manganese noduleto the culture medium is 1: 30, taking 20 ml of leachate obtained after 1 st domestication as a strain liquid, the volume ratio of the strain liquid to the culture medium is 1: 9, and then carrying out 2 nd domestication for 6 days, wherein in the domestication process, a bacterium-producing pyrite mineral leaching agent is added to control the pH value to be 2.0;
(III) inoculation: 40 g of pyrite and 100 g of manganese nodule which are reducing agents with the particle size of-100 meshes are added into a culture medium, the weight ratio of the culture medium to manganese oxide ore is 18: 1, the weight ratio of the manganese nodule to the reducing agents is 5: 2, the infusion of 1.(2) is taken as a seed solution, the volume ratio of the seed solution to the culture medium is 1: 10, and the original pH value is adjusted to 2 by adding a bacterium-producing pyrite infusion agent;
(IV) leaching: and (3) after inoculation, leaching by using a circulating reactor, controlling the temperature at 30 ℃ in the leaching process, adding a bacterial pyrite leaching agent, controlling the pH value at 2, and finishing leaching when the color of the leaching solution is changed from black brown yellow and the pH value of the leaching solution does not rise after the pH value of the leaching solution is reduced, so as to obtain the leaching solution containing Mn, Fe, Co, Ni and Cu. Measuring the leaching amounts of Mn, Fe, Co, Ni and Cu by an atomic absorption method; measuring the pH value by using a domestic 302PH meter; the strain was observed with a domestic XSX-2 microscope and directly counted on a hemocytometer. The result is:
leaching time is 5 days, leaching rate: 95.92% of cobalt, 93.95% of nickel, 99.7% of manganese, 53.35% of copper, 66.13% of zinc and 15.13% of molybdenum.
Claims (5)
1. A microbial catalytic oxidation-reduction coupling leaching method for valuable metals in manganese oxide ore comprises the following specific leaching steps:
preparing a bacterial pyrite leaching agent:
(1) eliminating the induction period of the strain on the pyrite:
the strain is as follows: thiobacillus ferrooxidans T.f
The culture medium adopts Leathen culture medium, and the pH value is 1.5-2.5;
2 or 3 times of domesticating strains:
a. 1, domestication: putting the crushed pyrite into a culture medium, wherein the weight ratio of the pyrite to the culture medium is 1: 50-1: 40, adding a strain liquid of Thiobacillus ferrooxidans T.f, wherein the volume ratio of the strain liquid to the culture medium is 1: 20-1: 15, and carrying out 1 st acclimation for 6-10 days;
b. and 2, domestication: placing the crushed pyrite into a culture medium, wherein the weight ratio of the pyrite to the culture medium is 1: 40-1: 20, taking a leaching solution obtained after the 1 st acclimation as a strain solution, and carrying out the 2 nd acclimation for 6-10 days, wherein the volume ratio of the strain solution to the culture medium is 1: 15-1: 10;
c. and 3, domestication: placing the crushed pyrite into a culture medium, wherein the weight ratio of the pyrite to the culture medium is 1: 20-1: 10, taking a leaching solution obtained after the 2 nd acclimation as a strain solution, and carrying out 3 rd acclimation for 6-10 days, wherein the volume ratio of the strain solution to the culture medium is 1: 10-1: 5;
(2) preparing a bacterial pyrite leaching agent:
a. seed expansion: crushing pyrite, adding the crushed pyrite into a culture medium, wherein the weight ratio of the pyrite tothe culture medium is 1: 20-3: 20, taking the pyrite leaching solution obtained in the step (1) b or the step (1) c as a seed solution, carrying out seed expansion, wherein the volume ratio of the seed solution to the culture medium is 1: 10-1: 5, and culturing for 3-5 days on a shaking table at the temperature of 25-38 ℃;
b. inoculation: crushing pyrite, adding the crushed pyrite into a culture medium, wherein the weight ratio of the pyrite to the culture medium is 1: 20-3: 20, taking the steep liquor after seed expansion as a seed liquor, and inoculating, wherein the volume ratio of the seed liquor to the culture medium is 1: 10-1: 5;
c. preparing a bacterial pyrite leaching agent: after inoculation, leaching by using a column leaching reactor or a gas lift reactor or a conical flask in a shaking table at normal temperature, preferably at 25-38 ℃, and filtering and centrifuging when the pH value of the leaching solution is less than 1 to obtain a bacterial pyrite leaching agent solution;
repeating the steps (2) a-c by using the prepared strain pyrite leaching agent liquid, adjusting the pH value by using the strain pyrite leaching agent liquid, and controlling the pH value to be between 1.5 and 2.5 to obtain a strain pyrite leaching agent;
it is characterized in that the leaching step also comprises:
(II) eliminating the induction period of the strain on manganese oxide ore:
the strain adopts Thiobacillus ferrooxidans T.f;
the culture medium adopts Leathen culture medium, and the pH value is 1.5-2.5;
2 or 3 times of domesticating strains:
(1) 1, domestication: putting crushed manganese oxide ore and pyrite into a culture medium, wherein the weight ratio of the manganese oxide ore tothe culture medium is 1: 60-1: 40, adding Thiobacillus ferrooxidans (Thiobacillus ferrooxidans T.f.), the volume ratio of a strain liquid to the culture medium is 1: 15-1: 10, the weight ratio of the manganese oxide ore to the pyrite is 1: 4-1: 2, carrying out 1 st domestication for 6-10 days, adding the bacterial pyrite leaching agent prepared in the step (1) in the domestication process, and controlling the pH value to be 1.5-2.5;
(2) and 2, domestication: putting crushed manganese oxide ore and pyrite into a culture medium, wherein the weight ratio of the manganese oxide ore to the culture medium is 1: 40-1: 20, taking a leaching solution obtained after 1 st domestication as a strain solution, the volume ratio of the strain solution to the culture medium is 1: 10-1: 5, the weight ratio of the manganese oxide ore to the pyrite is 1: 2-4: 3, and then carrying out 2 nd domestication for 6-10 days, wherein in the domestication process, the bacterial pyrite leaching agent prepared in the step (1) is added, and the pH value is controlled to be 1.5-2.5;
(3) and 3, domestication: putting the crushed manganese oxide ore and pyrite into a culture medium, taking a leachate obtained after 2 nd domestication as a strain liquid, taking the volume ratio of the strain liquid to the culture medium as 1: 20-1: 15, taking the leachate as a strain liquid, taking the weight ratio of the strain liquid to the pyrite as 4: 3-2: 1, carrying out 3 rd domestication for 6-10 days, adding the bacterial raw pyrite leaching agent prepared in the step (1) in the domestication process, and controlling the pH value to be 1.5-2.5;
(III) inoculation: adding reducing agents pyrite and manganese oxide ore into a culture medium, wherein the weight ratio of the manganese oxide ore to the culture medium is 1: 60-1: 15, the weight ratio of the manganese oxide ore to the pyrite is 1: 4-2: 1, adding the immersion liquid of (II) (2) or (II) (3) as a seed liquid, inoculating, wherein the volume ratio of the seed liquid to the culture medium is 1: 15-1: 2, adding a bacterium-producing pyrite immersion agent, and adjusting the initial pH value to 1-6;
(IV) leaching: and after inoculation, heap leaching, tank leaching and leaching by using a conical flask on a shaking table or a circulating reactor, wherein in the leaching process, aeration and anaerobic treatment are not needed, the temperature is normal temperature, and in the leaching process, a bacterial pyrite leaching agent can be added or not added, so that the pH of the leaching solution continuously drops and does not rise any more, and the leaching is finished.
2. The microbial catalytic oxidation-reduction coupling leaching method of valuable metals in manganese oxide ore according to claim 1, characterized in that: in the step (III), a bacterium-producing pyrite leaching agent is added, and the initial pH value is adjusted to 1-3.
3. The microbial catalytic oxidation-reduction coupling leaching method of valuable metals in manganese oxide ore according to claim 1, characterized in that: in the step (IV), the leaching temperature is controlled to be between 25 and 38 ℃.
4. The microbial catalytic oxidation-reduction coupling leaching method of valuable metals in manganese oxide ore according to claim 1, characterized in that: in the step (IV), the bacterial pyrite leaching agent is added in the leaching process to control the pH value to be 1-6.
5. The microbial catalytic oxidation-reduction coupling leaching method of valuable metals in manganese oxide ore according to claim 1, characterized in that: in the step (IV), thebacterial pyrite leaching agent is added in the leaching process to control the pH value to be 1-3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001302388A CN1147598C (en) | 2000-10-31 | 2000-10-31 | Microbe-catalytic oxidization-reduction compling process for extracting valuable metals from manganese oxide ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001302388A CN1147598C (en) | 2000-10-31 | 2000-10-31 | Microbe-catalytic oxidization-reduction compling process for extracting valuable metals from manganese oxide ore |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1351180A true CN1351180A (en) | 2002-05-29 |
| CN1147598C CN1147598C (en) | 2004-04-28 |
Family
ID=4594048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001302388A Expired - Fee Related CN1147598C (en) | 2000-10-31 | 2000-10-31 | Microbe-catalytic oxidization-reduction compling process for extracting valuable metals from manganese oxide ore |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1147598C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422358C (en) * | 2002-08-15 | 2008-10-01 | 北京有色金属研究总院 | Bioleaching process of sulfide mineral ore or concentrate or tailing containing alkaline veinstone |
| CN102162029A (en) * | 2011-01-21 | 2011-08-24 | 天津工业生物技术研究所 | Microbiological oxidation and reduction coupling leaching method for valuable metal in manganese oxide ore |
| CN103290216A (en) * | 2013-06-21 | 2013-09-11 | 北京理工大学 | Method for biological reduction extraction of manganese in manganese dioxide ore |
| CN114011858A (en) * | 2021-10-28 | 2022-02-08 | 浙江工业大学 | Method for in-situ rapid film forming, passivation and acid production inhibition on surface of sulfide mineral |
-
2000
- 2000-10-31 CN CNB001302388A patent/CN1147598C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422358C (en) * | 2002-08-15 | 2008-10-01 | 北京有色金属研究总院 | Bioleaching process of sulfide mineral ore or concentrate or tailing containing alkaline veinstone |
| CN102162029A (en) * | 2011-01-21 | 2011-08-24 | 天津工业生物技术研究所 | Microbiological oxidation and reduction coupling leaching method for valuable metal in manganese oxide ore |
| CN102162029B (en) * | 2011-01-21 | 2013-02-13 | 天津工业生物技术研究所 | Microbiological oxidation and reduction coupling leaching method for valuable metal in manganese oxide ore |
| CN103290216A (en) * | 2013-06-21 | 2013-09-11 | 北京理工大学 | Method for biological reduction extraction of manganese in manganese dioxide ore |
| CN114011858A (en) * | 2021-10-28 | 2022-02-08 | 浙江工业大学 | Method for in-situ rapid film forming, passivation and acid production inhibition on surface of sulfide mineral |
| CN114011858B (en) * | 2021-10-28 | 2022-08-12 | 浙江工业大学 | Method for in-situ rapid film forming, passivation and acid production inhibition on surface of sulfide mineral |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1147598C (en) | 2004-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102329957B (en) | Method for continuously leaching sulfide ore by using synergy of autotrophic ore leaching bacteria and heterotrophic ore leaching bacteria | |
| CN1869198A (en) | Bacterial strain for leaching out ore or clean ore comprising metallic sulfide ore component and leaching method thereof | |
| CA2257126A1 (en) | Method and apparatus for biocatalyzed anaerobic oxidation of metal sulfides | |
| CN101993835B (en) | Arsenic-resistant bacteria and method for performing oxidation treatment on high-arsenic gold concentrate by using same | |
| CN101333599A (en) | Cyanidation aurum-extracting method for preprocessing high-arsenic complex refractory gold ore by oxidation with arsenic resistant strains | |
| Lee et al. | Leaching of Mn, Co, and Ni from manganese nodules using an anaerobic bioleaching method | |
| CN109112306B (en) | Method for treating refractory gold concentrate by combining ozone oxidation and microbial oxidation | |
| CN103014336B (en) | Preparation and method for treating high-arsenic and high-sulfur gold ore | |
| CN103031434B (en) | Refractory gold ore desulfurizing and dearsenifying method | |
| Hao et al. | Responses of bacterial community to potential heap construction methods of fine-grained copper tailings in column bioleaching system | |
| CN107858507B (en) | A kind of complex method improving sulfur oxidizing bacterium kind Chalcopyrite Leaching efficiency | |
| Dan et al. | Reductive leaching of manganese from manganese dioxide ores by bacterial-catalyzed two-ores method | |
| CN1147598C (en) | Microbe-catalytic oxidization-reduction compling process for extracting valuable metals from manganese oxide ore | |
| CN104531990B (en) | Biological gold extraction process of antimony-bearing complex refractory gold ore and microorganism used in same | |
| CN109250882A (en) | A kind of method of animal waste heavy metal removing | |
| CN108148771B (en) | Low-temperature fluorine-resistant leaching-ore bacteria and bioleaching process for uranium-containing ores by using same | |
| CN1132945C (en) | Microbe leaching-out method of valuable metals from deep-sea polymetal nodule | |
| CN103088222B (en) | Process for treating refractory gold ores | |
| CN1858276A (en) | Method for extracting metal copper using microbe and its use | |
| CN108486368B (en) | Method for leaching arsenic-containing carbonaceous gold ore by pyrolusite high pressure-non-cyanidation | |
| RU2560627C2 (en) | Method of leaching of valuable components and rare-earth elements from cinder material | |
| CN101899570B (en) | Preoxidation treating method for leaching arsenic golden ores by using drum type reactor organisms | |
| CN111321294B (en) | Method for improving leaching efficiency of chalcopyrite by directionally regulating and controlling indigenous microbial community | |
| CN107119188A (en) | It is a kind of that the molten method for releasing manganese in extraction manganese oxide ore of diluted acid is reduced based on nitrococcus | |
| CN103205571B (en) | Treatment process for high-carbon high-arsenic gold ores |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20040428 Termination date: 20111031 |