CN110117564B - Method for forming biological membrane by enriching thiobacillus ferrooxidans through hollow fiber membrane, hollow fiber membrane reactor and application - Google Patents

Method for forming biological membrane by enriching thiobacillus ferrooxidans through hollow fiber membrane, hollow fiber membrane reactor and application Download PDF

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CN110117564B
CN110117564B CN201910395361.3A CN201910395361A CN110117564B CN 110117564 B CN110117564 B CN 110117564B CN 201910395361 A CN201910395361 A CN 201910395361A CN 110117564 B CN110117564 B CN 110117564B
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杨远坤
谌书
王彬
周日宇
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Southwest University of Science and Technology
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Abstract

The invention discloses a method for forming a biological membrane by enriching thiobacillus ferrooxidans with a hollow fiber membrane, the hollow fiber membrane reactor and application thereof.A reaction system taking the hollow fiber membrane reactor as a core is built, a culture medium and an inoculum are added for carrying out enrichment culture of thiobacillus ferrooxidans and forming the biological membrane; supplying a mixed gas containing hydrogen to the surface of the membrane in a bubble-free gas outlet mode through the hollow fiber membrane reactor; stabilizing the temperature of the hollow fiber membrane reactor to be 25-35 ℃ by adopting a water bath heating mode; after running for several days, discharging culture solution through a sampling port to obtain the hollow fiber membrane reactor with the membrane surface enriched with the thiobacillus ferrooxidans biological membrane; a hollow fiber membrane reactor enriched with a biological membrane is used to generate ferric sulfate solution and Schneider minerals; the invention realizes the separation of the ferrous oxide thiobacillus culture and the utilization, can be circularly carried out between the culture and the utilization, and solves the problem that the culture solution can not be repeatedly utilized.

Description

Method for forming biological membrane by enriching thiobacillus ferrooxidans through hollow fiber membrane, hollow fiber membrane reactor and application
Technical Field
The invention relates to the field of microbial culture and application, in particular to a method for forming a biological membrane by enriching thiobacillus ferrooxidans through a hollow fiber membrane, a hollow fiber membrane reactor and application.
Background
The method realizes the efficient recovery of valuable metal resources in the solid wastes, and is one of important ways for realizing circular economy, solving global problems of exhaustion of mineral resources and the like. Valuable metals are leached from solid wastes by utilizing Acidithiobacillus ferrooxidans (A.f bacteria for short), the method has the characteristics of simple process control, environmental protection and the like, and is a hotspot for research in the field of hydrometallurgy. However, in the utilization process, ferric ions, sulfate ions, typical monovalent cations (mainly potassium ions, sodium ions and ammonium ions) and the like in the leachate easily form jarosite, schwerer minerals and other ferric jarosite residues to tightly cover the surface of the leachate, so that the mass transfer process between A.f bacteria and solid waste is blocked, further A.f bacteria die greatly, and the leaching efficiency of valuable metals is obviously reduced; in addition, a large amount of ferric iron ions in the leaching solution form ferric jarosite slag, which can significantly reduce the oxidation-reduction potential of the leaching solution and further affect the leaching efficiency of valuable metals. A.f bacteria leaching technique has the defect that the industrial application is limited. Therefore, the condition for forming the trivalent iron vitriol slag is destroyed, and the adoption of the leaching liquid without typical univalent cations is one of the important links for the large-scale application of the A.f bacteria leaching technology.
A.f bacteria are chemoautotrophic bacteria, and can oxidize ferrous ions into ferric ions (or oxidize hydrogen into water) under aerobic conditions. The growth and metabolism period is longer, therefore, activation and proliferation are usually needed in the liquid culture medium, when A.f bacteria in the liquid culture medium are the maximum in quantity and activity, the bacteria culture solution is used as a leaching agent to directly leach valuable metals in the solid waste. Since typical monovalent cations are nutrients necessary for the growth of A.f bacteria, in order to use a leachate containing no typical monovalent cations, the bacteria must be separated from the culture broth and reused.
In recent years, rapid development of cell immobilization technology has made it possible to solve this problem. In particular to a method for fixing the thiobacillus ferrooxidans, which mainly comprises an adsorption method and an embedding method. The adsorption method adopts a micropore medium or particles with large specific surface area, and fixes bacteria on the surface of the medium through passive adsorption (mechanical separation and physical adsorption) so as to separate the bacteria from the culture solution; the embedding method adopts curing agents such as gel and calcium alginate to fix the bacteria into small balls, and then the bacteria are separated from the culture solution by filtration. However, as the research and application go deeper, it is found that A.f bacteria passively adsorbed easily fall off from the surface of the medium, and the medium surface is covered by trivalent iron vitriol slag; in the embedding method, the bacteria are covered by the embedding material, so that mass transfer between the bacteria and the leaching solution is influenced, and the embedding material has certain toxicity to the bacteria, so that the defects of low bacterial activity, weak practicability and the like exist. In addition, regardless of the adsorption method or the entrapment method, the culture solution in which the bacteria were originally cultured is difficult to reuse after the bacteria were separated, which further increases the cost for practical use.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for forming a biological membrane by enriching thiobacillus ferrooxidans through hollow fibers, so that the separation of the culture and utilization of thiobacillus ferrooxidans is realized, and the problem that a culture solution cannot be recycled is solved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for forming a biological membrane by enriching thiobacillus ferrooxidans through a hollow fiber membrane is characterized in that a mixed gas containing hydrogen is supplied to the surface of the membrane by the hollow fiber membrane in a bubble-free gas outlet mode, so that thiobacillus ferrooxidans is enriched and cultured, and a thiobacillus ferrooxidans biological membrane is formed on the surface of the hollow fiber membrane.
Further, the method for forming the biological membrane by enriching the thiobacillus ferrooxidans by the hollow fiber membrane comprises the following steps:
(1) building a reaction system with a hollow fiber membrane reactor as a core, adding a mixture of a liquid culture medium and an inoculum into the hollow fiber membrane reactor through a sampling port, wherein the volume ratio of the inoculum to the liquid culture medium is 5-20%, and then opening a culture solution circulating pump for enrichment culture and forming a biological membrane;
(2) opening a gas source switch, adjusting a pressure reducing valve to control the gas inlet pressure, and supplying mixed gas containing hydrogen to the surface of the membrane in a bubble-free gas outlet mode through the hollow fiber membrane reactor;
(3) opening a water bath circulating system, and stabilizing the temperature of the hollow fiber membrane reactor to be 25-35 ℃ by adopting a water bath heating mode;
(4) and after the hollow fiber membrane reactor is operated for several days, closing the culture solution circulating pump, and discharging the culture solution through the sampling port (the culture solution can be repeatedly used for culturing and recovering the biological membrane on the surface of the membrane), thereby obtaining the hollow fiber membrane reactor with the membrane surface enriched with the thiobacillus ferrooxidans biological membrane.
Further, in the method for forming a biofilm by enriching a thiobacillus ferrooxidans in a hollow fiber membrane as described above, the liquid medium in the step (1) is composed of the following components: (NH)4)2SO4,132mg/L;K2HPO4,41mg/L;MgSO4·7H2O,490mg/L;CaCl2·2H2O,9mg/L;KCl,52mg/L;ZnSO4·7H2O,1mg/L;CuSO4·5H2O,2mg/L;FeSO4·7H2O,70mg/L;MnSO4·H2O,1mg/L;NaMoO4·5H2O,0.5mg/L;CoCl2·6H2O,0.5mg/L;Na2SeO4·10H2O,1mg/L;NiCl2·6H2O,1mg/L, the balance being water, the pH of the medium being 2.
Further, in the method for forming a biofilm by enriching thiobacillus ferrooxidans in the hollow fiber membrane as described above, the inoculum in step (1) is a mixed inoculum containing thiobacillus ferrooxidans.
Further, in the method for forming a biological membrane by enriching the thiobacillus ferrooxidans in the hollow fiber membrane, the gas source in the step (2) is a mixed gas containing hydrogen, and the volume ratio of the hydrogen in the mixed gas is not less than 50%.
A hollow fiber membrane reactor with a Thiobacillus ferrooxidans biological membrane attached to the surface of the hollow fiber membrane obtained by any one of the methods.
Use of a hollow fibre membrane reactor based on the above for producing a ferric sulphate leach liquor in bioleaching.
Applications as described above, including discontinuous flow means for producing a high strength ferric sulphate leach liquor and continuous flow means for producing a low strength ferric sulphate leach liquor;
the discontinuous flow mode comprises the following specific steps:
a reaction system is built by adopting a hollow fiber membrane reactor attached with a biological membrane; adding a ferrous sulfate solution through a sampling port of the reaction system, and then opening a culture solution circulating pump to start ferrous ion oxidation; opening an air pump to supply air in a bubble-free air outlet mode through the hollow fiber membrane reactor; opening a water bath circulating system, and stabilizing the temperature of the hollow fiber membrane reactor to be 25-35 ℃ in a water bath heating mode; after reacting for 48 hours, closing the culture solution circulating pump, and obtaining a ferric sulfate solution through a sampling port; when the hollow fiber membrane reactor oxidizes Fe2+After the capacity of the hollow fiber membrane reactor is reduced by 50 percent, the biological membrane recovery is carried out on the hollow fiber membrane reactor again;
the specific steps in the continuous flow mode are as follows:
a hollow fiber membrane reactor attached with a biological membrane is adopted to build a new reaction system; adding a ferrous sulfate solution into the culture tank, and then opening a culture solution circulating pump to start ferrous ion oxidation; opening an air pump to supply air in a bubble-free air outlet mode through the hollow fiber membrane reactor; opening a water bath circulating system, and stabilizing the temperature of the hollow fiber membrane reactor to be 25-35 ℃ in a water bath heating mode; when the concentration of ferric ions in the culture solution reaches the required concentration, the generated ferric sulfate solution enters a liquid storage tank;
when the hollow fiber membrane reactor oxidizes Fe2+After the capacity of the hollow fiber membrane reactor is reduced by 50 percent, the biological membrane recovery is carried out on the hollow fiber membrane reactor again.
Use of a hollow fibre membrane reactor based on the above for producing schwann minerals in bioleaching.
The application as described above, comprising the steps of:
(1) building a new reaction system for the hollow fiber membrane reactor attached with the biological membrane; adding a ferrous sulfate solution through a sampling port, and then opening a culture solution circulating pump to start ferrous ion oxidation; turning on an air pump to ensure that the hollow fiber membrane is bubble-free to outgas; opening a water bath circulating system, and stabilizing the temperature of the hollow fiber membrane reactor to be 25-35 ℃ in a water bath heating mode; after reacting for 48 hours, closing the culture solution circulating pump, and separating minerals at the bottom of the reactor through a sampling port; cleaning and drying the minerals to obtain schneiderian minerals;
(2) and when the capability of the hollow fiber membrane reactor for generating the Schlemm mineral is reduced by 50%, the biological membrane recovery is carried out on the hollow fiber membrane reactor again.
The method for generating the enriched thiobacillus ferrooxidans biological membrane on the surface of the hollow fiber membrane, the hollow fiber membrane reactor and the application have the following advantages that:
the adopted bacterial inoculum uses mixed bacterial inoculum containing thiobacillus ferrooxidans, such as acid mine wastewater, coal mine wastewater and the like, compared with pure thiobacillus ferrooxidans, mixed bacterial culture is not afraid of contamination, and the operation requirement and the management cost of a reactor can be greatly reduced; in addition, the cost for purchasing pure thiobacillus ferrooxidans or screening and purifying bacteria from mixed bacteria inoculum can be saved.
The invention adopts green energy, namely hydrogen as an electron donor to replace the traditional ferrous sulfate to culture bacteria, can avoid trivalent iron vitriol slag generated in the traditional ferrous oxide thiobacillus culture stage, and the final product of the hydrogen is water without secondary pollution.
The invention adopts the hollow fiber membrane to provide hydrogen, bacteria are actively adsorbed to the surface of the hollow fiber membrane to obtain growth energy to form a biological membrane, and the problem that the traditional adsorption method is easy to fall off due to passive adsorption is solved.
The method is simple to operate, realizes the separation of the ferrous oxide thiobacillus culture and the utilization, can be circularly carried out between the culture and the utilization, and solves the problem that the culture solution can not be recycled.
Drawings
FIG. 1 is a reaction system in example 1;
FIG. 2 is a reaction system in example 2;
FIG. 3 is a reaction system in example 3;
FIG. 4A is a photograph of the surface of a hollow fiber membrane before culture in example 1;
FIG. 4B is a photograph of the surface of the hollow fiber membrane after enrichment of the biofilm in example 1;
FIG. 4C is a photograph under a microscope (magnification 400) of the biofilm in example 1;
FIG. 5A is the relative proportion of species at the phylum level before and after the culture in example 1;
FIG. 5B is the relative proportion of species at the seed level before and after the culture in example 1;
FIG. 6 is an electron micrograph of a Schneider mineral synthesized in example 3.
Detailed Description
To make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be described clearly and completely by describing specific embodiments, and it is obvious that the described embodiments are a part of embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in FIG. 1, the hollow fiber membrane reactor in the reaction system of the invention can adopt a commercially available hollow fiber membrane module, and the invention adopts a self-made common glass double-layer reactor for assembly: the reactor body is cylindrical, the bottom of the reactor body is conical, the height of the reactor body is 20 cm, and the diameter of the reactor body is 8 cm. The reactor body is provided with an interlayer, and the thickness of the interlayer is 1cm (the interlayer is used for water bath constant temperature). The inner layer of the main body is provided with a hollow fiber membrane and is connected with an external air inlet pipeline through a pipeline, and the effective volume is 450mL (minus the volume occupied by the hollow fiber membrane); the water drop device in the culture system is a water drop aeration device, the culture system is made of common glass and is cylindrical, the bottom of the water drop device is conical, the height of the water drop device is 10 cm, the diameter of the water drop device is 3 cm, the effective volume of the water drop device is 40mL, the top of the water drop device is covered and compacted by a microporous filter membrane, and the aperture of the water drop device is 0.22 micrometer.
The hollow fiber membrane adopted by the hollow fiber membrane reactor is a gas permeable membrane capable of realizing bubble-free gas release in a certain pressure range, and the specific size and brand of the hollow fiber membrane are not particularly limited. The invention adopts a hydrogen permeable membrane produced by Mitsubishi company of Japan, and the hydrogen permeable membrane can realize bubble-free air outlet within the range of 0.001-0.1 MPa.
Example 1
Enrichment of thiobacillus ferrooxidans and biofilm formation:
a reaction system with a hollow fiber membrane reactor as a core is constructed according to the attached figure 1, and then 450mL of liquid culture medium (comprising (NH) is added into the hollow fiber membrane reactor through a sampling port4)2SO4,132;K2HPO4,41;MgSO4·7H2O,490;CaCl2·2H2O,9;KCl,52;ZnSO4·7H2O,1;CuSO4·5H2O,2;MnSO4·H2O,1;FeSO4·7H2O,70;NaMoO4·5H2O,0.5;CoCl2·6H2O,0.5;Na2SeO4·10H2O,1;NiCl2·6H2O,1, the balance of water (the unit is mg/L, the pH of the culture medium is adjusted to 2.0 by 5mol/L sulfuric acid)) and 50mL of acid mine wastewater, a culture solution circulating pump is opened, enrichment culture is carried out, and a biological membrane is formed; opening a high-pressure gas cylinder valve, adjusting a pressure reducing valve to control the inlet pressure to be 0.06Mpa, and supplying a mixed gas of hydrogen and carbon dioxide in a bubble-free gas outlet mode through a hollow fiber membrane reactor (the volume ratio of the hydrogen to the carbon dioxide in the mixed gas is 4: 1); opening a water bath circulating system, and stabilizing the temperature of the hollow fiber membrane reactor to be 25-35 ℃ in a water bath heating mode; and after the reactor successfully runs for 10 days, closing the culture solution circulating pump, and discharging the culture solution through the sampling port (the culture solution can be repeatedly used for culturing and recovering the biological membrane on the surface of the membrane), thereby obtaining the hollow fiber membrane reactor with the membrane surface enriched with the thiobacillus ferrooxidans biological membrane.
The results are shown in FIGS. 4A-4C and FIGS. 5A-5B. As can be seen from FIGS. 4A to 4C, after 10 days of culture, the surface of the hollow fiber membrane is smooth to the biofilm with abundant attachment, and the hollow fiber membrane is covered with the filamentous biofilm from the surface to the outside, the inner layer is thicker, and the outer layer is thinner; fig. 5A to 5B show species changes from inoculum to biofilm, and it can be seen from fig. 5A to 5B that, after enrichment culture and biofilm formation, species become more single from multiple species in acid mine wastewater, and the ratio of thiobacillus ferrooxidans (aciidithiobacillus ferrooxidans) is up to 93%.
Example 2
Production of iron sulphate leach liquors useful for bioleaching, both in discontinuous flow mode (high strength iron sulphate leach liquor) and in continuous flow mode (low strength iron sulphate leach liquor):
(1) the method comprises the following specific steps in a discontinuous flow mode: constructing a new reaction system for the hollow fiber membrane reactor attached with the biological membrane according to the attached figure 2; 500mL of ferrous sulfate solution (Fe in solution) was added through a sampling port of the reaction system2+Adjusting pH to 2.0 with 5mol/L sulfuric acid at a concentration of 9g/L, and opening the culture solution circulation pump and water valve 2 (water valve 1 and water valve)3 off), ferrous ion oxidation is started; opening an air pump (a filter membrane is arranged at the air inlet of the air pump to prevent dust from entering the air pump), adjusting a pressure reducing valve to control the air inlet pressure, and supplying air in a bubble-free air outlet mode through the hollow fiber membrane reactor; opening a water bath circulating system, and stabilizing the temperature of the hollow fiber membrane reactor to be 25-35 ℃ in a water bath heating mode; after 48 hours of reaction, the culture solution circulating pump is closed, and 500mL of ferric sulfate solution (Fe in solution) can be obtained at one time through the sampling port3+The concentration was 8.75. + -. 0.25 g/L).
(2) The specific steps in a continuous flow mode are as follows: constructing a new reaction system for the hollow fiber membrane reactor attached with the biological membrane according to the attached figure 2; adding ferrous sulfate solution (Fe in solution) into the culture tank2+Adjusting the pH value to be 2.0 by using 5mol/L sulfuric acid with the concentration of 0.5-5 g/L, and then opening a culture solution circulating pump, a water valve 2 and a water valve 3 (closing the water valve 1); after the culture solution is filled in the hollow fiber membrane reactor, closing the water valve 3 and starting ferrous ion oxidation; opening an air pump (a filter membrane is arranged at the air inlet of the air pump to prevent dust from entering the air pump), adjusting a pressure reducing valve to control the air inlet pressure, and supplying air in a bubble-free air outlet mode through the hollow fiber membrane reactor; opening a water bath circulating system, and stabilizing the temperature of the hollow fiber membrane reactor to be 25-35 ℃ in a water bath heating mode; when the concentration of ferric ions in the culture solution reaches the required concentration, the water valves 1-3 are reasonably controlled, so that the hollow fiber membrane reactor continuously generates ferric sulfate solution with stable concentration and enters the liquid storage tank (in this way, soluble solution Fe3+The concentration is 0.5-5 g/L, and the details are shown in Table 1).
TABLE 1 production of ferric sulfate concentration in continuous flow mode in example 2
Figure BDA0002057995430000081
(3) When the hollow fiber membrane reactor oxidizes Fe2+After the capacity of the membrane is reduced by 50 percent, the method of the first embodiment (no inoculum is added at the moment) is adopted, and the culture solution is repeatedly utilized to recover the biological membrane of the hollow fiber membrane reactor, so that the 'culture/utilization' circulation continuous feeding is realizedAnd (6) rows.
Example 3
Production of schlerian minerals:
(1) constructing a new reaction system for the hollow fiber membrane reactor attached with the biological membrane according to the attached figure 3; 500mL of ferrous sulfate solution (solution Fe) was added through the sampling port2+Adjusting the pH value to 3.0 with 5mol/L sulfuric acid at the concentration of 9 g/L), and then opening a culture solution circulating pump to start ferrous ion oxidation; opening an air pump to introduce air into the hollow fiber membrane, and adjusting a pressure reducing valve to ensure that the hollow fiber membrane is bubble-free to outgas; then a water bath circulating system is opened, and the temperature of the hollow fiber membrane reactor is stabilized to be 25-35 ℃ in a water bath heating mode; after reacting for 48 hours, closing the culture solution circulating pump, and separating minerals at the bottom of the reactor through a sampling port; the schlerian mineral is obtained after the mineral is cleaned and dried, and the appearance of the schlerian mineral is shown in figure 6.
(2) When the hollow fiber membrane reactor oxidizes Fe2+After the capacity of the hollow fiber membrane reactor is reduced by 50 percent, the method of the first embodiment (no inoculum is added at this time) is adopted, and the culture solution is repeatedly used for recovering the biological membrane of the hollow fiber membrane reactor, so that the 'culture/utilization' circulation is continuously carried out, and the culture solution can be repeatedly used.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (7)

1. A method for forming a biological membrane by enriching thiobacillus ferrooxidans through a hollow fiber membrane is characterized by comprising the following steps: the method comprises the following steps:
(1) building a reaction system with a hollow fiber membrane reactor as a core, adding a mixture of a liquid culture medium and an inoculum into the hollow fiber membrane reactor through a sampling port, wherein the volume ratio of the inoculum to the liquid culture medium is 5-20%, and then opening a culture solution circulating pump for enrichment culture and forming a biological membrane;
(2) opening a gas source switch, adjusting a pressure reducing valve to control the gas inlet pressure, and supplying mixed gas containing hydrogen to the surface of the membrane in a bubble-free gas outlet mode through the hollow fiber membrane reactor;
(3) opening a water bath circulating system, and stabilizing the temperature of the hollow fiber membrane reactor to be 25-35 ℃ by adopting a water bath heating mode;
(4) and after the hollow fiber membrane reactor runs for several days, closing the culture solution circulating pump, and discharging the culture solution through the sampling port to obtain the hollow fiber membrane reactor with the membrane surface enriched with the thiobacillus ferrooxidans biological membrane.
2. The method for forming a biofilm by enriching thiobacillus ferrooxidans with a hollow fiber membrane according to claim 1, wherein: the liquid culture medium in the step (1) consists of the following components: (NH)4)2SO4,132mg/L;K2HPO4,41mg/L;MgSO4·7H2O,490mg/L;CaCl2·2H2O,9mg/L;KCl,52mg/L;ZnSO4·7H2O,1mg/L;CuSO4·5H2O,2mg/L;FeSO4·7H2O,70mg/L;MnSO4·H2O,1mg/L;NaMoO4·5H2O,0.5mg/L;CoCl2·6H2O,0.5mg/L;Na2SeO4·10H2O,1mg/L;NiCl2·6H2O,1mg/L, the balance being water, the pH of the medium being 2.
3. The method for forming a biofilm by enriching thiobacillus ferrooxidans with a hollow fiber membrane according to claim 1, wherein: the inoculum in the step (1) is a mixed bacterium inoculum containing thiobacillus ferrooxidans.
4. The method for forming a biofilm by enriching thiobacillus ferrooxidans with a hollow fiber membrane according to claim 1, wherein: in the step (2), the gas source is a mixed gas containing hydrogen, and the volume ratio of the hydrogen in the mixed gas is not less than 50%.
5. A hollow fiber membrane reactor with a Thiobacillus ferrooxidans biological membrane attached to the surface of the hollow fiber membrane obtained by the method of any one of claims 1 to 4.
6. Use of a hollow fiber membrane reactor according to claim 5 for producing a ferric sulphate leach liquor in bioleaching, wherein: comprises an intermittent flow mode for producing high-concentration ferric sulfate leaching solution and a continuous flow mode for producing low-concentration ferric sulfate leaching solution;
the discontinuous flow mode comprises the following specific steps:
a reaction system is built by adopting a hollow fiber membrane reactor attached with a biological membrane; adding a ferrous sulfate solution through a sampling port of the reaction system, and then opening a culture solution circulating pump to start ferrous ion oxidation; opening an air pump to supply air in a bubble-free air outlet mode through the hollow fiber membrane reactor; opening a water bath circulating system, and stabilizing the temperature of the hollow fiber membrane reactor to be 25-35 ℃ in a water bath heating mode; after reacting for 48 hours, closing the culture solution circulating pump, and obtaining a ferric sulfate solution through a sampling port; when the hollow fiber membrane reactor oxidizes Fe2+After the capacity of the hollow fiber membrane reactor is reduced by 50 percent, the biological membrane recovery is carried out on the hollow fiber membrane reactor again;
the specific steps in the continuous flow mode are as follows:
a hollow fiber membrane reactor attached with a biological membrane is adopted to build a new reaction system; adding a ferrous sulfate solution into the culture tank, and then opening a culture solution circulating pump to start ferrous ion oxidation; opening an air pump to supply air in a bubble-free air outlet mode through the hollow fiber membrane reactor; opening a water bath circulating system, and stabilizing the temperature of the hollow fiber membrane reactor to be 25-35 ℃ in a water bath heating mode; when the concentration of ferric ions in the culture solution reaches the required concentration, the generated ferric sulfate solution enters a liquid storage tank;
when the hollow fiber membrane reactor oxidizes Fe2+After the capacity of the hollow fiber membrane reactor is reduced by 50 percent, the biological membrane recovery is carried out on the hollow fiber membrane reactor againAnd (5) repeating.
7. Use of a hollow fiber membrane reactor according to claim 5 for producing schwann minerals in bioleaching, comprising the steps of:
(1) building a new reaction system for the hollow fiber membrane reactor attached with the biological membrane; adding a ferrous sulfate solution through a sampling port, and then opening a culture solution circulating pump to start ferrous ion oxidation; turning on an air pump to ensure that the hollow fiber membrane is bubble-free to outgas; opening a water bath circulating system, and stabilizing the temperature of the hollow fiber membrane reactor to be 25-35 ℃ in a water bath heating mode; after reacting for 48 hours, closing the culture solution circulating pump, and separating minerals at the bottom of the reactor through a sampling port; cleaning and drying the minerals to obtain schneiderian minerals;
(2) and when the capability of the hollow fiber membrane reactor for generating the Schlemm mineral is reduced by 50%, the biological membrane recovery is carried out on the hollow fiber membrane reactor again.
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