CN102642930B - Method for treatment of metal waste water by sulfate reducing bacteria growing up with electric current - Google Patents
Method for treatment of metal waste water by sulfate reducing bacteria growing up with electric current Download PDFInfo
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- 239000002351 wastewater Substances 0.000 claims abstract description 28
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
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- 229910001385 heavy metal Inorganic materials 0.000 claims description 19
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- 239000000243 solution Substances 0.000 claims description 5
- 229910019626 (NH4)6Mo7O24 Inorganic materials 0.000 claims description 3
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
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- 238000012258 culturing Methods 0.000 claims description 3
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- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
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- 230000009467 reduction Effects 0.000 abstract description 15
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- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000000370 acceptor Substances 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 230000001404 mediated effect Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
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- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
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- 238000004065 wastewater treatment Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
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- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
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- 229910001431 copper ion Inorganic materials 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
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- Micro-Organisms Or Cultivation Processes Thereof (AREA)
Abstract
The invention belongs to the technical field of treatment of waste water, and particularly relates to a method for reduction of sulfate into sulfide and treatment of metal waste water by sulfate reducing bacteria growing up with electric current. The sulfate reducing bacteria provided by the invention is a mixing bacteria group, which comprises Desulfobulbus propinonicus, geobacter sulfurreducens. Under the condition of lacking organic carbon resource, an electrode is used as the only electronic donator for growing, sulfate is reduced into sulfide via bioelectrical chemistry, and the sulfide is applied to the treatment of metal waste water. According to the method provided by the invention, the defect that organic carbon resource is needed to be used as the electronic donator is overcome, the operation is simple, the secondary pollution is zero, the cost is low, and is particularly suitable for the treatment on organic carbon metal waste water of mine waste water, metal smelting waste water, electric plating waste water and the like.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a method for reducing sulfate into sulfide by sulfate reducing bacteria growing by current and applying the sulfide to heavy metal wastewater treatment.
Background
With the development of modern industry, a large amount of heavy metal wastewater is generated every year, and sulfide is an important means for extracting valuable metals. The conventional biological method is to dissimilatory reduce the sulfate to H by sulfate reducing bacteria2S (CN101506104A) or sulfate reducing bacteria produce biological sulfur-iron composite material (CN101935100A), under the control of different pH values, the selective precipitation of metal sulfide can be realized to remove heavy metal ions in waste water and recover valuable metals, and the method is used for removing heavy metal ions in waste water and recovering valuable metalsHas the characteristics of low cost and strong adaptability.
However, the growth of sulfate-reducing bacteria requires a suitable organic carbon source as an electron donor, which is expensive and costly, and has the problem of secondary pollution of the treated water by the additional organic substrate. Patents using solid waste such as straw as an alternative carbon source (CN101434919B) have reported, but the straw needs 10-30 days of fermentation pretreatment and has a long period. Therefore, the availability of organic carbon sources is an important factor for restricting heavy metal pollution, especially low-carbon wastewater.
Bioelectrochemistry is a new method for treating heavy metal polluted water by combining a biological method and an electrochemical method. The treatment principle is that pollutants in the sewage are degraded under the dual actions of biology and electrochemistry, and the weak current can stimulate the metabolic activity of microorganisms. The bioelectrochemical method has been rapidly developed in recent years as an environment-friendly method. Hydrogen-mediated sulfate reduction processes have been extensively studied, including microbial-assisted electrochemical hydrogen production (c.m. cordas et al, 2008; l.yu et al, 2011) electronic shuttle-assisted hydrogen production (Lojou et al, 2002) and direct hydrogen supply (xuhui latitude, 2009). Because the water solubility of hydrogen is low, the reduction process mediated by hydrogen has the defects of low efficiency, extra energy consumption and the like.
Aiming at the restriction factor of hydrogen as an electron donor for sulfate reduction, the phenomenon that the polarized electrode is used as a direct electron donor for the growth, proliferation, enzyme activity and metabolic activity improvement and sulfate reduction to sulfide is not reported yet.
Disclosure of Invention
The invention aims to invent a method for reducing sulfate into sulfide by sulfate reducing bacteria growing by current and treating heavy metal wastewater. The sulfate reducing bacteria in the invention are mixed flora, including desulfobulb Propionicus, Geobacter sulfureruccus. The method is characterized in that sulfate reducing bacteria grow by taking an electrode as a unique electron donor under the condition of lacking organic carbon, sulfate is reduced into sulfide through a bioelectrochemical way, and the sulfide is applied to treatment of heavy metal wastewater. The invention overcomes the defect that the prior art needs an organic carbon source as an electron donor.
The invention is realized by the following steps:
construction of a bioelectrochemical device
The bioelectrochemical device is a double-chamber reactor configuration (figure 1) and comprises a potentiostat 4, a lead 5, a cathode chamber 1 and an anode chamber 2. A working electrode 6 and a reference electrode 7 are inserted into the cathode chamber 1, and activated sludge of the municipal sewage plant is added; an auxiliary electrode 8 is inserted into the anode chamber 2; the two chambers are separated by a diaphragm 3.
Preparation of cathode and anode compartment solutions
Anode chamber
0.05mol/L phosphate buffer solution (pH 7.0)
Cathode chamber
Na2HPO4·12H2O 10.9g L-1，NaH2PO4 3.0g L-1，NaHCO3 2.0g L-1，KCl100mg L-1，MgCl2 40mg L-1，NH4Cl 310mg L-1，CaCl2 50mg L-1，NaCl 10mg L-1，FeCl2 25mg L-1，CoCl2·2H2O 5mg L-1，MnCl2·4H2O 5mg L-1，AlCl32.5mg L-1，(NH4)6Mo7O24 15mg L-1，H3BO3 5mg L-1，NiCl2·6H2O 0.5mg L-1，CuCl2·2H2O 3.5mg L-1，ZnCl2 5mg L-1，180～200mg L-1Sulfates as electron acceptors and modulateCatholyte pH was 7.2.
Biocathode preparation
Biofilm of microorganisms
Inoculating activated sludge of urban sewage plant, and introducing H2As an electron donor, and adding sulfate as an electron acceptor for enrichment culture for 2-3 months. Inoculating the enriched autotrophic sulfate-reducing bacteria source into the cathode chamber of the constructed bioelectrochemical reactor, not electrifying, and continuously electrifying H2And (5) stirring and culturing. Successful biofilm formation is shown when the flora is enriched on the cathode electrode.
Acclimation of biocathodes
After the microorganisms finish film forming on the cathode electrode, argon is introduced into the reactor to drive away residual H2And carrying out electrified domestication of-400 mV (vs. Ag/AgCl), wherein when the removal efficiency of the sulfate reaches a stable state, the construction of the biological cathode is successful.
Operation of a bioelectrochemical reactor
Filling a sulfate culture medium containing 20mg/L-600mg/L into a cathode chamber containing a cathode biological membrane; phosphate buffer solution was charged into the anode chamber. Argon gas was then introduced into each chamber for 20 minutes to ensure that all the air in the reactor was removed, and the chambers were sealed separately. And finally, connecting the device into a potentiostat through a lead, connecting the working electrode with the cathode of the potentiostat, connecting the auxiliary electrode with the anode of the potentiostat, connecting the reference electrode with the reference electrode of the potentiostat, and setting the electrode potential range to be-400 mV to-700 mV (vs. Ag/AgCl). The concentration of sulfide in the catholyte reaches 50mgL-1The catholyte is replaced when the heavy metal ions are treated, and the replaced catholyte containing sulfide is used for treating the heavy metal ions.
The invention also relates to the application of the method for treating heavy metal wastewater by using the sulfate reducing bacteria growing by current in the treatment of low organic carbon heavy metal wastewater in mine wastewater, metal smelting wastewater and electroplating wastewater.
The invention has the beneficial effects that:
(1) an organic carbon source is not needed, the electrode is directly used as the only electron donor for the growth of the sulfate reducing bacteria, the sulfate is reduced into sulfide through a bioelectrochemical approach, the secondary pollution is avoided, and the operation is simple.
(2) The invention does not need hydrogen as an electron donor, the provided electrode has low potential, the energy is saved, and the electrode does not need to use expensive catalyst and has low cost.
(3) The method has application value in removing metal ions in the low organic carbon heavy metal wastewater.
The invention is particularly suitable for treating low organic carbon heavy metal wastewater such as mine wastewater, metal smelting wastewater, electroplating wastewater and the like.
Drawings
FIG. 1 is a schematic view of a bioelectrochemical device of the present invention. Wherein 1 cathode chamber; 2 an anode chamber; 3, a diaphragm; 4, a constant potential rectifier; 5, conducting wires; 6 a working electrode; 7 a reference electrode; 8 auxiliary electrode
FIG. 2 shows the time course of sulfate reduction and sulfide formation at a potential of-400 mV (vs. Ag/AgCl).
FIG. 3 is a graph of cumulative charge and sulfide formation over time.
FIG. 4 is a batch test sulfate reduction cyclic voltammetry scan.
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to the accompanying drawings and examples. The embodiments are provided to facilitate a better understanding of the invention and are not intended to limit the invention.
Example 1: sulfate reduction and sulfide formation with electrodes as the sole electron donor
Construction of a bioelectrochemical reaction apparatus
The bioelectrochemical device is a double-chamber reactor configuration (figure 1) and comprises a potentiostat 4, a lead 5, a cathode chamber 1 and an anode chamber 2. A working electrode 6 and a reference electrode 7 are inserted into the cathode chamber 1, and activated sludge of a municipal sewage plant is added; an auxiliary electrode 8 is inserted into the anode chamber 2; the two chambers are separated by a diaphragm 3.
Preparation of cathode and anode compartment solutions
Anode chamber
0.05mol/L phosphate buffer solution (pH 7.0)
Cathode chamber
Na2HPO4·12H2O 10.9g L-1，NaH2PO4 3.0g L-1，NaHCO3 2.0g L-1，KCl100mg L-1，MgCl2 40mg L-1，NH4Cl 310mg L-1，CaCl2 50mg L-1，NaCl 10mg L-1，FeCl2 25mg L-1，CoCl2·2H2O 5mg L-1，MnCl2·4H2O 5mg L-1，AlCl32.5mg L-1，(NH4)6Mo7O24 15mg L-1，H3BO3 5mg L-1，NiCl2·6H2O 0.5mg L-1，CuCl2·2H2O 3.5mg L-1，ZnCl2 5mg L-1，180～200mg L-1Sulfate was used as the electron acceptor and the catholyte pH was adjusted to 7.2.
Biocathode preparation
Biofilm of microorganisms
Inoculating activated sludge of urban sewage plant, and introducing H2As an electron donor, and adding sulfate as an electron acceptor for enrichment culture for 2-3 months. Enriching autotrophic sulfate-reducing bacteriaInoculating the source into the cathode chamber of the bioelectrochemical reactor constructed above, not electrifying, and continuously electrifying H2And (5) stirring and culturing. Successful biofilm formation is shown when the flora is enriched on the cathode electrode.
Acclimation of biocathodes
After the microorganisms finish film forming on the cathode electrode, argon is introduced into the reactor to drive away residual H2And carrying out electrification domestication for 30d by-400 mV (vs. Ag/AgCl), wherein when the removal efficiency of the sulfate reaches a stable state, the construction of the biological cathode is successful.
Operation of a bioelectrochemical reactor
Filling a sulfate culture medium containing 60mg/L-200mg/L into a cathode chamber containing a cathode biological membrane; phosphate buffer solution was charged into the anode chamber. Argon gas was then introduced into each chamber for 20 minutes to ensure that all the air in the reactor was removed, and the chambers were sealed separately. And finally, connecting the device into a potentiostat through a lead, connecting the working electrode with the negative electrode of the potentiostat, connecting the auxiliary electrode with the positive electrode of the potentiostat, connecting the reference electrode with the reference electrode of the potentiostat, and setting the electrode potential to be 400mV (vs. Ag/AgCl).
After the bioelectrochemical device is started, batch tests are carried out, the current change of the working electrode is continuously monitored through the electrochemical workstation, and the reduction of sulfate and the generation of sulfide are quantitatively detected. The results of the blank and three batch tests are shown in table 1:
TABLE 1 reduction of sulfate and sulfide formation and sulfate removal in batch runs
Wherein,aOCV: an open circuit voltage;bN.D.: not detected.
FIGS. 2 and 3 show the results of the third period of acclimatization, in which the data were repeatedly measured three times and the initial sulfate concentration was182.70±1.91mg L-1The reaction time is 10 days, and the sulfate concentration at the end is 34.56 +/-7.17 mg L-1. The hydrogen sulfide generation concentration is 48.64 +/-4.10 mg L-1. The number of moles of electrons producing hydrogen sulfide per liter of solution at the end of 10d was 1173.83C L-1The number of moles of electrons per liter of solution passing through the cathode electrode was 1838.48C L-1The current utilization efficiency was 71.83%.
The cyclic scanning analysis of the biological cathode electrode has the scanning range of-0.75-0.5V and the scanning speed of 5mV s-1As shown in fig. 4, a pair of similar cytochrome protein redox peaks appeared at 0.10and-0.2V (vs. ag/AgCl), and at the same time, a single reduction peak appeared at-0.7V (vs. ag/AgCl), which is presumed to be a hydrogen reduction peak, and this experiment used a voltage of-0.4V (vs. ag/AgCl), which did not reach the-0.7V (vs. ag/AgCl) voltage required for hydrogen reduction, and the presence of hydrogen was not detected in the experiment, and these results can be presumed that the cathode microorganism directly obtained electrons from the electrode through the bacterial membrane protein itself for sulfate reduction rather than through hydrogen mediated process.
Example 2: sulfide reduction of metallic copper ion test
Soluble sulfide produced by reduction of sulfate reducing bacteria has S2-、HS-、H2S, their morphology is pH-dependent, according to literature reports H when pH < 6.52S concentration is large, HS between pH 7 and 13-Mainly with a pH of > 13 and S2-Mainly comprises the following steps. The bioelectrochemical reaction was performed according to the procedure of example 1, and since the catholyte contained a buffer solution and the pH of the catholyte was about 8 after sulfate reduction, the sulfides in the catholyte should be HS-Therefore, when the concentration of the sulfide in the reactor continuously reaches more than 50mg/L, the effluent of the reactor is fed into the reactor according to the ratio of 1: 1 and contains 100mg/L of Cu2+Forming copper sulfide precipitate after the low-concentration wastewater, and detecting Cu in the wastewater2+Content, Cu of supernatant after precipitation2+The content is less than 5mg/L, Cu2+The removal rate of (a) is more than 95%.
Claims (2)
1. A method for treating heavy metal wastewater by using sulfate reducing bacteria growing by current is characterized in that
The method comprises the following specific steps:
(1) construction of a bioelectrochemical device
The bioelectrochemical device is in a double-chamber reactor configuration and comprises a potentiostat (4), a lead (5), a cathode chamber (1) and an anode chamber (2), wherein a working electrode (6) and a reference electrode (7) are inserted into the cathode chamber (1), and activated sludge of an urban sewage plant is added; an auxiliary electrode (8) is inserted into the anode chamber (2); the two chambers are separated by a diaphragm (3);
(2) preparation of cathode and anode compartment solutions
Anode chamber
0.05mol/L phosphate buffer solution with the pH value of 7.0,
cathode chamber
Na2HPO4·12H2O10.9g L-1,NaH2PO43.0g L-1,NaHCO32.0g L-1，KCl100mg L-1,MgCl240mg L-1,NH4Cl310mg L-1,CaCl250mg L-1，NaCl10mg L-1,FeCl225mg L-1,CoCl2·2H2O5mg L-1,MnCl2·4H2O5mg L-1,AlCl32.5mg L-1,(NH4)6Mo7O2415mg L-1,H3BO35mg L-1,NiCl2·6H2O0.5mg L-1,CuCl2·2H2O3.5mg L-1,ZnCl25mg L-1，180～200mg L-1Sulfate is used as an electron acceptor, and the pH value of the catholyte is adjusted to 7.2;
(3) biocathode preparation
A. Biofilm of microorganisms
Inoculating activated sludge of urban sewage plant, and introducing H2As an electron donor, and adding sulfate as an electron acceptor for enrichment culture for 2-3 months; inoculating the enriched autotrophic sulfate-reducing bacteria source into the cathode chamber of the constructed bioelectrochemical reactor, not electrifying, and continuously electrifying H2Stirring and culturing, and when the flora is enriched on the cathode electrode, the film formation is successful;
B. acclimation of biocathodes
After the microorganisms finish film forming on the cathode electrode, argon is introduced into the reactor to drive away residual H2Electrifying and domesticating the biological cathode by-400 mV (vs. Ag/AgCl), and when the removal efficiency of the sulfate reaches a stable state, indicating that the construction of the biological cathode is successful;
(4) operation of a bioelectrochemical reactor
Filling a sulfate culture medium containing 20mg/L-600mg/L into a cathode chamber containing a cathode biological membrane; loading phosphate buffer solution into the anode chamber; then argon is respectively introduced into the two chambers for 20 minutes to ensure that the air in the reactor is completely removed, and then the two chambers are respectively sealed; finally, the device is connected with a potentiostat through a lead, the working electrode is connected with the negative electrode of the potentiostat, the auxiliary electrode is connected with the positive electrode of the potentiostat, the reference electrode is connected with the reference electrode of the potentiostat, and the electrode potential range is set to be-400 mV to-700 mV (vs. Ag/AgCl); the concentration of sulfide in the catholyte reaches 50mg L-1The catholyte is replaced when the heavy metal ions are treated, and the replaced catholyte containing sulfide is used for treating the heavy metal ions.
2. Use of the method according to claim 1 in the treatment of low organic carbon heavy metal wastewater from mine wastewater, metal smelting wastewater, electroplating wastewater.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210091967 CN102642930B (en) | 2012-03-31 | 2012-03-31 | Method for treatment of metal waste water by sulfate reducing bacteria growing up with electric current |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210091967 CN102642930B (en) | 2012-03-31 | 2012-03-31 | Method for treatment of metal waste water by sulfate reducing bacteria growing up with electric current |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102642930A CN102642930A (en) | 2012-08-22 |
| CN102642930B true CN102642930B (en) | 2013-07-31 |
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| CN102925348B (en) * | 2012-11-11 | 2013-10-09 | 中国船舶重工集团公司第七二五研究所 | Device for detecting concentration of sulfate-reducing bacteria (SRB) |
| CN103319002B (en) * | 2013-06-27 | 2015-04-15 | 中国科学院过程工程研究所 | Method for biological treatment of sulfate wastewater employing synchronous electric catalysis of anode and cathode |
| CN103663884B (en) * | 2013-12-30 | 2015-07-08 | 合肥工业大学 | Method for enhancing degradation of organic arsenic in waste water of livestock breeding into pentavalent arsenic by utilizing weak potential |
| CN103898005B (en) * | 2014-01-09 | 2016-11-23 | 浙江大学 | Electro-chemical activity antibacterial and screening technique thereof |
| CN104310573A (en) * | 2014-11-19 | 2015-01-28 | 江南大学 | Combination electrode preparation method and application of combination electrode preparation method in bioelectricity Fenton system |
| CN105060504B (en) * | 2015-08-12 | 2017-04-05 | 北京化工大学 | A kind of two MFC of batch (-type) inactivity output-parallel improve the method that voltage processes heavy metal wastewater thereby |
| CN106345437B (en) * | 2016-11-08 | 2018-12-25 | 太原理工大学 | The preparation and its application in water process that conducting polymer consolidates sulfur materials |
| CN106630019B (en) * | 2016-11-08 | 2018-03-09 | 太原理工大学 | A kind of method of automatically controlled reduction simple substance removal of sulphur heavy metal ions in wastewater |
| CN108046427A (en) * | 2018-01-09 | 2018-05-18 | 衢州学院 | Low C/S is than the anaerobic bio-treated method of sulfate-containing organic wastewater under room temperature |
| CN111717965B (en) * | 2019-03-20 | 2022-06-28 | 中国石油化工股份有限公司 | Electro-filtration sterilization method for sulfate reducing bacteria |
| CN110078209B (en) * | 2019-05-16 | 2021-11-16 | 桂林电子科技大学 | Method for forming cadmium sulfur ore by reducing sulfate with microorganism |
| CN111054740B (en) * | 2019-12-27 | 2021-04-16 | 浙江大学 | Device and method for in-situ remediation of cadmium and lead polluted farmland soil by sulfate reduction system driven by microbial electrochemistry |
| CN113371818A (en) * | 2021-06-24 | 2021-09-10 | 广东石油化工学院 | Method for strengthening nitrogen/sulfur-containing wastewater autotrophic treatment of MEC (methanol-organic carbon) biological cathode |
| CN113845217A (en) * | 2021-11-02 | 2021-12-28 | 中山大学 | Method and device for removing refractory organic pollutants through sulfur-mediated bioelectrochemistry enhancement |
| CN114855000B (en) * | 2022-04-28 | 2023-08-22 | 湖北绿钨资源循环有限公司 | Method for separating and removing impurities from tungsten and molybdenum in tungsten smelting process |
| CN117904212A (en) * | 2024-03-01 | 2024-04-19 | 中山大学 | Biological preparation method and application of zero-valent iron sulfide |
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| CN2852128Y (en) * | 2005-12-09 | 2006-12-27 | 中国科学院海洋研究所 | Dual electrolytic cell for studying hydrogen permeation behavior of metal in sea mud containing sulfate-reducing bacteria |
| CN101503244B (en) * | 2009-03-20 | 2011-06-29 | 清华大学 | Strengthened autotrophs desulphurization apparatus with complex function |
| US9257709B2 (en) * | 2010-12-23 | 2016-02-09 | Stc.Unm | Paper-based fuel cell |
| CN102170006B (en) * | 2011-04-07 | 2013-02-06 | 重庆大学 | Micro-organism fuel battery capable of degrading volatile organic matters |
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