CN110790361B - Bioelectrochemical sulfur recovery system and method for treating sulfide-containing waste gas/wastewater - Google Patents
Bioelectrochemical sulfur recovery system and method for treating sulfide-containing waste gas/wastewater Download PDFInfo
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Abstract
The invention discloses a bioelectrochemical sulfur recovery system for treating sulfide-containing waste gas/wastewater, which comprises a reaction tank, wherein the reaction tank comprises an anode chamber, an anode arranged in the anode chamber, a cathode arranged in the cathode chamber, and an ion exchange membrane arranged between the anode chamber and the cathode chamber, wherein anolyte in the anode chamber is high-concentration reduced electronic medium aqueous solution; the cathode electrolyte in the cathode chamber adopts a bacterial culture medium containing oxidation state electronic media, and electroactive bacteria are added into the cathode electrolyte. The bioelectrochemical system avoids using anode reaction mediated by bacteria and adopts the anode reaction mediated by an electronic medium in a primary battery to selectively oxidize hydrogen sulfide, thereby obtaining high-quality elemental sulfur particles; the system can recover high-purity elemental sulfur, can also recover electric energy, has stable electricity generation effect, and can synchronously realize high-efficiency stable treatment of the waste gas/wastewater containing hydrogen sulfide and capacity.
Description
Technical Field
The invention relates to the technical field of waste water and waste gas treatment and sulfur resource recovery, in particular to a method for treating hydrogen sulfide waste gas/waste water and recovering elemental sulfur and electric energy by using an electronic media primary battery bioelectrochemical desulfurization system enhanced by iron-oxidizing bacteria.
Background
Hydrogen sulfide is a highly toxic and highly corrosive gas, and is widely present in waste gases and waste waters produced in the coal mine, petrochemical, leather, and other industries. Particularly, when high-sulfur-content wastewater is treated, the concentration of hydrogen sulfide generated along with the treatment can reach a high level, and if the hydrogen sulfide cannot be timely and effectively removed, environmental pollution, equipment corrosion and even harm to human life safety are often caused. On the other hand, sulfur is an important industrial raw material and is widely applied to the chemical fields of rubber, fertilizer, medicine, production and the like. Currently, sulfur is mainly derived from ores and crude oil, and these sources have the disadvantage of high preparation cost, so that it is very important to find an environmentally sustainable sulfur resource approach. The method for recovering elemental sulfur from sulfur-containing industrial waste gas and natural gas is an ideal solution, can not only reduce the problems of environmental pollution, equipment corrosion and the like in waste water and waste gas treatment, but also provide a sustainable sulfur resource production way.
Currently, the methods for treating hydrogen sulfide waste gas in the industry mainly include wet desulfurization (such as LO-CAT technology), dry desulfurization, claus technology, electrochemical technology, and micro-oxidation. However, these techniques often have the disadvantages of severe reaction conditions, high energy consumption, high equipment cost, complex process, etc., and are not suitable for treating the low-concentration hydrogen sulfide waste gas.
In contrast, biological methods generally have the characteristics of low treatment cost, mild reaction conditions, and the like. Conventional biological treatment methods for hydrogen sulfide include biofilters, membrane bioreactors, airlift bioreactors, and the like. However, these processes tend to oxidize hydrogen sulfide to various sulfur oxides such as thiosulfate, sulfite and sulfate during the reaction, thus making it difficult to recover elemental sulfur and also generating new contaminants.
In recent years, the bio-electrochemical system desulfurization technology is also beginning to be applied to the treatment of hydrogen sulfide-containing waste gas/water. The technology can remove hydrogen sulfide and recover electric energy, thereby having better application prospect. However, the current bioelectrochemical desulfurization system has the following problems: (1) the sulfur oxidation selectivity is low, and bacteria can oxidize sulfur ions to generate elemental sulfur and byproducts such as thiosulfate, sulfite and sulfate, so that the elemental sulfur is difficult to effectively recover; (2) the electricity generation efficiency of the bioanode formed by bacteria is low and unstable; (3) elemental sulfur is easy to deposit on the surface of the electrode, so that the long-term stable operation of the system is influenced by the passivation of the electrode. The present invention is directed to solving the above problems.
Disclosure of Invention
The invention aims to provide a high-efficiency, stable and low-cost bioelectrochemical system capable of continuously treating hydrogen sulfide waste gas/waste water and simultaneously realizing high-quality elemental sulfur and stable electric energy recovery aiming at the defects of the conventional bioelectrochemical system in the aspects of hydrogen sulfide waste gas/waste water treatment and resource recovery application.
In order to solve the above technical problems, a bioelectrochemical sulfur recovery system for treating sulfide-containing waste gas/water according to a first aspect of the present invention is a bioelectrochemical desulfurization system for a galvanic cell with an enhanced iron-oxidizing bacteria, comprising a reaction cell, the reaction cell including an anode chamber, an anode disposed in the anode chamber, a cathode disposed in the cathode chamber, and an ion exchange membrane disposed between the anode chamber and the cathode chamber, wherein: the anolyte in the anode chamber is a reduced electronic medium aqueous solution; the cathode electrolyte in the cathode chamber adopts a bacterial culture medium containing oxidation state electronic media, and iron-oxidizing bacteria are added into the cathode electrolyte.
In an embodiment of the present invention, the electrode material for preparing the anode is selected from materials with good conductivity, preferably: stainless steel, carbon material.
In an embodiment of the present invention, the electrode material for preparing the cathode is selected from carbon materials with good biocompatibility, preferably: carbon felt, carbon cloth, carbon paper, and the like.
In an embodiment of the present invention, the reduced electron mediator aqueous solution is an iodide aqueous solution, including but not limited to potassium iodide; the concentration range is 0.01-1 mol/L; preferably in high concentrations, e.g. 0.5-1 mol/l.
In an embodiment of the present invention, the oxidation state electron mediator contained in the catholyte is a trivalent iron salt, such as ferric sulfate.
Wherein the iron-oxidizing bacteria are preferably Thiobacillus ferrooxidans.
In one embodiment of the invention, the bacteria culture medium is LX5 mineral salt culture medium ((NH)4)2SO4 3.5g/L、KCl 0.119g/L、K2HPO40.058 g/L、Ca(NO3)2·4H2O 0.0168g/L、MgSO4·7H2O 0.583g/L、FeSO4·7H2O44.2 g/L, pH is 2.5).
In an embodiment of the invention, the primary cell reactor with enhanced iron-oxidizing bacteria further comprises an external circuit connected to the anode and the cathode, respectively. The anode reduction state electron mediator and the cathode oxidation state electron mediator can form a primary battery through an external circuit, and spontaneous oxidation-reduction reaction is carried out.
Furthermore, the anode chamber is provided with an aeration port and an air outlet for hydrogen sulfide waste gas, the waste gas aeration hole is positioned at the lower part or the bottom of the outer side of the anode chamber, and the air outlet is positioned at the top of the anode chamber.
Furthermore, the cathode chamber is provided with an air aeration hole and an air outlet hole, the air aeration hole is positioned at the lower part or the bottom of the outer side of the cathode chamber, and the air outlet hole is positioned at the top of the cathode chamber.
An iron-oxidizing bacteria enhanced electronic-media primary cell bioelectrochemical desulfurization system comprises a reaction tank, wherein the reaction tank comprises an anode chamber, an anode arranged in the anode chamber, a cathode arranged in the cathode chamber, and an ion exchange membrane arranged between the anode chamber and the cathode chamber, an anolyte in the anode chamber is a high-concentration reduced-state electronic-media aqueous solution, wherein the reduced-state electronic media are oxidized on the surface of the anode to generate oxidized-state electronic media, and the oxidized-state electronic media oxidize sulfur ions in the anode chamber to generate high-purity elemental sulfur particles; the catholyte in the cathode chamber adopts a bacterial culture medium containing high-concentration oxidation state electronic media, wherein the oxidation state electronic media are reduced to reduction state electronic media on the surface of the cathode, and the catholyte is added with iron-oxidizing bacteria to oxidize the reduction state electronic media into oxidation state electronic media so as to maintain the high-concentration oxidation state electronic media in the cathode chamber.
The invention provides a method for treating sulfide-containing waste gas/water and recovering high-purity elemental sulfur and electric energy by using an electronic media primary battery bioelectrochemical sulfur recovery system enhanced by iron-oxidizing bacteria, which comprises the following steps:
(1) conveying the waste gas/wastewater containing hydrogen sulfide to an anode chamber, oxidizing a reduced-state electronic medium contained in the anode chamber on the surface of an anode to generate an oxidized-state electronic medium, oxidizing sulfur ions in the anode chamber by the oxidized-state electronic medium to generate high-purity elemental sulfur particles, and discharging the gas after removing the hydrogen sulfide;
(2) the electrolyte bacteria culture medium in the cathode chamber contains oxidation state electronic media which are reduced into reduction state electronic media on the surface of the cathode; continuously pumping air into the cathode chamber to allow iron-oxidizing bacteria to grow, and exhausting gas in the cathode chamber through an exhaust port;
(3) and discharging the anolyte periodically, and recovering the generated elemental sulfur particles from the anolyte.
In one embodiment of the invention, the anolyte enriched with the electron mediator after the sulfur particles are removed is returned to the anode chamber for recycling.
In one embodiment of the invention, the anode chamber I-Oxidation reaction and Fe in cathode chamber3+The reduction reaction forms electron transfer through an external circuit, thereby forming a chemical primary battery. The electrons of the external circuit can be collected by a capacitor or used directly to drive an electrical device.
The amount of hydrogen sulfide off-gas treated depends on the rate of formation of the oxidized electron mediator in the anode compartment, which depends on the concentrations of the reduced electron mediator in the anode and the oxidized electron mediator in the cathode in the galvanic cell, the higher the concentration of these, the greater the amount of hydrogen sulfide off-gas treated.
The method for treating sulfide-containing waste gas/wastewater and recovering high-purity elemental sulfur and electric energy by using the electronic media primary battery bioelectrochemical sulfur recovery system based on iron-oxidizing bacteria enhancement comprises the following steps:
(1) conveying the waste gas/wastewater containing hydrogen sulfide to an anode chamber, wherein the reduced electronic medium in the anode chamber is an aqueous solution electrolyte, the reduced electronic medium is oxidized on the surface of an anode to generate an oxidized electronic medium, and the oxidized electronic medium oxidizes sulfur ions in the anode chamber to generate high-purity elemental sulfur particles;
oxidizing sulfur ions to generate solid elemental sulfur particles, and discharging gas from which hydrogen sulfide is removed through an air outlet;
(2) continuously pumping air into the cathode chamber through an aeration port of the cathode chamber by an air pump for bacterial growth, and discharging indoor gas through an exhaust port;
(3) and collecting and recovering the generated elemental sulfur particles from the anolyte periodically, and returning the anolyte rich in the electron media after the sulfur particles are removed to the anode chamber for recycling.
Compared with other existing processes for treating hydrogen sulfide waste gas/wastewater, the method has the following advantages:
(1) the bioelectrochemical system avoids using anode reaction mediated by bacteria and adopts anode reaction mediated by electron medium in a primary battery for selectively oxidizing hydrogen sulfide, thereby obtaining high-quality elemental sulfur particles; compared with the prior art, the microbial electrochemical method can only obtain sulfate radicals, but can not obtain elemental sulfur;
(2) the desulfurization system based on the electronic medium primary battery has stable electricity generation effect, can recover high-purity elemental sulfur and electric energy while performing hydrogen sulfide waste gas/wastewater treatment, and realizes energy-producing waste gas/wastewater treatment, while the existing microbial electrochemical method does not generate electricity;
(3) iron-oxidizing bacteria are added into a cathode chamber of the system, and reduced-state electronic media generated in the cathode chamber are oxidized again by the iron-oxidizing bacteria to generate oxidized-state electronic media, so that the continuous regeneration of the oxidized-state electronic media is realized, and the system is economical and applicable and can stably run; the cathode chamber of the existing microbial electrochemical method is added with mixed bacteria;
(4) the invention is a closed electronic medium redox circulation system, can realize continuous treatment of hydrogen sulfide waste gas/wastewater only by continuously aerating air into the cathode chamber, and has simple and convenient process operation and easy implementation;
(5) after the elemental sulfur generated in the anode chamber is periodically recovered, the anolyte can be recycled for a long time.
The invention firstly provides a bioelectrochemical desulfurization system constructed based on an electronic medium primary battery with redox activity for removing hydrogen sulfide and recycling resources. The system adopts high-concentration electronic medium aqueous solution as electrolytic cell anolyte and catholyte, generates oxidized electronic medium in an anode chamber through oxidation-reduction reaction spontaneously generated by electronic medium in an anode chamber and electronic medium in a cathode chamber, and simultaneously generates reduced electronic medium in the cathode chamber. The oxidation state electronic medium generated in the anode chamber can specifically oxidize the sulfur ions into elemental sulfur, thereby avoiding the generation of other by-products and realizing the recovery of high-quality elemental sulfur resources. Iron-oxidizing bacteria are added into the cathode chamber, and the reduced-state electron mediator generated by the cathode is oxidized into an oxidized-state electron mediator by virtue of the bacteria so as to ensure that the concentration of the oxidized-state electron mediator in the cathode chamber is maintained at a high level. Thus, stable electric energy can be recovered from the hydrogen sulfide waste gas treatment process through the system. The system for treating the hydrogen sulfide waste gas and recycling resources has the advantages of high efficiency, stability, simple equipment, low cost and the like, and provides a process for treating the hydrogen sulfide waste gas/wastewater, which can continuously produce energy and recycle high-quality sulfur resources.
Drawings
Fig. 1 is a schematic diagram of a bioelectrochemical desulfurization system for treating sulfide-containing flue gas/wastewater according to an embodiment of the present invention, in which 1 is an anode chamber, also referred to as a sulfur recovery chamber, 2 is an anode, 3 is a cathode chamber, also referred to as an iron circulation chamber, 4 is a cathode, 5 is an ion exchange membrane, and 6 is an external circuit.
FIG. 2 is I-Oxidation products I3 -Cumulative kinetic plots showing Fe in the cathode compartment of the primary iron-iodine cell of example 13+Concentration vs. anode I3 -The influence of the production rate of (c);
FIG. 3 shows the anode chamber S2-Removal kinetics diagram showing kinetics data of removal of sulfide ions (initial concentration of sulfide ions is 1mM) in example 1, and Fe3+The effect of concentration on the rate of sulfur ion removal;
FIG. 4 shows the power generation effect, cathode total iron concentration and ferrous iron concentration changes of the complete desulfurization system in the process of treating hydrogen sulfide waste gas after adding Acidithiobacillus ferrooxidans into the cathode chamber in example 2;
FIG. 5 is an EDS profile of the anode compartment recovery of elemental sulfur in example 2;
FIG. 6 is an XPS characterization of elemental sulfur recovered from the anode compartment in example 2;
FIG. 7 is a curve showing the change of the concentration of sulfur ions in the anode chamber during the batch treatment of sodium sulfide wastewater by the bioelectrochemical system in example 3.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples. It should be understood that these examples are for illustrative purposes and are not intended to limit the scope of the present invention. The conditions used in the examples may be further adjusted according to the conditions of the particular manufacturer, and the conditions not specified are generally the conditions in routine experiments.
Introduction and summary
The present invention is illustrated by way of example and not by way of limitation. It should be noted that references to "an" or "one" embodiment in this disclosure are not necessarily to the same embodiment, but to at least one.
Various aspects of the invention are described below. It will be apparent, however, to one skilled in the art that the present invention may be practiced according to only some or all aspects of the present invention. For purposes of explanation, specific numbers, materials and configurations are set forth in order to provide a thorough understanding of the present invention. It will be apparent, however, to one skilled in the art that the present invention may be practiced without specific details. In other instances, well-known features are omitted or simplified in order not to obscure the present invention.
Various operations will be described as multiple discrete steps in turn, and in a manner that is most helpful in understanding the present invention; however, the description in order should not be construed as to imply that these operations are necessarily order dependent.
Various embodiments will be described in terms of typical classes of reactants. It will be apparent to those skilled in the art that the present invention may be practiced using any number of different types of reactants, not just those provided herein for purposes of illustration. Furthermore, it will also be apparent that the invention is not limited to any particular hybrid example.
Example 1
The bioelectrochemical desulfurization system for treating sulfide-containing exhaust gas/wastewater shown in fig. 1 comprises a reaction cell including an anode chamber 1 (also referred to as a sulfur recovery chamber in this embodiment), an anode 2 disposed in the anode chamber 1, a cathode chamber 3 (an iron circulation chamber in this embodiment) having a water inlet and outlet, a cathode 4 disposed in the cathode chamber 3, an ion exchange membrane 5 disposed between the anode chamber 1 and the cathode chamber 3, and an external circuit 6 connected to the anode and the cathode, respectively.
In the bioelectrochemical desulfurization system of the present invention, the anolyte is a 0.01-1M aqueous solution of an iodide, such as potassium iodide, and the standard redox potential of the substance should be between 0.14V (when in a reduced state relative to a standard hydrogen electrode) and 0.771V (when in an oxidized state). The catholyte contains 0.01-1M aqueous ferric sulfate solution and contains mineral salt components of Acidithiobacillus ferrooxidans. I is-Oxidized on the surface of the anode to form I3 -。Fe3+Is reduced to generate Fe on the surface of the cathode2+,Fe2+Oxidation to Fe by oxygen catalyzed by Acidithiobacillus ferrooxidans3+。
In example 1, carbon paper electrodes were used for both the anode and the cathode. The external circuit for connecting the anode and cathode is a titanium wire. The anolyte was 0.20M KI and the catholyte contained 0.10M Fe2(SO4)3、3.50g/L(NH4)2SO4,0.119g/L KCl、0.058g/L K2HPO4、0.0168g/L Ca(NO3)2·4H2O、0.583g/L MgSO4·7H2O (pH 2.5). The acidophilic thiobacillus ferrooxidans bacterial liquid is centrifuged for 15 minutes at 10000g, then bacterial cells are collected, washed by 0.05M dilute sulfuric acid, resuspended and then added into a cathode chamber.
EXAMPLE 2 Bioelectrochemical desulfurization method for treating waste gas containing hydrogen sulfide
1% of H2S(99%N2) Gas is introduced into the anode chamber of the embodiment 1 of the invention to simulate the discharge of hydrogen sulfide waste gas into the system, and the anode electrolyte is uniformly mixed by a stirrer in the whole reaction process; air is continuously pumped into the cathode chamber by an air pump, a catholyte sample is periodically collected, and the total iron and ferrous iron concentration is measured.
FIG. 2 is I-Oxidation products I3 -Cumulative kinetic plots showing Fe in the cathode compartment of a primary iron-iodine cell3+Concentration vs. anode I3 -The influence of the production rate of (c); FIG. 3 shows the anode chamber S2-Removal kinetics, showing kinetics data for sulfide ion removal (initial concentration of sulfide ion of 1mM), and Fe3+The effect of concentration on the rate of sulfur ion removal; referring to fig. 2 and 3, the cathode Fe is maintained3+And an anode I-The optimal concentration ratio is 1: 1, cathode Fe3+The higher the concentration, the higher the anode I3 -The faster the rate of ion generation, the better the hydrogen sulfide treatment.
FIG. 4 shows the electrogenesis effect, cathode total iron concentration and ferrous iron concentration change of the complete desulfurization system in the process of treating hydrogen sulfide waste gas after adding acidophilic thiobacillus ferrooxidans into the cathode chamber, and Fe in the catholyte after adding acidophilic thiobacillus ferrooxidans into the cathode chamber2+Can be effectively oxidized to generate Fe3+To maintain high concentration of Fe in catholyte3+. The bioelectrochemical desulfurization system generates more stable output current in the process of treating the hydrogen sulfide waste gas/wastewater.
FIG. 5 shows an EDS profile for elemental sulfur recovery in the anode compartment; the method specifically comprises the following steps:
element(s) | By weight% | Atom% |
|
100 | 100 |
And referring to the XPS characterization chart of elemental sulfur recovered from the anode chamber of fig. 6, the particles recovered from the anode were identified as elemental sulfur particles by EDS and XPS characterization. This demonstrates that the system is effective in recovering elemental sulfur from hydrogen sulfide off-gas.
If 0.20M aqueous ferric ion and 0.20M aqueous iodide ion are used as the catholyte and anolyte, respectively, a 100ml galvanic cell system can handle about 108L of exhaust gas containing 1000ppm hydrogen sulfide per day.
EXAMPLE 3 bioelectrochemical desulfurization method for batch treatment of wastewater containing sodium sulfide
The artificial preparation contains about 50mg/L S2-The sodium sulfide wastewater of the invention is introduced into the anode chamber of the embodiment 1 of the invention to simulate the process of sulfide wastewater batch treatment by the bioelectrochemical desulfurization system. The anolyte adopts a bacterial mineral salt culture medium dissolved with 0.2M KI, the catholyte adopts a bacterial mineral salt culture medium dissolved with 0.1M ferric sulfate, and the components of the bacterial mineral salt culture medium are consistent with those of the culture medium in the embodiment 1. Mixing the anode electrolyte uniformly by a stirrer in the whole reaction process; air is continuously pumped into the cathode chamber by an air pump, an anolyte sample is periodically collected, and the concentration of the sulfur ions is measured.
Referring to fig. 7, a graph of the change in the concentration of sulfide ions, the bioelectrochemical desulfurization system exhibited a relatively stable sulfide ion removal effect during the batch treatment of sodium sulfide simulated wastewater, which confirms the potential of the system for the treatment of sulfide wastewater.
The above-described specific embodiments are merely preferred embodiments of the present invention, and it should be noted that, for those skilled in the art, various modifications or substitutions can be made without departing from the principle of the present invention, and these modifications or substitutions should also be regarded as the protection scope of the present invention.
Claims (8)
1. The method for treating the sulfide-containing waste gas/wastewater by the bioelectrochemical sulfur recovery system is characterized by comprising the following steps of: the method comprises the following steps:
(1) conveying the waste gas/wastewater containing hydrogen sulfide to an anode chamber, wherein the anode chamber contains a reduced electronic medium aqueous solution electrolyte, the reduced electronic medium is oxidized on the surface of the anode to generate an oxidized electronic medium, the oxidized electronic medium oxidizes sulfur ions in the anode chamber to generate high-purity elemental sulfur particles, and the gas from which the hydrogen sulfide is removed is discharged;
(2) the electrolyte bacteria culture medium in the cathode chamber contains oxidation state electronic media which are reduced into reduction state electronic media on the surface of the cathode; continuously pumping air into the cathode chamber to supply the active bacteria to grow, and exhausting the air in the cathode chamber through an exhaust port;
(3) discharging anolyte periodically, and recovering elemental sulfur particles generated by the anolyte;
anode chamber I-Oxidation reaction and Fe in cathode chamber3+The reduction reaction forms electron transfer through an external circuit, and then a chemical primary battery is formed;
a bioelectrochemical sulfur recovery system for treating sulfide-containing waste gas/water comprises a reaction tank, wherein the reaction tank comprises an anode chamber, an anode arranged in the anode chamber, a cathode arranged in the cathode chamber, and an ion exchange membrane arranged between the anode chamber and the cathode chamber, and anolyte in the anode chamber is a reduced state electronic medium aqueous solution; the cathode electrolyte in the cathode chamber adopts a bacterial culture medium containing oxidation state electronic media, and iron-oxidizing bacteria are added into the cathode electrolyte.
2. The method of claim 1, wherein the anode is made of an electrode material selected from the group consisting of stainless steel and carbon materials.
3. The method of claim 1, wherein the electrode material for preparing the cathode is selected from a carbon material having good biocompatibility.
4. The method of claim 1, wherein the reduced aqueous electronic mediator solution is an aqueous iodide solution.
5. The method of claim 1 wherein the reduced aqueous electron mediator solution is potassium iodide; the concentration is in the range of 0.01-1 mol/L.
6. The method of claim 1 wherein the catholyte solution comprises an oxidized form of the mediator of electrons in the trivalent iron salt form.
7. The method of treating sulfide-containing waste gas/water in a bioelectrochemical sulfur recovery system according to claim 1, wherein said bacterial culture medium is LX5 mineral salt culture medium.
8. The method of claim 1, wherein the anolyte enriched with the electron mediator after removal of sulfur particles is returned to the anode compartment for recycling.
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CN105470546A (en) * | 2016-01-04 | 2016-04-06 | 武汉理工大学 | Method for recovering sulfur in wastewater by using microbial fuel cell |
CN108529714A (en) * | 2018-05-08 | 2018-09-14 | 中国科学技术大学苏州研究院 | The method of optical electro-chemistry reaction tank and its Treatment of Hydrogen Sulfide Waste Gas and waste water |
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CN101385180A (en) * | 2006-02-14 | 2009-03-11 | 马赫内托特殊阳极有限公司 | Device comprising a new cathode system and method for generating electrical energy with use thereof |
CN105470546A (en) * | 2016-01-04 | 2016-04-06 | 武汉理工大学 | Method for recovering sulfur in wastewater by using microbial fuel cell |
CN108529714A (en) * | 2018-05-08 | 2018-09-14 | 中国科学技术大学苏州研究院 | The method of optical electro-chemistry reaction tank and its Treatment of Hydrogen Sulfide Waste Gas and waste water |
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