CN113816502A - Method and device for continuously removing hexavalent chromium in underground water by utilizing synthesis gas through microorganisms - Google Patents
Method and device for continuously removing hexavalent chromium in underground water by utilizing synthesis gas through microorganisms Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/2806—Anaerobic processes using solid supports for microorganisms
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
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- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Biodiversity & Conservation Biology (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
- Removal Of Specific Substances (AREA)
Abstract
One or more embodiments of the present disclosure relate to the field of water pollution treatment technology, and in particular, to a method and an apparatus for continuously removing hexavalent chromium from groundwater by using syngas. The method comprises the following steps: mixing the synthesis gas and hexavalent chromium polluted underground water to obtain hexavalent chromium polluted water containing the synthesis gas, wherein the synthesis gas consists of hydrogen, carbon monoxide and carbon dioxide; introducing hexavalent chromium polluted water containing synthesis gas into a reactor inoculated with microorganisms to perform hexavalent chromium reduction reaction; wherein the microorganism reduces hexavalent chromium to trivalent chromium using the syngas as an electron donor during the hexavalent chromium reduction reaction. The method can efficiently remove hexavalent chromium in the groundwater.
Description
Technical Field
One or more embodiments of the present disclosure relate to the field of water pollution treatment technology, and in particular, to a method and an apparatus for continuously removing hexavalent chromium from groundwater by using syngas.
Background
Hexavalent chromium is a swallowable poison and can invade the body through the digestive tract, causing vomiting, abdominal pain, etc., and possibly causing genetic defects. According to experimental research, hexavalent chromium affects the breeding of mice when the mice are fed with a large dose of hexavalent chromium, so that the number of newborn mice per litter is reduced, and the weight of fetal mice is reduced. While chromium metal, trivalent or tetravalent chromium does not have these toxicities.
Therefore, hexavalent chromium in the underground water is reduced to trivalent chromium which is easy to precipitate, and the hexavalent chromium in the underground water can be removed, so that the effect of purifying the water quality of the underground water is achieved.
Disclosure of Invention
The embodiment of the specification describes a method and a device for continuously removing hexavalent chromium in underground water by using synthesis gas through microorganisms, and the hexavalent chromium in the underground water can be efficiently removed.
In a first aspect, the embodiments of the present specification provide a method for continuously removing hexavalent chromium in groundwater by using synthesis gas with microorganisms, the method comprising: mixing the synthesis gas and hexavalent chromium polluted underground water to obtain hexavalent chromium polluted water containing the synthesis gas, wherein the synthesis gas consists of hydrogen, carbon monoxide and carbon dioxide; introducing hexavalent chromium polluted water containing synthesis gas into a reactor inoculated with microorganisms to perform hexavalent chromium reduction reaction; wherein the microorganism reduces hexavalent chromium to trivalent chromium using the syngas as an electron donor during the hexavalent chromium reduction reaction.
In some embodiments, the synthesis gas-containing hexavalent chromium-contaminated water body is a synthesis gas-saturated hexavalent chromium-contaminated water body.
In some embodiments, the volume ratio of hydrogen, carbon monoxide and carbon dioxide in the syngas is 2:2: 1.
In some embodiments, the reactor is filled with a mixture of soil sediment and quartz sand, the microorganisms are indigenous microorganisms in the soil sediment; wherein, in the mixture, the weight ratio of the soil sediment to the quartz sand is 1: 10.
in some embodiments, the initial concentration of hexavalent chromium in the hexavalent chromium-contaminated groundwater is 0.25 mM; the temperature of the reactor during the hexavalent chromium reduction reaction is between 20 ℃ and 24 ℃; the hydraulic retention time during the hexavalent chromium reduction reaction was 24 hours.
In a second aspect, the embodiments of the present specification provide a method for continuously removing hexavalent chromium in underground water by using a microorganism through synthesis gas, the method employs a long-term continuous flow column experimental apparatus, the experimental apparatus includes an air bag, an aeration bottle, a peristaltic pump, a reactor and a water collecting bottle, which are arranged in sequence, wherein the reactor is inoculated with the microorganism, the air bag contains the synthesis gas, the aeration bottle contains the hexavalent chromium-polluted underground water, and the synthesis gas consists of hydrogen, carbon monoxide and carbon dioxide; the method comprises the following steps: filling the synthetic gas in the gas bag into the hexavalent chromium polluted underground water in the aeration bottle through a gas pump to prepare a hexavalent chromium polluted water body containing the synthetic gas; introducing the hexavalent chromium polluted water containing the synthesis gas into the reactor by using the peristaltic pump to perform a hexavalent chromium reduction reaction; wherein during the hexavalent chromium reduction reaction, the microorganism reduces hexavalent chromium to trivalent chromium using the syngas as an electron donor; and the hexavalent chromium polluted water body subjected to the hexavalent chromium reduction reaction flows into the water collecting bottle.
In a third aspect, the embodiment of the present specification provides a long-term continuous flow column experimental apparatus for continuously removing hexavalent chromium in underground water, the experimental apparatus includes an air bag, an aeration cylinder, a peristaltic pump, a reactor and a water collecting cylinder, which are arranged in sequence, wherein microorganisms are inoculated in the reactor, the air bag contains synthesis gas, the aeration cylinder contains hexavalent chromium-polluted underground water, and the synthesis gas consists of hydrogen, carbon monoxide and carbon dioxide; the synthetic gas in the gas bag is filled into the hexavalent chromium polluted underground water in the aeration bottle under the action of a gas pump so as to prepare hexavalent chromium polluted water containing the synthetic gas; the peristaltic pump is used for introducing hexavalent chromium polluted water containing synthesis gas into the reactor to carry out hexavalent chromium reduction reaction; wherein during the hexavalent chromium reduction reaction, the microorganism reduces hexavalent chromium to trivalent chromium using the syngas as an electron donor; the water collecting bottle is used for containing the water body treated by the hexavalent chromium reduction reaction.
In some embodiments, the reactor is a device that maintains the microorganisms in a light-tight and anaerobic environment.
In some embodiments, the reactor is a plexiglas column with a column body coated with aluminum foil.
In a fourth aspect, the embodiments of the present specification provide the use of the experimental apparatus provided in the third aspect for removing hexavalent chromium from groundwater.
The method and the device for continuously removing hexavalent chromium in underground water by using the synthesis gas by using the microorganisms provided by the embodiment of the specification can efficiently reduce the hexavalent chromium in the underground water to generate trivalent chromium which is non-toxic and difficult to migrate, so that the hexavalent chromium is removed from the underground water.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 shows an experimental setup provided in the examples of this specification;
FIG. 2 shows the dynamic changes of Cr (VI) concentration of inlet water and outlet water and the corresponding reduction rate and reduction rate.
Detailed Description
It is to be understood that the scope of the invention is not to be limited to the specific embodiments described below; it is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments, and is not intended to limit the scope of the present invention; in the description and claims of the present application, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, and materials used in the examples, any methods, devices, and materials similar or equivalent to those described in the examples may be used in the practice of the invention in addition to the specific methods, devices, and materials used in the examples, in keeping with the knowledge of one skilled in the art and with the description of the invention.
Microorganisms can anaerobically oxidize various electron donors, releasing electrons. These electrons can reduce the highly toxic, easily migrating hexavalent chromium to a less toxic, easily precipitating trivalent chromium. Among the common electron donors that microorganisms can anaerobically oxidize include: organic matter, zero-valent iron, zero-valent sulfur, hydrogen, methane, etc.
Wherein, organic matters such as glucose, lactate, formate, acetate, butyrate, citrate and the like are common organic electron donors for reducing hexavalent chromium by microorganisms. The organic electron donor has high bioavailability, and the microorganism can obtain more energy from the oxidation process, so that the high toxicity of hexavalent chromium is relieved. However, organic electron donors tend to excite larger biomass, causing clogging of processing equipment.
Zero-valent iron is a highly efficient hexavalent chromium chemical reducing agent and is biologically effective as an electron donor. However, under alkaline conditions, the resulting precipitate prevents the biochemical reduction reaction from continuing. Zero-valent sulfur is non-toxic, low in cost and insoluble in water, but the main disadvantage is that the products (sulfate and acid) after the electrons are released by microbial oxidation affect the reaction operation and the effluent quality.
Hydrogen and methane are renewable clean energy sources, have wide sources and low price, and are ideal electron donors. Compared with organic electron donors, the organic electron donors generate less excessive biomass and effectively prevent treatment equipment from being blocked. But the preparation and purification of the compounds have large energy consumption and high cost, and potential safety hazards exist in the production and use processes.
In view of the above situation, thisThe application embodiment provides a method for continuously removing hexavalent chromium in underground water by utilizing synthesis gas through microorganisms. Among these, syngas is a mixed gas that can be produced by the thermal gasification of non-renewable and renewable energy sources. Syngas contains mainly hydrogen, carbon monoxide and carbon dioxide. The synthesis gas exists in the incomplete combustion process of industrial fuel in great amount, and has great yield, easy trapping, low cost and no need of separation and purification. The synthesis gas can be used as industrial fuel, but the volumetric energy density of the synthesis gas is less than 13MJ/m3) Only accounts for about 40 percent of natural gas, and the direct use of the natural gas as fuel has lower efficiency. Synthesis gas can be converted to methane and short chain fatty acids by anaerobic microbial technology. However, anaerobic processes for converting syngas to methane and short chain fatty acids are difficult to control, resulting in unstable yields. The hydrogen and the carbon monoxide in the synthesis gas are efficient microorganism electron donors, and have active biochemical properties and high bioavailability. Carbon dioxide is also an important component of syngas, can be used as an inorganic carbon source required by autotrophic microorganisms, and has the advantage of low biomass. Thus, syngas has great potential as a microbial electron donor and carbon source.
In the embodiment of the application, a long-term continuous flow column experiment is designed, and the high efficiency of the synthesis gas as an electron donor for reducing hexavalent chromium by microorganisms and the stability of a reduction product are proved. Thereby providing a scheme for removing hexavalent chromium in underground water by microorganisms by taking synthesis gas as an electron donor. The scheme can reduce hexavalent chromium in the underground water into trivalent chromium, wherein the trivalent chromium can be precipitated in situ and is difficult to migrate.
Next, the scheme provided in the embodiments of the present application will be specifically described.
FIG. 1 shows an experimental setup used in a long-term continuous flow column experiment designed according to an embodiment of the present application. The experimental device can be called as a long-term continuous flow column experimental device. Wherein the organic glass cylinder is used as a reactor for reducing hexavalent chromium. Basic size of organic glass cylinder: height 25cm, inner diameter 5 cm. The column body is coated with aluminum foil, and the inlet and outlet ports and the sampling port are well sealed. During the running period of the long-term continuous flow column experiment, the experimental device is kept sealed in the whole experiment process, so that no gas escapes and no environmental gas enters. During operation, the synthetic gas is continuously introduced into the aeration cylinder through the air pump through the air inlet pipe and then circularly returned to the air bag through the air outlet pipe, the synthetic gas is supplemented into the air bag every day, and sufficient gas supply is ensured. The synthesis gas saturated hexavalent chromium polluted water body flows upwards into the column through the peristaltic pump, and the effluent and the outlet gas are collected in the water collecting bottle and the connecting air bag through the water outlet pipe.
50g of soil sediment around a Panzhihua metal smelting plant in Sichuan province and 500g of quartz sand are completely mixed and filled in the space in the column. Wherein the soil deposit contains microorganisms. These microorganisms are indigenous to the soil deposit.
Synthesizing hexavalent chromium polluted underground water, wherein the water body comprises the following components in percentage by weight (mg/L): CaCl2 246.4、MgCl2·6H2O 1057.2、NaCl 445.9、KCl 28.3、KH2PO429.9% hexavalent chromium by Ka2Cr2O4Is provided in the form of (1). Before the synthesized hexavalent chromium polluted underground water is used, nitrogen degassing is carried out on the synthesized hexavalent chromium polluted underground water for 30 minutes. Among them, the synthesized hexavalent chromium polluted groundwater can be called hexavalent chromium polluted water body or synthesized hexavalent chromium polluted water body or hexavalent chromium polluted groundwater. During the operation period of the long-term continuous flow column experiment, the synthesis gas is continuously aerated by the air pump to synthesize the hexavalent chromium polluted water body (namely, the synthesis gas is continuously injected into the synthesized hexavalent chromium polluted water body), and the hexavalent chromium polluted water body saturated by the synthesis gas is obtained. Wherein the amount of the synthesized hexavalent chromium polluted water body is 300mL, and the flow of the air pump is 0.45L/min. The synthesis gas saturated hexavalent chromium polluted water body flows upwards into the column through the peristaltic pump.
Wherein the synthesis gas consists of hydrogen, carbon monoxide and carbon dioxide. Wherein the volume ratio of the hydrogen to the carbon monoxide to the carbon dioxide is 2:2: 1.
During the long-term continuous flow column experiment operation, air is supplemented into the air bag connected with the air pump every day. The long-term continuous flow column experiment was carried out over a period of 115 days (d) in 3 stages, each stage maintaining the temperature of the experimental apparatus at 22. + -. 2 ℃.
Wherein, the operation conditions of each stage are shown in Table 1.
TABLE 1 conditions at various stages in aquifers and corresponding Cr (VI) reduction efficiencies
Specifically, in the 1-2 stage, synthesis gas with normal proportion (namely the volume ratio of hydrogen to carbon monoxide to carbon dioxide is 2:2:1) is used, in the 3 stage, carbon dioxide-free synthesis gas is used, nitrogen is used for replacing carbon dioxide, and the content of the rest components is unchanged. At each stage, the dynamic changes in hexavalent chromium concentration, reduction rate, and reduction rate are monitored. The experimental runs and manipulations were maintained at room temperature (22. + -. 2 ℃). Meanwhile, two groups (2 groups by 3) of serum bottle control reactors are arranged, 250mL of serum bottles are added, 2g of soil sediment and 240mL of synthesized hexavalent chromium polluted water are added, the residual headspace is filled with synthesis gas, and the serum bottles which are supplied with the synthesis gas but are not inoculated serve as a non-biological control group. An inoculated control group with nitrogen gas instead of syngas was used as a biological control, and the initial hexavalent chromium concentration was 0.25 mM.
Collecting organic glass column effluent every day, respectively measuring and determining hexavalent chromium concentration and total chromium concentration by using an ultraviolet-visible spectrophotometer and an inductively coupled plasma mass spectrometer, and monitoring the removal effect. The results are shown in FIG. 2. In stage 1, the reduction rate of 0.25mM hexavalent chromium is 95.1 + -3.1% under 24 hours hydraulic retention time, and the corresponding reduction rate of hexavalent chromium is 0.23 + -0.01 mM/d. After the addition of 0.5mM hexavalent chromium in stage 2, the reduction rate is only reduced to 73.2. + -. 5.4%, but the reduction rate is increased to 0.36. + -. 0.02 mM/d. In stage 3, a carbon dioxide-free synthesis gas is supplied, the remaining operating conditions correspond to those of stage 1, and the hexavalent chromium reduction rate and the reduction rate are reduced to 81.6. + -. 3.7% and 0.20. + -. 0.01mM/d compared to stage 1. Meanwhile, hexavalent chromium was hardly removed in the control group, indicating that hexavalent chromium reduction is mediated by microorganisms using syngas as an electron donor, not chemical reduction.
1mL of the biological samples after each stage was also collected along with 1mL of inoculum for high throughput 16S rRNA gene sequencing and analysis of microbial community succession. Results for the microbial community indicated that: there are two major hexavalent chromium reduction routes. The Pseudomonas can reduce hexavalent chromium heterotrophically, or directly oxidize carbon monoxide to couple hexavalent chromium reduction; hydrogenophaga also has great potential in the direct electronic reduction of hexavalent chromium by oxidation of hydrogen and carbon monoxide. Another leading process is a synergistic approach between different microorganisms in the aquifer, in which Methanobacterium can convert carbon monoxide, carbon dioxide and methane into mono-and bi-carbon organics, which are further utilized by the heterotrophic hexavalent chromium reducing bacteria to reduce hexavalent chromium.
After the experiment, the precipitate in the column was collected, and the crystal structure and valence state of the hexavalent chromium-producing product were measured using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). XRD analysis showed that the precipitate was mainly Cr (OH)3XPS further confirms that hexavalent chromium is reduced to produce trivalent chromium which is non-toxic and difficult to migrate.
The above results demonstrate that this biological system has a certain high load bearing capacity and is robust against cr (vi) load fluctuations in groundwater (simulated groundwater for synthetic hexavalent chromium-contaminated water). In addition, the carbon dioxide in the synthesis gas is used as a high-quality microbial inorganic carbon source, and the removal performance of hexavalent chromium is improved, so that the carbon dioxide in the synthesis gas is not required to be removed, the use amount of an alkali washing solvent can be saved, and the operating cost and the environmental pollution risk of waste alkali liquor are reduced.
The total chromium removal rate of each stage is 90.4 +/-3.2%, 68.0 +/-4.0% and 77.2 +/-2.8% in sequence, which indicates that a large amount of hexavalent chromium reduction product precipitate is generated. XRD analysis showed that the precipitate was mainly Cr (OH)3XPS further confirms that hexavalent chromium is reduced to produce trivalent chromium which is non-toxic and difficult to migrate.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A method for continuously removing hexavalent chromium in underground water by using synthesis gas through microorganisms is characterized by comprising the following steps:
mixing the synthesis gas and hexavalent chromium polluted underground water to obtain hexavalent chromium polluted water containing the synthesis gas, wherein the synthesis gas consists of hydrogen, carbon monoxide and carbon dioxide;
introducing hexavalent chromium polluted water containing synthesis gas into a reactor inoculated with microorganisms to perform hexavalent chromium reduction reaction;
wherein the microorganism reduces hexavalent chromium to trivalent chromium using the syngas as an electron donor during the hexavalent chromium reduction reaction.
2. The process of claim 1 wherein the synthesis gas-containing hexavalent chromium-contaminated water body is a synthesis gas-saturated hexavalent chromium-contaminated water body.
3. The process according to claim 1 or 2, characterized in that the volume ratio of hydrogen, carbon monoxide and carbon dioxide in the synthesis gas is 2:2: 1.
4. The method of claim 1, wherein the reactor is filled with a mixture of soil sediment and quartz sand, and the microorganisms are indigenous microorganisms in the soil sediment; wherein, in the mixture, the weight ratio of the soil sediment to the quartz sand is 1: 10.
5. the method of claim 1 wherein the initial concentration of hexavalent chromium in the hexavalent chromium-contaminated groundwater is 0.25 mM;
the temperature of the reactor during the hexavalent chromium reduction reaction is between 20 ℃ and 24 ℃;
the hydraulic retention time during the hexavalent chromium reduction reaction was 24 hours.
6. A method for continuously removing hexavalent chromium in underground water by utilizing synthesis gas through microorganisms is characterized in that a long-term continuous flow column experimental device is applied to the method, the experimental device comprises an air bag, an aeration cylinder, a peristaltic pump, a reactor and a water collecting cylinder which are sequentially arranged, wherein microorganisms are inoculated in the reactor, the air bag contains the synthesis gas, the aeration cylinder contains the hexavalent chromium-polluted underground water, and the synthesis gas consists of hydrogen, carbon monoxide and carbon dioxide;
the method comprises the following steps:
filling the synthetic gas in the gas bag into the hexavalent chromium polluted underground water in the aeration bottle through a gas pump to prepare a hexavalent chromium polluted water body containing the synthetic gas;
introducing the hexavalent chromium polluted water containing the synthesis gas into the reactor by using the peristaltic pump to perform a hexavalent chromium reduction reaction; wherein during the hexavalent chromium reduction reaction, the microorganism reduces hexavalent chromium to trivalent chromium using the syngas as an electron donor;
and the hexavalent chromium polluted water body subjected to the hexavalent chromium reduction reaction flows into the water collecting bottle.
7. A long-term continuous flow column experimental device for continuously removing hexavalent chromium in underground water is characterized by comprising an air bag, an aeration cylinder, a peristaltic pump, a reactor and a water collecting cylinder which are sequentially arranged, wherein microorganisms are inoculated in the reactor, the air bag contains synthesis gas, the aeration cylinder contains hexavalent chromium-polluted underground water, and the synthesis gas consists of hydrogen, carbon monoxide and carbon dioxide;
wherein the content of the first and second substances,
the synthesis gas in the gas bag is filled into the hexavalent chromium polluted underground water in the aeration bottle under the action of a gas pump so as to prepare a hexavalent chromium polluted water body containing the synthesis gas;
the peristaltic pump is used for introducing hexavalent chromium polluted water containing synthesis gas into the reactor to carry out hexavalent chromium reduction reaction; wherein during the hexavalent chromium reduction reaction, the microorganism reduces hexavalent chromium to trivalent chromium using the syngas as an electron donor;
the water collecting bottle is used for containing the water body treated by the hexavalent chromium reduction reaction.
8. The apparatus of claim 7, wherein the reactor is a means of maintaining the microorganisms in a light-tight and anaerobic environment.
9. The apparatus of claim 7, wherein the reactor is a plexiglas column with a column shaft coated with aluminum foil.
10. Use of the apparatus of any one of claims 7 to 9 for removing hexavalent chromium from ground water.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SU1198020A1 (en) * | 1984-01-13 | 1985-12-15 | Институт Микробиологии И Вирусологии Им.Д.К.Заболотного | Method of biological purification of waste water from compounds of sexivalent chromium |
US5569596A (en) * | 1995-01-04 | 1996-10-29 | The Board Of Regents Of The University Of Oklahoma | Method for bacterial reduction of chromium (VI) |
US20110017663A1 (en) * | 2009-07-21 | 2011-01-27 | The Regents Of The University Of Michigan | System and method for simultaneous biologically mediated removal of contaminants from contaminated water |
CN113426542A (en) * | 2021-07-02 | 2021-09-24 | 昆明理工大学 | Detoxification and stabilization method for hexavalent chromium-containing historical remaining tailings and surrounding soil |
-
2021
- 2021-10-15 CN CN202111201585.XA patent/CN113816502A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SU1198020A1 (en) * | 1984-01-13 | 1985-12-15 | Институт Микробиологии И Вирусологии Им.Д.К.Заболотного | Method of biological purification of waste water from compounds of sexivalent chromium |
US5569596A (en) * | 1995-01-04 | 1996-10-29 | The Board Of Regents Of The University Of Oklahoma | Method for bacterial reduction of chromium (VI) |
US20110017663A1 (en) * | 2009-07-21 | 2011-01-27 | The Regents Of The University Of Michigan | System and method for simultaneous biologically mediated removal of contaminants from contaminated water |
CN113426542A (en) * | 2021-07-02 | 2021-09-24 | 昆明理工大学 | Detoxification and stabilization method for hexavalent chromium-containing historical remaining tailings and surrounding soil |
Non-Patent Citations (2)
Title |
---|
L.A. DU PREEZ等: "Biological Sulphate Removal from Mining Effiuents Utilizing Producer Gas as Energy Source", 《4TH INTERNATIONAL MINERAL WATER ASSOCIATION CONGRESS》 * |
李永峰等, 哈尔滨工业大学出版社 * |
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