CN113426542A - Detoxification and stabilization method for hexavalent chromium-containing historical remaining tailings and surrounding soil - Google Patents
Detoxification and stabilization method for hexavalent chromium-containing historical remaining tailings and surrounding soil Download PDFInfo
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- CN113426542A CN113426542A CN202110750684.7A CN202110750684A CN113426542A CN 113426542 A CN113426542 A CN 113426542A CN 202110750684 A CN202110750684 A CN 202110750684A CN 113426542 A CN113426542 A CN 113426542A
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- soil
- hexavalent chromium
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- 239000002689 soil Substances 0.000 title claims abstract description 85
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000001784 detoxification Methods 0.000 title claims abstract description 11
- 230000006641 stabilisation Effects 0.000 title claims abstract description 9
- 238000011105 stabilization Methods 0.000 title claims abstract description 9
- 238000000197 pyrolysis Methods 0.000 claims abstract description 34
- 239000002028 Biomass Substances 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000011651 chromium Substances 0.000 claims abstract description 17
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000007873 sieving Methods 0.000 claims abstract description 9
- 239000000706 filtrate Substances 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 239000002699 waste material Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000010902 straw Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 230000000087 stabilizing effect Effects 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 4
- 240000008042 Zea mays Species 0.000 claims description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 2
- 235000005822 corn Nutrition 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000000717 retained effect Effects 0.000 claims 4
- 239000010907 stover Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 7
- 238000009825 accumulation Methods 0.000 abstract description 5
- 239000002154 agricultural waste Substances 0.000 abstract description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract 1
- 230000002950 deficient Effects 0.000 abstract 1
- 239000010419 fine particle Substances 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000002893 slag Substances 0.000 description 6
- 238000002791 soaking Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003900 soil pollution Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003583 soil stabilizing agent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/06—Reclamation of contaminated soil thermally
- B09C1/065—Reclamation of contaminated soil thermally by pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C19/00—Other disintegrating devices or methods
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
- B02C23/08—Separating or sorting of material, associated with crushing or disintegrating
- B02C23/16—Separating or sorting of material, associated with crushing or disintegrating with separator defining termination of crushing or disintegrating zone, e.g. screen denying egress of oversize material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
Landscapes
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Food Science & Technology (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a detoxification and stabilization method for chromium-polluted tailings and surrounding soil, which comprises the steps of grinding and sieving the tailings or the soil in a tailing area, and mixing the ground and sieved soil with biomass and a catalyst to obtain a mixture; and pyrolyzing the mixture, controlling the moisture content of air, pyrolyzing the mixture in a high-temperature oxygen-deficient environment, and reducing hexavalent chromium in the soil. According to the method, hexavalent chromium in the soil is reduced through co-pyrolysis of the biomass and the chromium-polluted soil, so that soil detoxification and chromium stabilization are realized, and the air problem caused by field accumulation and burning waste of agricultural wastes is reduced. The method reduces hexavalent chromium by utilizing hydrogen and carbon monoxide generated by pyrolysis of biomass under the action of a catalyst in an anoxic environment, so that reducing gas is fully contacted with the hexavalent chromium in fine-particle soil, the hexavalent chromium in the soil is removed to the maximum extent, the temperature of the soil after pyrolysis is lower than 55 ℃, the soil after pyrolysis is soaked in lime water at an outlet for cooling, solid-liquid separation is carried out, the obtained filter residue can be directly applied to the soil, and the filtrate is recycled.
Description
Technical Field
The invention belongs to the technical field of pollution treatment, and particularly relates to a hexavalent chromium-containing historical remaining tailing detoxification and stabilization method, which realizes low-cost harmless reduction of hexavalent chromium in tailing polluted areas.
Background
With the vigorous development of Chinese economy, mining gradually becomes a strong industry for flourishing development in various regions, but the environmental problem caused by open-air accumulation of mining and selecting tailings is worried about. Under long-term weathering and rain leaching, a large amount of heavy metals in the tailings enter the soil, and serious soil pollution is caused. Hexavalent chromium is very soluble in water, is easily migrated from soil to groundwater, and has great toxicity. Therefore, hexavalent chromium in the polluted soil of the tailing area is reduced, and the method has important significance for preventing and treating soil and water pollution.
Along with the enhancement of the environmental supervision, especially, the waste straws of the rural crops are forbidden to be burnt, so that a large amount of crop straws are accumulated in the field. As a new energy source, biochar has high heat value, low cost and zero emission and is highly concerned at home and abroad. Therefore, the field agricultural wastes have certain significance as the raw materials of the biochar.
The existing soil hexavalent chromium detoxification has the following problems: coal and biomass are mixed and pyrolyzed to generate reducing gas to reduce hexavalent chromium, and the method is high in cost and not beneficial to large-scale popularization. After the hexavalent chromium in the soil of the tailing area is reduced, the phenomenon of yellowing is easy to occur, namely the hexavalent chromium is oxidized into hexavalent chromium. Cannot be stabilized at one time. And the soil stabilizer cannot be completely and effectively stabilized, and leakage can occur under the long-term oxidation and leaching environments, so that the soil detoxification and stabilization efficiency is reduced.
Disclosure of Invention
Aiming at the defects existing in the problems, the invention provides a detoxification and stabilization method of history left tailings containing hexavalent chromium and surrounding soil, which reduces the toxicity of hexavalent chromium reduction and improves the availability of biochar.
The invention discloses a hexavalent chromium-containing historical remaining tailings detoxifying and stabilizing method, which comprises the following steps:
grinding the soil to be treated, and sieving;
(1) grinding the soil to be treated, and sieving;
(2) waste crop straws are dried, crushed and dried to prepare standby biomass;
(3) mixing the obtained standby biomass with the soil and the catalyst which are treated in the step (1) for pyrolysis to reduce hexavalent chromium in the soil into trivalent chromium and adsorb the trivalent chromium in the biochar to obtain pyrolyzed soil;
(4) after the temperature of the pyrolyzed soil is lower than 55 ℃, placing the pyrolyzed soil in lime water for cooling, and performing solid-liquid separation;
(5) and (4) paving the filter residue treated in the step (4) at room temperature, airing for 2 hours, and directly reusing the filtrate for fixing the pyrolyzed soil.
Preferably, the content of the hexavalent chromium in the historical remaining tailings and the surrounding soil comprises 1500-6000 mg/kg of chromium.
Preferably, the sieving is 60-100 mesh sieving.
Preferably, the biomass straw is dried outdoors for 48-54 hours, crushed to 2-5cm and dried in a drying oven at 45-55 ℃ for 36 hours, so that the water content of the biomass straw is lower than 40%.
Preferably, the biomass is crop straws such as corn stalks, straws and the like; can be prepared separately or mixed in any proportion.
Preferably, the selected catalyst is potassium carbonate, and the catalyst, soil and biomass are mixed in proportion and pyrolyzed for 40-60 min.
Preferably, the mass ratio of the soil, the biomass and the catalyst is 4:12:3, the biomass and the catalyst are uniformly mixed, the mixture is placed at the bottom of a pyrolysis container, and the soil is flatly laid on the mixture.
Preferably, the pyrolysis conditions are: the pyrolysis heating rate is 10 ℃/min, the pyrolysis temperature is 500-.
Preferably, the mass fraction of the lime water is 0.5-0.8%, and the cooling time is 20-50 min.
Preferably, the filter residue obtained after solid-liquid separation is dried for 2 hours at room temperature, and the filtrate can be used for fixing the soil after pyrolysis again.
Preferably, the drying room temperature of the filter residue is 25 ℃ or above, the tiling thickness is not higher than 3cm, and the tiling mode is not limited.
The invention relates to a reaction equation:
because the biomass is pyrolyzed to generate a large amount of reducing gas at the temperature of 500-600 ℃, the following reactions can occur at high temperature:
C+O2=CO2 2C+O2=2CO
C+H2O=CO+H2 C+CO2=2CO
CO+H2O=CO2+H2 C+2H2=CH4
CH4+H2O=CO+3H2
reducing gases CO, H2Reacting with hexavalent chromium at high temperature to reduce hexavalent chromium into trivalent chromium, thereby achieving the purpose of detoxification.
The biochar is soaked in lime water, so that the reduced trivalent chromium can be stabilized to the maximum extent, and the biochar can be directly applied to soil or used for other purposes.
Cr3++Ca(OH)2→Cr(OH)3↓+Ca2+
Because the soil has a large amount of carbonate and potassium ions, the product does not cause secondary pollution to the soil even if applied to the soil, has low price, can catalyze the gasification of biomass to the maximum extent, improves the gas yield and accelerates the reaction process.
Compared with the prior art, the beneficial results of the invention are as follows:
1. the invention promotes the generation of a large amount of reducing gas by controlling the temperature, the moisture and the gas retention time in the biomass pyrolysis process, thereby achieving the aim of reducing hexavalent chromium. Low cost and simple operation.
2. The biochar produced by the invention can be applied to soil to adsorb heavy metals and solidify carbon, so that the application of fertilizers is reduced.
3. According to the invention, the biochar is soaked in the lime water, and the trivalent chromium can be stabilized to the maximum extent by soaking the biochar in the lime water because the biochar has large and many gaps.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the embodiments are a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
Example 1:
the chromium slag and soil mixture in a chromium slag accumulation plant in a certain city of Zhejiang province has hexavalent chromium content of 3500 mg/kg.
Screening the soil containing hexavalent chromium, grinding and sieving by a 60-mesh sieve.
The waste crop straws are dried outdoors for 48 hours, crushed to 2-5cm and dried in a drying oven at 45 ℃ for 36 hours until the water content is lower than 40 percent, so that the standby biomass is prepared.
Selecting potassium carbonate as a catalyst, mixing the catalyst, soil and biomass in proportion, and pyrolyzing for 50 min; adjusting the mass ratio of soil, biomass and catalyst to be 4:12:3, uniformly mixing the biomass and the catalyst, placing the mixture at the bottom of a pyrolysis container, and spreading soil on the mixture; the pyrolysis conditions are as follows: the pyrolysis temperature rise rate is 10 ℃/min, the pyrolysis temperature is 550 ℃, the pyrolysis time is 60min, and the amount of introduced water vapor during pyrolysis is 1.5 g/min. When the temperature is reduced to 55 ℃ and the temperature of the pyrolyzed soil is 45 ℃, soaking the pyrolyzed soil in 0.5 mass percent lime water.
Carrying out solid-liquid separation, airing the obtained filter residue for 2 hours at room temperature, and reusing the filtrate for fixing the pyrolyzed soil; the filter residue was dried at room temperature of 27 ℃.
Taking three mixed samples of the detoxified and filtered residue soil, and measuring the contents of hexavalent chromium in the three mixed samples to be respectively 0.16mg/kg, 0.21mg/kg and 0.14mg/kg which are all lower than the national standard.
Example 2:
the content of hexavalent chromium in a mixture of the chromium slag and soil in a chromium slag accumulation field in the city of Yunnan Trijing is 3300 mg/kg.
Screening the soil containing hexavalent chromium, grinding and sieving by a 80-mesh sieve.
The waste crop straws are dried outdoors for 48 hours, crushed to 3-4cm and dried in a drying oven at 15 ℃ for 36 hours until the water content is lower than 40 percent, so as to prepare the standby biomass.
Selecting potassium carbonate as a catalyst, mixing the catalyst, soil and biomass in proportion, and pyrolyzing for 2 hours; and adjusting the mass ratio of the soil, the biomass and the catalyst to be 4:10:3, uniformly mixing the biomass and the catalyst, placing the mixture at the bottom of the pyrolysis container, and paving the soil on the mixture. The pyrolysis conditions are as follows: the pyrolysis temperature rise rate is 10 ℃/min, the pyrolysis temperature is 500 ℃, the pyrolysis time is 40min, and the amount of introduced water vapor during pyrolysis is 0.5 g/min. And when the temperature is reduced to 55 ℃, soaking the pyrolyzed soil in 0.7 mass percent of lime water.
Carrying out solid-liquid separation, airing the obtained filter residue for 2 hours at room temperature, and reusing the filtrate for fixing the pyrolyzed soil; the filter residue was dried at room temperature of 27 ℃.
Three mixed samples are taken from the detoxified residue soil, and the contents of hexavalent chromium in the three mixed samples are measured to be 1.19mg/kg, 1.23mg/kg and 1.17mg/kg respectively, which do not meet the national standard.
Example 3
The content of hexavalent chromium in a mixture of the chromium slag and soil in a chromium slag accumulation field in the city of Yunnan Trijing is 3300 mg/kg.
Screening the soil containing hexavalent chromium, grinding and sieving by a 80-mesh sieve.
The waste crop straws are dried outdoors for 48 hours, crushed to 2-4cm and dried in a drying oven at 25 ℃ for 36 hours until the water content is lower than 40 percent, so that the standby biomass is prepared.
Selecting potassium carbonate as a catalyst, mixing the catalyst, soil and biomass in proportion, and pyrolyzing for 2 hours; adjusting the mass ratio of soil, biomass and catalyst to be 4:12:3, uniformly mixing the biomass and the catalyst, placing the mixture at the bottom of a pyrolysis container, and spreading soil on the mixture; the pyrolysis conditions are as follows: the pyrolysis temperature rise rate is 10 ℃/min, the pyrolysis temperature is 500 ℃, the pyrolysis time is 40min, and the amount of introduced water vapor during pyrolysis is 0.5 g/min. And when the temperature is reduced to 30 ℃, soaking the pyrolyzed soil in 0.7 mass percent of lime water.
Carrying out solid-liquid separation, airing the obtained filter residue for 2 hours at room temperature, and reusing the filtrate for fixing the pyrolyzed soil; the filter residue was dried at room temperature of 27 ℃.
Taking three mixed samples of the detoxified residue soil, and measuring the contents of hexavalent chromium in the three mixed samples to be respectively 0.21mg/kg, 0.24mg/kg and 0.15mg/kg which are lower than the national standard.
The above is only a preferred embodiment of the present invention and is not limited to the above, and it will be appreciated by those skilled in the art that various changes and modifications can be made in the invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention shall be included in the scope of the present invention.
Claims (10)
1. A detoxification and stabilization method for hexavalent chromium-containing historical remaining tailings and surrounding soil is characterized by comprising the following steps:
(1) grinding the soil to be treated, and sieving;
(2) waste crop straws are dried, crushed and dried to prepare standby biomass;
(3) mixing the obtained standby biomass with the soil and the catalyst which are treated in the step (1) for pyrolysis to reduce hexavalent chromium in the soil into trivalent chromium and adsorb the trivalent chromium in the biochar to obtain pyrolyzed soil;
(4) after the temperature of the pyrolyzed soil is lower than 55 ℃, placing the pyrolyzed soil in lime water for cooling, and performing solid-liquid separation;
(5) and (5) paving the filter residue treated in the step (4) at room temperature, and airing to obtain the detoxified soil, wherein the filtrate can be returned to the step (4) to be used for fixing the pyrolyzed soil again.
2. The method of claim 1 wherein said historical tailings containing hexavalent chromium and surrounding soils are detoxified and stabilized to a chromium content in the range of 1500-6000 mg/kg.
3. The process for the detoxification and stabilization of hexavalent chromium-containing historical retained tailings and surrounding soils as claimed in claim 1, wherein said screening is through a 60-100 mesh screen.
4. The method for detoxifying and stabilizing hexavalent chromium-containing historical remaining tailings and surrounding soil according to claim 1, wherein the biomass straw is dried outdoors for 48-54 hours, crushed to 2-5cm, and dried in a drying oven at 45-55 ℃ for 36 hours to achieve a water content of less than 40%.
5. The method for detoxifying and stabilizing hexavalent chromium-containing historical retained tailings and surrounding soil according to claim 1, wherein the biomass is crop straw such as corn stover and straw; can be prepared separately or mixed in any proportion.
6. The method of detoxifying and stabilizing hexavalent chromium containing historical tailings and surrounding soil as claimed in claim 1, wherein the selected type of catalyst is potassium carbonate, and the catalyst, soil, and biomass are mixed in proportion and pyrolyzed for 40-60 min.
7. The method of claim 1 wherein said soil, biomass and catalyst are mixed uniformly in a mass ratio of 4:12:3, the mixture is placed at the bottom of a pyrolysis vessel, and soil is spread thereon.
8. The method for detoxifying and stabilizing hexavalent chromium-containing historical retained tailings and surrounding soil according to claim 1, wherein the pyrolysis conditions are: the pyrolysis heating rate is 10 ℃/min, the pyrolysis temperature is 500-.
9. The method for detoxifying and stabilizing hexavalent chromium-containing historical remaining tailings and surrounding soil according to claim 1, wherein the mass fraction of the limewater is 0.5-0.8%, and the cooling time is 20-50 min.
10. The method for detoxifying and stabilizing hexavalent chromium containing historical retained tailings and surrounding soil according to claim 1, wherein said filter residue is dried at room temperature of 25 ℃ and above and laid flat at a thickness of no greater than 3 cm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113816502A (en) * | 2021-10-15 | 2021-12-21 | 中国地质大学（北京） | Method and device for continuously removing hexavalent chromium in underground water by utilizing synthesis gas through microorganisms |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113816502A (en) * | 2021-10-15 | 2021-12-21 | 中国地质大学（北京） | Method and device for continuously removing hexavalent chromium in underground water by utilizing synthesis gas through microorganisms |
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