CN115010207B - Method for repairing toxic, harmful and refractory organic pollutants in wetland by utilizing copper slag photocatalysis reinforcement - Google Patents
Method for repairing toxic, harmful and refractory organic pollutants in wetland by utilizing copper slag photocatalysis reinforcement Download PDFInfo
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- CN115010207B CN115010207B CN202210133553.9A CN202210133553A CN115010207B CN 115010207 B CN115010207 B CN 115010207B CN 202210133553 A CN202210133553 A CN 202210133553A CN 115010207 B CN115010207 B CN 115010207B
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- 239000010949 copper Substances 0.000 title claims abstract description 94
- 239000002893 slag Substances 0.000 title claims abstract description 89
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 82
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 39
- 231100000331 toxic Toxicity 0.000 title claims abstract description 34
- 230000002588 toxic effect Effects 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 13
- 230000002787 reinforcement Effects 0.000 title claims abstract description 12
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000002344 surface layer Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 150000001879 copper Chemical class 0.000 claims abstract description 8
- 230000001105 regulatory effect Effects 0.000 claims abstract description 8
- 230000003213 activating effect Effects 0.000 claims abstract description 7
- 230000001276 controlling effect Effects 0.000 claims abstract description 7
- 125000004122 cyclic group Chemical group 0.000 claims abstract 2
- 239000002699 waste material Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000002351 wastewater Substances 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 7
- 230000000536 complexating effect Effects 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000010842 industrial wastewater Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims 2
- 238000009360 aquaculture Methods 0.000 claims 1
- 244000144974 aquaculture Species 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 3
- 230000000593 degrading effect Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 230000003014 reinforcing effect Effects 0.000 abstract 1
- CDOWNLMZVKJRSC-UHFFFAOYSA-N 2-hydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1 CDOWNLMZVKJRSC-UHFFFAOYSA-N 0.000 description 16
- 230000015556 catabolic process Effects 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 8
- 238000005286 illumination Methods 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- HJLSLZFTEKNLFI-UHFFFAOYSA-N Tinidazole Chemical compound CCS(=O)(=O)CCN1C(C)=NC=C1[N+]([O-])=O HJLSLZFTEKNLFI-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229960005053 tinidazole Drugs 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- C02F1/008—Control or steering systems not provided for elsewhere in subclass C02F
-
- 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
- C02F2101/30—Organic compounds
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2103/20—Nature of the water, waste water, sewage or sludge to be treated from animal husbandry
-
- 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
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
-
- 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
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/20—Total organic carbon [TOC]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Water Treatment By Sorption (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for repairing toxic and harmful refractory organic pollutants in a wetland by utilizing copper slag photocatalysis reinforcement, which comprises the steps of activating copper slag (crushing, grinding, calcining, adding acid for reaction, drying to excite the activity of metal elements in the copper slag), paving the activated copper slag on the surface layer of the wetland to be repaired, regulating and controlling the concentration ratio of metal ions in the copper slag to soluble organic matters (DOM) in a polluted water body of the wetland, so that the DOM in the polluted water body and the metal ions in the copper slag are fully complexed to form DOM-metal complexes, and under the condition of sunlight, the DOM-metal complexes generate photoinduced electron transfer to generate hydroxyl free radicals, thereby reinforcing and degrading refractory organic pollutants in the polluted water body of the wetland. The method is simple to operate and low in cost, can thoroughly degrade toxic, harmful and refractory organic pollutants in the wetland, is not easy to produce secondary pollution, and realizes cyclic utilization of copper slag resources.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a method for repairing toxic, harmful and refractory organic pollutants in a wetland by utilizing copper slag photocatalysis reinforcement.
Background
Copper slag is waste produced in the copper production process. The stacking of copper slag occupies a large amount of land, the environmental load is continuously increased, the infiltration of heavy metal can pollute soil and water resources during stacking, dust in the copper slag can pollute the atmosphere, and the health of human beings is endangered. The development difficulty of the new technology for comprehensively utilizing the copper slag resources is high, the large-scale consumption and the high-valued comprehensive utilization of the resources are limited, and huge resource waste is caused.
Although the wetland can cooperatively remove nutrient substances and organic pollutants in water body through a physical-chemical-biological composite restoration mechanism formed between plants, matrixes and microorganisms, has the advantages of low construction and use cost, simple operation and maintenance, low energy consumption and the like, the wetland also has certain limitations in pollutant treatment, such as low-temperature environment, insufficient oxygen content of the wetland and the like, and organic pollutants which are easy to cause toxicity, harm and difficult degradation can not reach ideal degradation efficiency through a wetland system. Aiming at the defects in the prior art, a method for repairing toxic, harmful and refractory organic pollutants in the wetland by utilizing copper slag photocatalysis reinforcement is provided. The soluble organic matter (DOM) in the polluted water body of the wetland to be repaired contains a large number of common chromophoric groups such as aromatic carboxyl, hydroxyl and carbonyl, and the like, so that the water body not only can absorb solar radiation and generate excited triplet DOM # 3 DOM * ) And some reactive oxygen species, also capable of complexing with metal ions, thereby affecting contaminant degradation. Aiming at the characteristics that uniform illumination can be obtained for photocatalysis under a sufficient illumination condition when the water depth in the wetland is shallower, hydroxyl radicals (OH) can be generated under the illumination condition after complexing of DOM and metal ions, the organic pollutants in the wetland are intensively degraded, copper slag is selected for waste utilization, the copper slag is enabled to be paved on the surface layer of the wetland after being activated, then the proportion of the metal ions in the copper slag and TOC values of DOM in the polluted water body of the wetland is regulated and controlled, DOM and metal ions are complexed to form DOM-metal complexes, active oxygen species mainly based on OH are generated by illumination, the organic pollutants which are difficult to degrade in the polluted water body of the wetland are intensively degraded, and toxic, harmful and difficult to degrade the pollutants in the organic wastewater into toxic, harmless micromolecular acid or mineralize the pollutants into CO 2 And water.
Disclosure of Invention
The invention provides a method for repairing toxic, harmful and refractory organic pollutants in a wetland by utilizing copper slag photocatalysis reinforcement, which utilizes soluble organic matters (DOM) in polluted water body of the wetland to be repaired and metal ions in copper slag to be fully complexed under the illumination condition to form DOM-metal complex to generate OH to strengthen the toxic, harmful and refractory organic pollutants in the wetland. The ratio of the molar concentration of metal ions in copper slag to the TOC value of soluble organic matters in the wetland polluted water is particularly important, and in a proper ratio range, the DOM-metal complex generates photoinduced electron transfer under the condition of sunlight to efficiently generate and OH to strengthen and degrade toxic, harmful and refractory organic pollutants in the wetland, so that the toxic, harmful and refractory pollutants are thoroughly degraded, the recycling is realized, the operation is simple, and the secondary pollution is not easy to generate.
The invention is realized in such a way that it comprises the following steps:
s1, firstly, activating waste copper slag, wherein the copper slag activation step comprises crushing and grinding, calcining, acid adding reaction, drying and measuring the metal content of the activated copper slag;
s2, adjusting the pH value of a polluted water body in the wetland to be repaired containing toxic and harmful organic pollutants difficult to degrade to 5-8, and measuring the TOC value of soluble organic matters in the polluted water body of the wetland to be repaired;
s3, directly paving the copper slag activated in the step 1 on the surface layer of the wetland to be repaired containing toxic and harmful organic pollutants difficult to degrade, and regulating and controlling the concentration ratio of metal ions in the copper slag to soluble organic matters in the wetland polluted water body to fully complex the metal ions in the copper slag with the soluble organic matters in the wetland polluted water body to form a DOM-metal complex;
s4, enclosing the water inlet and the water outlet of the wetland by using a baffle plate, and insolating the polluted water body of the wetland to be repaired containing toxic and harmful hardly-degradable organic pollutants paved in the step 3 for 7-21 days, wherein after sunlight illumination, DOM-metal complex in the polluted water body of the wetland to be repaired is photo-induced to generate hydroxyl free radicals with high reactivity, so that the toxic and harmful hardly-degradable organic pollutants can be degraded into small molecular acids or mineralized into small molecular acids without selectivityCO 2 And water, meanwhile, the copper slag can absorb part of pollutants, the polluted water body in the wetland to be repaired is discharged from the water outlet after being treated, and the water inlet is discharged into the organic wastewater to be treated again, so that the wastewater can be circularly treated.
Preferably, in the step S1, the copper slag is activated by crushing and grinding the waste copper slag to 10-100 meshes, ensuring that the porosity is 30-50% after being paved on a wetland, calcining for 2-6 hours at 600-800 ℃, then adding sulfuric acid solution for reaction and activation for 20-60 minutes, wherein the drying temperature is 400-500 ℃, and the drying time is 10-24 hours.
Further, in the step S1, the copper slag is crushed and ground to 30 meshes, calcined for 6 hours at 600 ℃, then added with sulfuric acid solution for reaction and activation for 45 minutes, and the drying temperature is 450 ℃ and the drying time is 18 hours.
Preferably, the pH value of the polluted water body in the wetland to be repaired containing the toxic and harmful refractory organic pollutants in the step S2 is adjusted to 7.
Preferably, the thickness of the copper slag paved on the surface layer of the wetland in the step S3 is 0.1-0.4 m.
Further, the copper slag paving thickness in the step S3 is 0.3m.
Preferably, the water depth of the wetland to be repaired containing the toxic and harmful organic pollutants difficult to degrade in the step S3 is 0.3-1 m, and the organic wastewater discharged from the water inlet of the wetland comprises one or more of culture wastewater, pharmaceutical wastewater and industrial wastewater.
Preferably, the soluble organic matters in the wetland to be repaired comprise heterogeneous hydrocarbon mixtures which can be dissolved in water, acid or alkali solution and consist of oxygen, nitrogen and sulfur-containing amino acid, aromatic, aliphatic and other functional groups.
Preferably, the metal ions in the copper slag after activation comprise Fe 3+ 、Cu 2+ One or more of Fe 3+ 、Cu 2+ The content of (C) is 45-350 mg/kg -1 。
Preferably, the sufficient complexing time between the metal ions in the copper slag and the soluble organic matters in the water body polluted by the wetland to be repaired is 30-120 min.
Preferably, the ratio of the molar concentration of metal ions in the copper slag to the TOC value of soluble organic matters in the wetland polluted water body is 1:1-4:1, and the DOM-metal complex can efficiently generate OH within the ratio range.
Further, the ratio of the molar concentration of metal ions in the copper slag to the TOC value of soluble organic matters in the wetland polluted water body is 2:1.
Preferably, the number of days of insolation in step S4 is 15d.
The invention has the beneficial effects that:
1. the invention fully utilizes the principle that DOM-metal complex generates photoinduced electron transfer to generate OH, so that soluble organic matters in the wetland and heavy metals in copper slag are complexed to generate OH under the illumination condition, and organic pollutants difficult to degrade in the wetland are enhanced and degraded, and other additional technologies are not needed, thus the invention has the advantages of simple process, low cost and convenient popularization and application.
2. The source of the metal ions used in the invention is waste copper slag, so that the method has the advantages of low cost and easily available raw materials, and can utilize the waste copper slag as resources, thereby realizing the development concept of treating waste with waste and being green and low in carbon.
3. As surface layer filler in the wetland, the waste copper slag not only can provide a source of metal ions and DOM to complex and generate OH to strengthen and degrade toxic, harmful and refractory organic pollutants in the wetland, but also can play roles in filtering and adsorbing the pollutants.
4. The method has the advantages of simple process, thorough degradation of toxic and harmful organic pollutants difficult to degrade in the wetland to be repaired, high efficiency and simple operation, and obvious environmental, economic and social benefits.
Detailed Description
The invention is further illustrated, but is not limited in any way, by the following examples, and any modifications based on the teachings of the invention are within the scope of the invention.
Example 1
The method comprises the steps of activating waste copper slag, crushing and grinding to 30 meshes, calcining at 600 ℃, adding 1mM sulfuric acid for reaction for 45min, and drying at 450 ℃ for 18h. Will contain toxic and harmful substancesAnd (3) regulating the pH value of the polluted water body in the wetland to be repaired of the refractory organic pollutants to 7, and measuring the TOC value of the soluble organic matters in the polluted water body of the wetland to be repaired to be 5mgC/L. The activated copper slag (wherein Fe 3+ 、Cu 2+ The content is 100 mg/kg -1 ) Paving the copper slag on the surface layer of the wetland to be repaired, and controlling the amount of copper slag paved to enable Fe to be generated 3+ 、Cu 2+ The molar concentration of the metal ions in the copper slag is 20 mu M, at the moment, the ratio of the molar concentration of the metal ions in the copper slag to the TOC value of DOM in the polluted water body is 4:1, the metal ions in the copper slag and the DOM in the wetland polluted water body are fully complexed to form DOM-metal complexes, the polluted water body of the wetland to be repaired stays and is insolated for 15d, after sunlight is irradiated, the DOM-metal complexes are photoinducted to generate OH, the OH can react with terephthalic acid to generate 2-hydroxy terephthalic acid, the content of the 2-hydroxy terephthalic acid is measured through a high performance liquid chromatograph, the content of the OH is calculated to be 2.6 mu M, and the degradation rate of nitrobenzene which is difficult to degrade in the effluent of the wetland is measured to reach 90.7%, and the degradation rate of tinidazole is measured to reach 91.5%.
Example 2
The method comprises the steps of activating waste copper slag, crushing and grinding to 30 meshes, calcining at 600 ℃, adding 1mM sulfuric acid for reaction for 45min, and drying at 450 ℃ for 18h. And (3) regulating the pH value of the polluted water body in the wetland to be repaired containing the toxic and harmful refractory organic pollutants to 7, and determining the TOC value of the soluble organic matters in the polluted water body of the wetland to be repaired to be 5mgC/L. The activated copper slag (wherein Fe 3+ 、Cu 2+ The content is 100 mg/kg -1 ) Paving the copper slag on the surface layer of the wetland to be repaired, and controlling the amount of copper slag paved to enable Fe to be generated 3+ 、Cu 2+ The molar concentration of the metal ions in the copper slag is 15 mu M, at the moment, the ratio of the molar concentration of the metal ions in the copper slag to the TOC value of DOM in the polluted water body is 3:1, the metal ions in the copper slag and the DOM in the wetland polluted water body are fully complexed to form DOM-metal complex, the polluted water body of the wetland to be repaired stays and is insolated for 15d, after sunlight is irradiated, the DOM-metal complex is photoinducted to generate OH, the OH can react with terephthalic acid to generate 2-hydroxy terephthalic acid, the content of the 2-hydroxy terephthalic acid is measured through a high performance liquid chromatograph, the content of the OH is calculated to be 3.2 mu M, and the humidity is measuredThe degradation rate of nitrobenzene which is an organic pollutant difficult to degrade in the ground effluent reaches 92.8 percent, and the degradation rate of tinidazole reaches 93.4 percent.
Example 3
The method comprises the steps of activating waste copper slag, crushing and grinding to 30 meshes, calcining at 600 ℃, adding 1mM sulfuric acid for reaction for 45min, and drying at 450 ℃ for 18h. And (3) regulating the pH value of the polluted water body in the wetland to be repaired containing the toxic and harmful refractory organic pollutants to 7, and determining the TOC value of the soluble organic matters in the polluted water body of the wetland to be repaired to be 5mgC/L. The activated copper slag (wherein Fe 3+ 、Cu 2+ The content is 100 mg/kg -1 ) Paving the copper slag on the surface layer of the wetland to be repaired, and controlling the amount of copper slag paved to enable Fe to be generated 3+ 、Cu 2+ The molar concentration of the metal ions in the copper slag is 10 mu M, at the moment, the ratio of the molar concentration of the metal ions in the copper slag to the TOC value of DOM in the polluted water body is 2:1, the metal ions in the copper slag and the DOM in the wetland polluted water body are fully complexed to form DOM-metal complexes, the polluted water body of the wetland to be repaired stays and is insolated for 15d, after sunlight is irradiated, the DOM-metal complexes are photoinducted to generate OH, the OH can react with terephthalic acid to generate 2-hydroxy terephthalic acid, the content of the 2-hydroxy terephthalic acid is measured through a high performance liquid chromatograph, the content of the OH is calculated to be 3.8 mu M, and the degradation rate of nitrobenzene which is difficult to degrade in the effluent of the wetland is measured to reach 94.7%, and the degradation rate of tinidazole is measured to reach 96.8%.
Example 4
The method comprises the steps of activating waste copper slag, crushing and grinding to 30 meshes, calcining at 600 ℃, adding 1mM sulfuric acid for reaction for 45min, and drying at 450 ℃ for 18h. And (3) regulating the pH value of the polluted water body in the wetland to be repaired containing the toxic and harmful refractory organic pollutants to 7, and determining the TOC value of the soluble organic matters in the polluted water body of the wetland to be repaired to be 5mgC/L. The activated copper slag (wherein Fe 3+ 、Cu 2+ The content is 100 mg/kg -1 ) Paving the copper slag on the surface layer of the wetland to be repaired, and controlling the amount of copper slag paved to enable Fe to be generated 3+ 、Cu 2+ The molar concentration of the metal ions in the copper slag is 5 mu M, and the ratio of the molar concentration of the metal ions in the copper slag to the TOC value of DOM in the polluted water body is 1:1, so that the metal ions in the copper slag and the polluted water body of the wetland are formedDOM is fully complexed to form a DOM-metal complex, the polluted water body of the wetland to be repaired stays for insolation for 15d, after sunlight is irradiated, the DOM-metal complex is photo-induced to generate OH which can react with terephthalic acid to generate 2-hydroxy terephthalic acid, the content of the 2-hydroxy terephthalic acid is measured by a high performance liquid chromatograph to further calculate the content of the OH to be 2.8 mu M, and the degradation rate of nitrobenzene which is an organic pollutant difficult to degrade in the effluent of the wetland is measured to reach 91.3 percent, and the degradation rate of tinidazole is measured to reach 92.2 percent.
Claims (6)
1. A method for repairing toxic, harmful and refractory organic pollutants in wetland by utilizing copper slag photocatalysis reinforcement is characterized by comprising the following steps:
s1, firstly, activating waste copper slag, wherein the copper slag activation step comprises crushing and grinding, calcining, acid adding reaction, drying and measuring the metal content of the activated copper slag; the copper slag activation step specifically comprises the steps of firstly crushing and grinding waste copper slag to 10-100 meshes, ensuring that the porosity is 30-50% after the waste copper slag is paved on a wetland, calcining for 2-6 hours at 600-800 ℃, then adding sulfuric acid solution for reaction and activation for 20-60 minutes, and finally drying at 400-500 ℃ for 10-24 hours;
s2, adjusting the pH value of a polluted water body in the wetland to be repaired containing toxic and harmful organic pollutants difficult to degrade to 5-8, and measuring the TOC value of soluble organic matters in the polluted water body of the wetland to be repaired;
s3, directly paving the copper slag activated by the S1 on the surface layer of the wetland to be repaired containing toxic and harmful refractory organic pollutants, and regulating and controlling the concentration ratio of metal ions in the copper slag to soluble organic matters in the wetland polluted water body to fully complex the metal ions in the copper slag with the soluble organic matters in the wetland polluted water body to form a DOM-metal complex; the thickness of the copper slag paved on the surface layer of the wetland is 0.1-0.4 m;
s4, enclosing the water inlet and the water outlet of the wetland by using a baffle plate, and insolating the polluted water body of the wetland to be repaired, which contains toxic, harmful and refractory organic pollutants and is paved with copper slag in the S3, for 7-21 d, discharging the polluted water body from the water outlet after the treatment of the polluted water body is finished, and re-discharging the organic wastewater to be treated into the water inlet to realize the cyclic treatment; the water depth of the wetland to be repaired containing the toxic and harmful organic pollutants difficult to degrade is 0.3-1 m.
2. The method for the photocatalytic reinforcement repair of toxic, harmful and refractory organic pollutants in a wetland by utilizing copper slag according to claim 1, wherein the organic wastewater discharged from the water inlet comprises one or more of aquaculture wastewater, pharmaceutical wastewater and industrial wastewater.
3. The method for the photocatalytic reinforcement repair of toxic, harmful and refractory organic pollutants in a wetland by utilizing copper slag according to claim 1, wherein the soluble organic matters in the wetland to be repaired comprise a heterogeneous hydrocarbon mixture which can be dissolved in water, acid or alkali solution.
4. The method for repairing toxic, harmful and refractory organic pollutants in wetland by photocatalysis reinforcement of copper slag according to claim 1, wherein the metal ions in the activated copper slag comprise Fe 3+ 、Cu 2+ One or two of Fe 3 + 、Cu 2+ The content of (C) is 45-350 mg/kg -1 。
5. The method for repairing toxic, harmful and refractory organic pollutants in the wetland by utilizing copper slag photocatalysis reinforcement according to claim 1, wherein the full complexing time of metal ions in the copper slag in S3 and soluble organic matters in polluted water bodies of the wetland to be repaired is 30-120 min.
6. The method for repairing toxic, harmful and refractory organic pollutants in the wetland by utilizing the photocatalysis reinforcement of copper slag, which is disclosed in claim 1, is characterized in that the ratio of the molar concentration of metal ions in the copper slag in S3 to the TOC value of soluble organic matters in the polluted water body of the wetland is 1:1-4:1.
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Application publication date: 20220906 Assignee: SHANGHAI YIKE GREEN ENGINEERING Co.,Ltd. Assignor: Kunming University of Science and Technology Contract record no.: X2024980013352 Denomination of invention: A method for enhancing the remediation of toxic, harmful, and recalcitrant organic pollutants in wetlands using copper mine slag photocatalysis Granted publication date: 20230721 License type: Open License Record date: 20240830 |