CN115010207A - Method for strengthening and repairing toxic, harmful and refractory organic pollutants in wetland by copper slag photocatalysis - Google Patents
Method for strengthening and repairing toxic, harmful and refractory organic pollutants in wetland by copper slag photocatalysis Download PDFInfo
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- CN115010207A CN115010207A CN202210133553.9A CN202210133553A CN115010207A CN 115010207 A CN115010207 A CN 115010207A CN 202210133553 A CN202210133553 A CN 202210133553A CN 115010207 A CN115010207 A CN 115010207A
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- 239000010949 copper Substances 0.000 title claims abstract description 87
- 239000002893 slag Substances 0.000 title claims abstract description 82
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 75
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 45
- 231100000331 toxic Toxicity 0.000 title claims abstract description 36
- 230000002588 toxic effect Effects 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 14
- 238000005728 strengthening Methods 0.000 title claims abstract description 12
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 30
- 239000002344 surface layer Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 150000001879 copper Chemical class 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 230000001276 controlling effect Effects 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 5
- 230000003213 activating effect Effects 0.000 claims abstract description 4
- 230000000536 complexating effect Effects 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002699 waste material Substances 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 230000015556 catabolic process Effects 0.000 claims description 14
- 238000006731 degradation reaction Methods 0.000 claims description 14
- 230000004913 activation Effects 0.000 claims description 11
- 239000002351 wastewater Substances 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 238000009360 aquaculture Methods 0.000 claims description 2
- 244000144974 aquaculture Species 0.000 claims description 2
- 230000000903 blocking effect Effects 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
- 238000005192 partition Methods 0.000 claims description 2
- 238000005067 remediation Methods 0.000 claims 3
- 238000007599 discharging Methods 0.000 claims 2
- 230000002787 reinforcement Effects 0.000 claims 1
- 238000005286 illumination Methods 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000005446 dissolved organic matter Substances 0.000 abstract 3
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 230000000593 degrading 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 14
- 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 6
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 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
- 230000007480 spreading Effects 0.000 description 4
- 238000003892 spreading Methods 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000006698 induction Effects 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
- 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 group 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
- 150000001875 compounds Chemical class 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle 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
- 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
- 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 strengthening and repairing toxic and harmful refractory organic pollutants in a wetland by utilizing copper slag photocatalysis, which comprises the steps of activating the copper slag (crushing, grinding, calcining, adding acid for reaction and 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 proportion of metal ions in the copper slag and Dissolved Organic Matter (DOM) concentration in a polluted water body of the wetland, fully complexing the DOM in the polluted water body and the metal ions in the copper slag to form a DOM-metal complex, and generating hydroxyl radicals by photoinduced electron transfer of the DOM-metal complex under the condition of solar illumination, thereby strengthening and degrading the refractory organic pollutants in the polluted water body of the wetland. The method has the advantages of simple operation and low cost, can thoroughly degrade toxic, harmful and non-degradable organic pollutants in the wetland, is not easy to generate 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 strengthening and repairing toxic and harmful refractory organic pollutants in a wetland by utilizing copper slag photocatalysis.
Background
Copper slag is a waste produced during copper production. 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 the stacking, and dust in the copper slag can pollute the atmosphere and harm the health of human beings. The development difficulty of the novel comprehensive utilization technology of copper slag resources is high, large-scale consumption and high-valued comprehensive utilization of resources are limited, and huge resource waste is caused.
The wetland can cooperatively remove nutrient substances and organic pollutants in a water body through a physical-chemical-biological compound restoration mechanism formed among plants, matrixes and microorganisms, and although the wetland has the advantages of low construction and use cost, simplicity and convenience in operation and maintenance, low energy consumption and the like, the wetland has certain limitations in pollutant treatment, and toxic, harmful and refractory organic pollutants such as low-temperature environment, insufficient wetland oxygen content and the like can not reach ideal degradation efficiency through a wetland system. Aiming at the defects in the prior art, a method for strengthening and repairing toxic, harmful and refractory organic pollutants in a wetland by utilizing copper slag photocatalysis 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, carbonyl and the like, and can absorb solar radiation and generate excited triplet DOM 3 DOM * ) And some reactive oxygen species, and can also complex with metal ions, thereby affecting contaminant degradation. Aiming at the water depth in the wetlandThe method has the advantages that uniform illumination can be obtained to provide sufficient illumination conditions for photocatalysis, hydroxyl free radicals (. OH) can be generated under the illumination conditions after DOM and metal ions are complexed to strengthen and degrade organic pollutants in the wetland, copper slag is selected to be utilized as wastes, is activated and then is paved on the surface layer of the wetland, the proportion of metal ions in copper slag and the TOC value of DOM in the wetland polluted water body is regulated, DOM and metal ions are complexed to form DOM-metal complexes, active oxygen species mainly containing. OH are generated through illumination to strengthen and degrade organic pollutants difficult to degrade in the wetland polluted water body, and toxic and harmful difficult to degrade pollutants in the organic wastewater can be degraded into non-toxic and harmless small molecular acid or mineralized into CO 2 And water.
Disclosure of Invention
The invention provides a method for strengthening and repairing toxic and harmful refractory organic pollutants in a wetland by utilizing copper slag photocatalysis, which utilizes soluble organic matters (DOM) in a polluted water body of the wetland to be repaired and metal ions in the copper slag to fully complex under the illumination condition to form DOM-metal complex, OH is generated, and the toxic and harmful refractory organic pollutants in the wetland are strengthened and degraded. The proportion of the molar concentration of metal ions in the copper ore slag to the TOC value of dissolved organic matters in the wetland polluted water body is particularly important, and in a proper proportion range, the DOM-metal complex is subjected to photoinduced electron transfer under the solar illumination condition to efficiently generate OH to strengthen and degrade toxic and harmful refractory organic pollutants in the wetland, so that the toxic and harmful refractory pollutants are thoroughly degraded, resource utilization is realized, the operation is simple, and secondary pollution is not easily generated.
The invention is realized by the following steps:
s1, firstly activating the waste copper slag, wherein the copper slag activation step comprises the steps of crushing, grinding, calcining, adding acid for reaction, drying and measuring the metal content of the activated copper slag;
s2, adjusting the pH value of the polluted water body in the wetland to be repaired, which contains the toxic and harmful degradation-resistant organic pollutants, to 5-8, and measuring the TOC value of dissolved 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, harmful and difficultly-degradable organic pollutants, and regulating and controlling the ratio of metal ions in the copper slag to the concentration of soluble organic matters in the wetland polluted water body to fully complex the metal ions in the copper slag and the soluble organic matters in the wetland polluted water body to form a DOM-metal complex;
s4, blocking a water inlet and a water outlet of the wetland by using a partition plate, solarizing the wetland polluted water body to be repaired containing the toxic and harmful refractory organic pollutants paved in the step (3) for 7-21 d, and after the wetland polluted water body to be repaired is irradiated by the sun, generating hydroxyl free radicals with high reaction activity by photoinduction of DOM-metal complex in the wetland polluted water body to be repaired, wherein the toxic and harmful refractory organic pollutants can be indiscriminately degraded into small molecular acid or mineralized into CO 2 And the copper slag can adsorb partial pollutants, the polluted water in the wetland to be repaired is discharged from the water outlet after the treatment is finished, and the water inlet is discharged into the organic wastewater to be treated again, so that the wastewater can be treated circularly.
Preferably, in the step S1, the copper slag activation needs to be carried out by firstly crushing and grinding the waste copper slag to 10-100 meshes, ensuring that the porosity is 30-50% after the waste copper slag is laid on a wetland, calcining the waste copper slag for 2-6 h at 600-800 ℃, then adding a sulfuric acid solution for reaction and activation for 20-60 min, wherein the drying temperature is 400-500 ℃, and the drying time is 10-24 h.
Further, in the step S1, the copper slag is crushed and ground to have a particle size of 30 meshes, calcined for 6 hours at 600 ℃, and then added with sulfuric acid solution for reaction and activation for 45 minutes, wherein 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 wetland surface layer in the step S3 is 0.1-0.4 m.
Further, the copper slag laying thickness in step S3 is 0.3 m.
Preferably, the water depth of the wetland to be repaired containing the toxic and harmful degradation-resistant organic pollutants in the step S3 is 0.3-1 m, and the organic wastewater discharged from the wetland water inlet comprises one or more of aquaculture wastewater, pharmaceutical wastewater and industrial wastewater.
Preferably, the dissolved organic matters in the wetland to be repaired comprise heterogeneous hydrocarbon mixtures which can be dissolved in water, acid or alkali solution and are composed of functional groups such as amino acids, aromatic groups, aliphatic groups and the like containing oxygen, nitrogen and sulfur.
Preferably, the metal ions in the copper slag after activation include Fe 3+ 、Cu 2+ One or more of (A), Fe 3+ 、Cu 2+ The content of (A) is 45-350 mg/kg -1 。
Preferably, the sufficient complexing time of the metal ions in the copper slag and the dissolved organic matters in the polluted water body of the wetland to be repaired is 30-120 min.
Preferably, the ratio of the molar concentration of metal ions in the copper ore slag to the TOC value of dissolved 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.
Furthermore, the ratio of the molar concentration of metal ions in the copper ore slag to the TOC value of dissolved organic matters in the wetland polluted water body is 2: 1.
Preferably, the number of days of exposure in step S4 is 15 days.
The invention has the beneficial effects that:
1. the invention fully utilizes the principle that the DOM-metal complex generates photoinduced electron transfer to generate OH after illumination, so that soluble organic matters in the wetland and heavy metals in copper slag are complexed to generate OH under the illumination condition, organic pollutants which are difficult to degrade in the wetland are degraded in an enhanced manner, other additional technologies are not needed, and the method is simple in process, low in cost and convenient to popularize and apply.
2. The metal ion source used in the invention is the waste copper slag, so that the cost is low, the raw materials are easy to obtain, the waste copper slag can be recycled, and the development concept of treating waste by waste and realizing green low carbon is practiced.
3. The waste copper slag is used as surface filler in the wetland, not only can provide metal ion source and DOM for complexing generation, OH can be provided for strengthening degradation of toxic, harmful and non-degradable organic pollutants in the wetland, but also the functions of filtering and adsorbing the pollutants can be achieved.
4. The method has simple process, thoroughly degrades the toxic and harmful refractory organic pollutants in the wetland to be repaired, is a high-efficiency and simple-operation treatment method, and has obvious environmental, economic and social benefits.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to be limiting in any way, and any variations which are made on the basis of the teaching of the invention are intended to fall within the scope of the invention.
Example 1
The waste copper slag is selected for activation, crushed and ground to 30 meshes, calcined at 600 ℃, added with 1mM sulfuric acid for reaction for 45min, and dried for 18h at 450 ℃. Adjusting 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 measuring the TOC value of the dissolved organic matters in the polluted water body of the wetland to be repaired to be 5 mgC/L. Activated copper slag (Fe among them) 3+ 、Cu 2+ The content is 100 mg/kg -1 ) Spreading on the surface layer of the wetland to be repaired, and controlling the amount of laid copper slag to ensure that Fe 3+ 、Cu 2+ The molar concentration of the organic pollutants difficult to degrade in the wet effluent is measured to be 20 mu M, 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 a DOM-metal complex, the wetland polluted water body to be repaired is kept for being exposed for 15d, after the water body is irradiated by the sun, the DOM-metal complex is subjected to light induction 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 by a high performance liquid chromatograph, the content of the OH is calculated to be 2.6 mu M, and the degradation rate of the nitrobenzene which is an organic pollutant difficult to degrade in the wet effluent is measured to be 90.7 percent, and the degradation rate of tinidazole is measured to be 91.5 percent.
Example 2
The waste copper slag is selected for activation, crushed and ground to 30 meshes, calcined at 600 ℃, added with 1mM sulfuric acid for reaction for 45min, and dried for 18h at 450 ℃. 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 measuring the TOC value of the dissolved organic matters in the polluted water body of the wetland to be repaired to be5 mgC/L. Activated copper slag (Fe among them) 3+ 、Cu 2+ The content is 100 mg/kg -1 ) Spreading on the surface layer of the wetland to be repaired, and controlling the amount of laid copper slag to ensure that Fe 3+ 、Cu 2+ The molar concentration of the organic pollutants difficult to degrade in the wet effluent is measured to be 15.8 percent, and the tinidazole degradation rate is measured to be 93.4 percent, wherein the molar concentration of the metal ions in the copper slag is 3:1, 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 are fully complexed with the DOM in the polluted water body of the wetland to form a DOM-metal complex, the polluted water body of the wetland to be repaired is kept for being exposed for 15d, after the water body is irradiated by the sun, the DOM-metal complex is subjected to light induction 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 by a high performance liquid chromatograph, the content of the OH is calculated to be 3.2 mu M.
Example 3
The waste copper slag is selected for activation, crushed and ground to 30 meshes, calcined at 600 ℃, added with 1mM sulfuric acid for reaction for 45min, and dried for 18h at 450 ℃. Adjusting 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 measuring the TOC value of the dissolved organic matters in the polluted water body of the wetland to be repaired to be 5 mgC/L. Activated copper slag (Fe among them) 3+ 、Cu 2+ The content is 100 mg/kg -1 ) Spreading on the surface layer of the wetland to be repaired, and controlling the amount of laid copper slag to ensure that Fe 3+ 、Cu 2+ The molar concentration of the copper ore slag is 10 mu M, the ratio of the molar concentration of metal ions in the copper ore slag to the TOC value of DOM in the polluted water body is 2:1, the metal ions in the copper ore slag are fully complexed with the DOM in the wetland polluted water body to form a DOM-metal complex, the wetland polluted water body to be repaired is left for being exposed for 15 days, after the wetland polluted water body is irradiated by the sun, the DOM-metal complex is photoinduced to generate OH, the OH can react with terephthalic acid to generate 2-hydroxy terephthalic acid, the content of the OH is measured by a high performance liquid chromatograph, the content of the OH is further calculated to be 3.8 mu M, and the degradation rate of nitrobenzene which is an organic pollutant difficult to degrade in the wet effluent water is measured to be 94.7 percent, and the degradation rate of tinidazole is 96.8 percent.
Example 4
The method comprises the steps of activating waste copper slag, crushing and grinding the waste copper slag into 30 meshes, calcining the waste copper slag at 600 ℃, adding 1mM sulfuric acid to react for 45min, and drying the mixture for 18h at 450 ℃. Adjusting 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 measuring the TOC value of the dissolved organic matters in the polluted water body of the wetland to be repaired to be 5 mgC/L. Activated copper slag (Fe among them) 3+ 、Cu 2+ The content is 100 mg/kg -1 ) Spreading on the surface layer of the wetland to be repaired, and controlling the amount of laid copper slag to ensure that Fe 3+ 、Cu 2+ The molar concentration of the organic pollutants difficult to degrade in the wet effluent is measured to be 5 mu M, 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, the metal ions in the copper slag and the DOM in the wetland polluted water body are fully complexed to form a DOM-metal complex, the wetland polluted water body to be repaired is kept for being exposed for 15d, after the water body is irradiated by the sun, the DOM-metal complex is subjected to light induction 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 by a high performance liquid chromatograph, the content of the OH is calculated to be 2.8 mu M, and the degradation rate of the nitrobenzene which is an organic pollutant difficult to degrade in the wet effluent is measured to be 91.3 percent, and the degradation rate of the tinidazole is measured to be 92.2 percent.
Claims (8)
1. A method for strengthening and repairing toxic and harmful refractory organic pollutants in a wetland by utilizing copper slag photocatalysis is characterized by comprising the following steps:
s1, firstly activating the waste copper slag, wherein the copper slag activation step comprises the steps of crushing, grinding, calcining, adding acid for reaction, drying and measuring the metal content of the activated copper slag;
s2, adjusting the pH value of the polluted water body in the wetland to be repaired, which contains the toxic and harmful degradation-resistant organic pollutants, to 5-8, and measuring the TOC value of dissolved 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, wherein the surface layer contains toxic and harmful degradation-resistant organic pollutants, and regulating and controlling the ratio of metal ions in the copper slag to the concentration of soluble organic matters in the wetland polluted water body so as 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, blocking the water inlet and the water outlet of the wetland by using a partition plate, solarizing the to-be-repaired wetland polluted water body containing toxic, harmful and difficultly-degradable organic pollutants paved in the step (3) for 7-21 d, discharging the polluted water body from the water outlet after the treatment is finished, and discharging the water inlet into the to-be-treated organic wastewater again to realize circular treatment.
2. The method for photocatalytic reinforcement and restoration of toxic, harmful and non-degradable organic pollutants in wetland according to claim 1, wherein the copper slag activation step comprises the steps of crushing and grinding the waste copper slag to 10-100 meshes, ensuring that the porosity is 30-50% after the waste copper slag is laid on the wetland, calcining for 2-6 h at 600-800 ℃, adding a sulfuric acid solution for reaction and activation for 20-60 min, and finally drying at 400-500 ℃ for 10-24 h.
3. The method for strengthening and repairing toxic and harmful refractory organic pollutants in the wetland by utilizing the photocatalysis of the copper slag according to claim 1, wherein the thickness of the copper slag paved on the surface layer of the wetland is 0.1-0.4 m.
4. The method for strengthening the remediation of toxic and harmful refractory organic pollutants in wetland according to claim 1, wherein the depth of water in the wetland to be remediated containing the toxic and harmful refractory organic pollutants is 0.3-1 m, and the organic wastewater discharged from the water inlet comprises one or more of aquaculture wastewater, pharmaceutical wastewater and industrial wastewater.
5. The method for photocatalytic remediation of toxic and harmful refractory organic pollutants from wetland according to claim 1, wherein the soluble organic matters in the wetland to be remediated comprise heterogeneous hydrocarbon mixtures soluble in water, acid or alkali solution.
6. According toThe method for photocatalytic enhancement of remediation of toxic and harmful refractory organic pollutants in wetland according to claim 1, wherein the metal ions in the activated copper slag comprise Fe 3+ 、Cu 2+ One or two of (A), (B), Fe 3 + 、Cu 2+ The content of (A) is 45-350 mg/kg -1 。
7. The method for strengthening and repairing toxic and harmful refractory organic pollutants in wetland by utilizing copper slag photocatalysis according to claim 1, wherein the sufficient complexing time of metal ions in the copper slag and dissolved organic matters in a polluted water body of the wetland to be repaired is 30-120 min in the step (3).
8. The method for photocatalytic enhancement and restoration of toxic and harmful refractory organic pollutants in wetland according to claim 1, wherein the ratio of the molar concentration of metal ions in the copper slag to the TOC value of dissolved organic matters in the wetland polluted water body in the step (3) is 1:1 to 4: 1.
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