CN114904908B - Bioelectrochemical soil pollution restoration device and method based on PLC control - Google Patents
Bioelectrochemical soil pollution restoration device and method based on PLC control Download PDFInfo
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- CN114904908B CN114904908B CN202210553442.3A CN202210553442A CN114904908B CN 114904908 B CN114904908 B CN 114904908B CN 202210553442 A CN202210553442 A CN 202210553442A CN 114904908 B CN114904908 B CN 114904908B
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- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000003900 soil pollution Methods 0.000 title claims abstract description 31
- 239000002689 soil Substances 0.000 claims abstract description 123
- 238000005507 spraying Methods 0.000 claims abstract description 112
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 238000011049 filling Methods 0.000 claims abstract description 42
- 239000005416 organic matter Substances 0.000 claims abstract description 34
- 244000005700 microbiome Species 0.000 claims abstract description 31
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- 238000003860 storage Methods 0.000 claims abstract description 18
- 230000015556 catabolic process Effects 0.000 claims abstract description 13
- 238000006731 degradation reaction Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- 238000005273 aeration Methods 0.000 claims description 53
- 238000005067 remediation Methods 0.000 claims description 31
- 239000003153 chemical reaction reagent Substances 0.000 claims description 28
- 230000000813 microbial effect Effects 0.000 claims description 28
- 239000002957 persistent organic pollutant Substances 0.000 claims description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 238000007254 oxidation reaction Methods 0.000 claims description 20
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 239000002738 chelating agent Substances 0.000 claims description 19
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 19
- 230000003647 oxidation Effects 0.000 claims description 19
- 239000001509 sodium citrate Substances 0.000 claims description 19
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 19
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 235000020774 essential nutrients Nutrition 0.000 claims description 9
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- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 238000002386 leaching Methods 0.000 claims description 7
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- 239000007921 spray Substances 0.000 claims description 7
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- 230000000593 degrading effect Effects 0.000 claims description 6
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- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 229910001200 Ferrotitanium Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 238000004891 communication Methods 0.000 claims description 3
- 239000013299 conductive metal organic framework Substances 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- 235000015097 nutrients Nutrition 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 claims description 3
- 229940068968 polysorbate 80 Drugs 0.000 claims description 3
- 238000010248 power generation Methods 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
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- 239000010936 titanium Substances 0.000 claims description 3
- 239000003987 organophosphate pesticide Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 15
- 239000011790 ferrous sulphate Substances 0.000 description 13
- 235000003891 ferrous sulphate Nutrition 0.000 description 13
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 13
- 239000007800 oxidant agent Substances 0.000 description 12
- 230000001590 oxidative effect Effects 0.000 description 12
- 230000008901 benefit Effects 0.000 description 9
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- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 5
- 239000004280 Sodium formate Substances 0.000 description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 5
- 229930006000 Sucrose Natural products 0.000 description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 5
- 239000008103 glucose Substances 0.000 description 5
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 5
- 239000001632 sodium acetate Substances 0.000 description 5
- 235000017281 sodium acetate Nutrition 0.000 description 5
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 5
- 235000019254 sodium formate Nutrition 0.000 description 5
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- 238000010525 oxidative degradation reaction Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000004016 soil organic matter Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 230000009102 absorption Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical group N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
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- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000019522 cellular metabolic process Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
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- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical group [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- 238000013508 migration Methods 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 210000004789 organ system Anatomy 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
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- 238000004065 wastewater treatment 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
- B09C1/08—Reclamation of contaminated soil chemically
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
-
- 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
- B09C1/085—Reclamation of contaminated soil chemically electrochemically, e.g. by electrokinetics
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
- H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
- H02J7/34—Parallel operation in networks using both storage and other dc sources, e.g. providing buffering
- H02J7/35—Parallel operation in networks using both storage and other dc sources, e.g. providing buffering with light sensitive cells
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical & Material Sciences (AREA)
- Biomedical Technology (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Microbiology (AREA)
- Molecular Biology (AREA)
- Mycology (AREA)
- Power Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a bioelectrochemical soil pollution restoration device and method based on PLC control, and belongs to the technical field of soil pollution restoration. The invention comprises a solar photovoltaic device, a storage battery, a biological filter bed, a supporting layer, a soil filling chamber, a bioelectrochemical reaction chamber and a PLC automatic control system, wherein the soil filling chamber is arranged above the bioelectrochemical reaction chamber through the supporting layer, and the biological filter bed is arranged above the soil filling chamber through the supporting layer; the soil filling room is provided with a first spraying system above, and the biological filter bed is provided with a second spraying system above. The invention cooperatively couples a solar photovoltaic system, advanced oxidation-bioelectrochemistry and a technology for repairing organic matter polluted soil by microorganisms, can obviously improve the degradation and repair efficiency of the organic matter in the soil, and realizes the automatic and intelligent operation control of the organic matter polluted soil repair.
Description
Technical Field
The invention relates to the technical field of soil pollution remediation, in particular to a bioelectrochemical soil pollution remediation device and method based on PLC control.
Background
Soil is the material basis upon which humans and organisms depend to survive and develop. With the rapid development of economy, the use amount of organic chemical products and organic pesticides is obviously increased, and a large amount of organic matters enter the soil-groundwater environment through leakage, seepage, sewage discharge and other ways each year, so that the organic matters become one of main sources of soil environmental pollution. The organic pollutant has the characteristics of low solubility, difficult degradation, strong biological residue, high ecological toxicity and the like, and damages the nervous system and the organ system, so that the organism is carcinogenic and teratogenic, thereby receiving the extensive attention of a plurality of environmental students. Organic pollutants migrate to deep soil after entering the soil and slowly dissolve in underground water after entering an aquifer, so that serious pollution of the underground water is caused, and serious threat is caused to human health and ecological safety. Therefore, the method has important significance in carrying out the repair work of the organic matter polluted soil.
Aiming at the current state of soil organic matter pollution, various repairing technologies such as physics (CN 203875107U), chemistry (CN 101053689) and biology (CN 104438298A) have been developed. Physical repair techniques include excavation landfill sealing, vapor extraction, thermal desorption, electric repair, and the like. The chemical restoration degrades organic chlorohydrocarbon in soil into low-toxic or nontoxic micromolecular substances through solvent extraction, leaching, chemical oxidation and the like. Bioremediation is the repair of contaminated soil mainly by means of plant or microbial absorption, degradation, transformation, cellular metabolism, etc. In practical application, physical remediation is affected by factors such as soil heterogeneity and permeability, and organic pollutants in soil cannot be thoroughly removed. The chemical restoration has strong applicability and short restoration time, is suitable for the soil with serious pollution, and has wide application prospect. The natural purification of organic pollutants by biological repair is slow and takes a long time, and is not suitable for pollution sites with serious pollution and sudden pollution and urgent need of development and utilization. The method has the advantages of low bioremediation cost, less influence on soil properties and ecological environment, in-situ remediation, no secondary pollution, environmental friendliness and the like, and is a green remediation technology.
The invention provides a soil organic matter pollution repair compound with strong applicability and high repair efficiency by cooperatively coupling surfactant-chelating agent enhanced advanced oxidation-bioelectrochemistry and microorganism repair technology by comprehensively comparing the characteristics of each repair methodA method of manufacturing the same. The organic strong oxidant comprises Fenton reagent, persulfate, permanganate and the like, wherein the persulfate has good stability, high safety and strong engineering applicability, and is the first choice of repair reagent. However, the persulfate has slower reaction with organic pollutants and poor degradation effect, and needs to generate sulfate radical (SO) with stronger oxidability under the actions of alkali, heat, transition metal and the like 4 And-), the degradation rate and degradation effect of the organic matters are improved. Because of high thermalization cost and inconvenient engineering implementation, the device adopts sodium citrate chelated ferrous sulfate to activate persulfate, and aims to improve the activation efficiency of sodium persulfate and SO 4 Concentration of · -is disclosed. In addition, the surfactant has the functions of solubilization, surface tension reduction and the like, can obviously improve the solubility of indissolvable organic matters adsorbed on soil particles, promotes the effective contact of the organic matters and an oxidant, and obviously improves the reaction rate.
The biological filter bed and aeration process is an aerobic waste water treatment process integrating various purification processes such as filtration, adsorption, biological action and the like, integrates biological oxidation and suspended matter interception, and has a certain oxidative degradation capability on organic pollutants.
The bioelectrochemical system is a novel bioremediation method integrating coupling of biological oxidation reduction and electrochemical reaction, the anode electrode can improve the adhesion of microorganisms on the electrode, and organic pollutants are oxidatively decomposed by utilizing the synergistic effect of biology and electrochemistry to promote electron transfer, so that the biodegradation rate is improved. Research shows that the external electric energy can improve the activity and diversity of microorganisms, maintain the stability of pollutant removal and obviously improve the removal rate of organic matters in the polluted soil.
Solar energy is clean and green renewable energy, and the bioelectrochemical system and the aeration device are driven by electric energy generated by solar energy photovoltaic, so that the remediation efficiency of polluted soil can be improved, and the remediation cost of soil pollutants can be greatly reduced. In addition, the PLC control system is used for realizing informatization, automation and intelligent operation control of organic matter polluted soil restoration, realizing real-time monitoring and acquisition of soil information and water quality information, saving manpower, material resources and financial resources and generating better ecological benefit and economic benefit.
Disclosure of Invention
1. Technical problem to be solved by the invention
Aiming at the defects and the shortcomings of the prior art, the invention provides a bioelectrochemical soil pollution restoration device and method based on PLC control, and aims at the defects of low efficiency, long time consumption, limited applicability and the like of the existing organic matter polluted soil restoration technology, and provides a advanced oxidation-bioelectrochemical soil pollution restoration device and method based on PLC control by taking a solar photovoltaic system as an electric driving force, which cooperatively couple the solar photovoltaic system, the advanced oxidation-bioelectrochemical and microorganism polluted soil restoration technology, can remarkably improve the degradation and restoration efficiency of organic pollutants in soil, and realize the automatic and intelligent operation control of organic matter polluted soil restoration.
2. Technical proposal
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
the invention relates to a bioelectrochemical soil pollution restoration device based on PLC control, which comprises a solar photovoltaic device, a storage battery, a bioelectrochemical filter bed, a supporting layer, a soil filling chamber, a bioelectrochemical reaction chamber and a PLC automatic control system, wherein the solar photovoltaic device comprises a solar photovoltaic panel and a photovoltaic panel controller, the solar photovoltaic panel is connected with the storage battery through the photovoltaic panel controller, the soil filling chamber is arranged above the bioelectrochemical reaction chamber through the supporting layer, and the bioelectrochemical filter bed is arranged above the soil filling chamber through the supporting layer;
the soil filling chamber is characterized in that a first spraying system is arranged above the soil filling chamber, an aeration pipeline is laid at the bottom of the biological filter bed, one end of the aeration pipeline is connected with an aeration device, a second spraying system is arranged above the biological filter bed, the input ends of the second spraying system and the first spraying system are respectively provided with a circulating water pump, and the input end of the circulating water pump is connected with an electromagnetic valve;
a three-dimensional grid battery is arranged in the bioelectrochemical reaction chamber, an anode electrode and a cathode electrode are arranged in the three-dimensional grid battery, and nano zero-valent iron is arranged on one side of the anode electrode;
the output end of the storage battery is connected with an aeration device, and the storage battery is also connected with an anode electrode and a cathode electrode in the bioelectrochemical reaction chamber;
the execution module of the PLC automatic control system comprises a circulating water pump, an electromagnetic valve, a second spraying system and a first spraying system.
Further, the PLC control system comprises a water quality acquisition system, a PLC controller and an execution module. The water quality acquisition system comprises a conductivity sensor, a COD sensor and NH 3 -N sensor, dissolved oxygen sensor, microbial sensor, organic matter detector, a/D converter; the water quality detection information is input into the PLC through the A/D converter;
the PLC is connected with the execution module to complete the automatic and intelligent operation control of the solar photovoltaic driven advanced oxidation-bioelectrochemical soil pollution restoration device, the PLC is connected with the management computer through the RS232 communication interface, and the PLC is also connected with the man-machine interaction device through the RS485 for man-machine interaction to process the input and output information of the soil pollution restoration device.
Further, the solar photovoltaic device provides green clean electric energy through solar power generation.
Further, the first spraying system and the second spraying system are controlled by a circulating water pump and a PLC automatic control system.
Further, the anode electrode of the three-dimensional grid battery is made of a conductive metal organic framework material, iron or a porous carbon material, and nano zero-valent iron is arranged at the position 5cm away from the anode; the cathode electrode is a graphite rod, titanium or stainless steel net, and the voltage range for driving the bioelectrochemical soil restoration is 0-2V.
Further, the soil filling chamber is filled with polluted soil, the concentration of organic matters in the soil is not lower than 100mg/kg, a sampling pore canal partition board is arranged in the soil filling chamber, a first spraying system is arranged above the soil filling chamber, the solution sprayed by the first spraying system is a surfactant-chelating agent reinforced advanced oxidation repair agent, and the components of the solution are surfactant, sodium persulfate, chelating agent, ferrous salt and pH regulator, and the chelating agent is citric acid or sodium citrate. Wherein, the dosage of the nonionic surfactant polysorbate 80 (Tween 80) is 0.5-1 times of the total organic matters in the polluted soil, the molar ratio of sodium persulfate to sodium citrate to ferrous salt to the pH regulator is 1-15:1-20:1-4, the pH range is 6-7, and the working procedure of the first spraying system is set by a PLC controller of a PLC automatic control system to control the additive amount and the adding time of the repairing reagent.
Further, the biological filter bed takes sand, broken stone, zeolite, ceramsite or plastics as a filter material, one side of the biological filter bed is provided with an aeration device, the aeration device comprises a blast aerator and an aeration pipeline arranged at the bottom of the filter bed, the blast aerator is communicated with the aeration pipeline, and the aeration pipeline is provided with aeration holes which can fully provide dissolved oxygen required by microorganisms.
Further, the solution sprayed by the second spraying system comprises carbon source, nitrogen source, phosphorus source, metal ions, nutrient elements necessary for microorganisms and microbial agents, and the spraying solution contains 0-120 g/L of carbon source, 0-12 g/L of nitrogen source, 0-6 g/L of phosphorus source and 0.15-2.0 g of MgSO (MgSO) in each liter of water 4 ·7H 2 O、10～20mg FeCl 3 、0.15～2.0g KH 2 PO 4 、0.06～1.2g CaCl 2 The method comprises the steps of carrying out a first treatment on the surface of the 0.8-5.5 ml/L of essential nutrient elements of microorganisms; and a proper amount of microbial agent, and the working program of the second spraying system is set through a PLC controller of the PLC automatic control system, so as to control the additive amount and the adding time of the solution.
Further, the soil pollutant type repaired by the repairing device is organic pollutants, including one or more of petroleum aromatic hydrocarbon, phenols, organochlorohydrocarbon and organophosphorus pesticides.
A method for bioelectrochemical soil pollution restoration device based on PLC control comprises the following steps:
step one: filling organic matter polluted soil into a soil filling chamber, starting a first spraying system to spray surfactant-chelating agent enhanced advanced oxidation reagent, and fully leaching the reagent into a polluted soil layer and oxidatively degrading organic pollutionThe eluted organic matters and the reacted solution enter a bioelectrochemical reaction chamber driven by solar energy photovoltaic, and an anode electrode in the reaction chamber adsorbs residual organic pollutants and degrades the pollutants into micromolecules and CO through low voltage provided by a storage battery 2 And H 2 O. In the reaction process, an organic matter detector is adopted to detect the concentration of organic matters in a soil filling chamber and a bioelectrochemical reaction chamber, the concentration is transmitted to a PLC (programmable logic controller) through an A/D (analog-to-digital) converter, after the concentration reaches a set limit value, the PLC starts an execution module, an electromagnetic valve is automatically opened, a reaction solution is discharged to a reagent collecting tank through a water outlet pipeline, a circulating water pump stops conveying a repairing reagent to a first spraying system, and the repairing reagent is stored in a reagent regulating tank;
step two: the PLC controller starts an execution module, a second spraying system and an aeration device controlled by the PLC controller synchronously work, the aeration device is started to convey gas to an aeration pipeline at the bottom of the biological filter bed for aeration, meanwhile, the second spraying system is started, spraying solution enters a restored soil layer through the biological filter bed, soil eluent is collected in a bioelectrochemical reaction chamber, and residual organic matters are continuously degraded by low voltage provided by microorganisms and a storage battery attached to an anode electrode through an electrode biological film in the reaction chamber. In the reaction process, a conductivity sensor, a COD sensor and NH are adopted 3 -N sensor, dissolved oxygen sensor, microorganism sensor, organic matter detector for detecting conductivity, COD, NH in soil filling chamber and bioelectrochemical reaction chamber 3 The concentration of N, DO, BOD and organic matters is transmitted to a PLC (programmable logic controller) through an A/D converter, when the concentration reaches a set limit value, the PLC starts an execution module, an electromagnetic valve is automatically opened, a reaction solution is discharged to a solution collecting tank through a water outlet pipeline, a circulating water pump stops conveying microbial agents to a second spraying system, the microbial agents are stored in a solution regulating tank, and an air blast aerator is closed to stop aeration;
step three: in the reaction process, the water quality acquisition system of the PLC control system is used for detecting the soil organic matters and the water quality information in real time, the detection information is transmitted to the PLC controller through the A/D converter, the PLC controller controls the execution module according to the concentration detection information, the circulating water pump, the electromagnetic valve, the first spraying system and the working program of the second spraying system are controlled through a circulating multi-stage mode, the circulating water pump alternately and continuously conveys the surfactant-chelating agent enhanced advanced oxidation reagent to the soil filling chamber and the biological filter bed through the first spraying system and the microbial solution through the second spraying system respectively, leaching oxidation of the organic matters and collaborative efficient degradation of microbial aerobe are continuously carried out, and thorough decomposition and removal of the organic matters are realized.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
aiming at the defects of low efficiency, long time consumption, limited applicability and the like of the existing organic matter contaminated soil remediation technology, the invention provides the advanced oxidation-bioelectrochemical soil pollution remediation device and the advanced oxidation-bioelectrochemical soil pollution remediation method based on PLC control by taking the solar photovoltaic system as the electric driving force, which are used for cooperatively coupling the solar photovoltaic system, the advanced oxidation-bioelectrochemical and microorganism organic matter contaminated soil remediation technology, so that the removal rate of organic pollutants can be obviously improved, the remediation efficiency of the organic pollutants in soil is obviously improved, and the automation and intelligent operation control of the organic matter contaminated soil remediation is realized.
The invention cooperatively couples a solar photovoltaic system, advanced oxidation-bioelectrochemistry and microorganism organic matter polluted soil restoration technology, realizes automatic and intelligent operation control of organic matter polluted soil restoration through a PLC control system, has the advantages of simple structure, strong applicability, reasonable design, convenient operation control and high efficiency of soil restoration, realizes real-time monitoring and acquisition of soil information through the PLC controller, saves manpower, material resources and financial resources, and can generate better ecological benefit and economic benefit.
Drawings
FIG. 1 is an overall view of the present invention;
FIG. 2 is a schematic diagram of a PLC control system according to the present invention;
FIG. 3 is a graph showing the average organic removal rate according to the present invention.
In the figure: 1. a solar photovoltaic panel; 2. a photovoltaic panel controller; 3. a storage battery; 4. an aeration device; 5. a second spray system; 6. a biological filter bed; 61. an aeration pipe; 7. a support layer; 8. a first spray system; 9. a soil loading chamber; 91. sampling pore canal partition plates; 10. a bioelectrochemical reaction chamber; 101. a three-dimensional grid cell; 102. an anode electrode; 103. a cathode electrode; 104. nano zero-valent iron; 11. a PLC automatic control system; 111. a circulating water pump; 112. a solenoid valve.
Detailed Description
The invention is further described below with reference to the accompanying drawings and examples:
example 1
As can be seen from fig. 1 to 3, the bioelectrochemical soil pollution restoration device based on PLC control of the present embodiment includes a solar photovoltaic device, a storage battery 3, a bioelectrochemical filter bed 6, a supporting layer 7, a soil filling chamber 9, a bioelectrochemical reaction chamber 10 and a PLC automatic control system 11, the solar photovoltaic device includes a solar photovoltaic panel 1 and a photovoltaic panel controller 2, the solar photovoltaic panel 1 is connected with the storage battery 3 through the photovoltaic panel controller 2, the soil filling chamber 9 is provided above the bioelectrochemical reaction chamber 10 through the supporting layer 7, and the bioelectrochemical filter bed 6 is provided above the soil filling chamber 9 through the supporting layer 7;
a first spraying system 8 is arranged above the soil filling chamber 9, an aeration pipeline 61 is laid at the bottom of the biological filter bed 6, one end of the aeration pipeline 61 is connected with an aeration device 4, a second spraying system 5 is arranged above the biological filter bed 6, the input ends of the second spraying system 5 and the first spraying system 8 are respectively provided with a circulating water pump 111, and the input end of the circulating water pump 111 is connected with an electromagnetic valve 112; the first spraying system 8 and the second spraying system 5 are controlled by a circulating water pump 111 and a PLC automatic control system 11.
A three-dimensional grid cell 101 is arranged in the bioelectrochemical reaction chamber 10, an anode electrode 102 and a cathode electrode 103 are arranged on the three-dimensional grid cell 101, and nano zero-valent iron 104 is arranged on one side of the anode electrode 102;
the anode electrode 102 of the three-dimensional grid cell 101 is made of conductive metal organic framework material, iron or porous carbon material, and nano zero-valent iron 104 is arranged at a position 5cm away from the anode; the cathode electrode 103 is a graphite rod, titanium or stainless steel mesh, and the voltage range for driving the bioelectrochemical soil restoration is 0-2V
The output end of the storage battery 3 is connected with an aeration device 4, and the storage battery 3 is also connected with an anode electrode 102 and a cathode electrode 103 in the bioelectrochemical reaction chamber 10; the solar photovoltaic device provides green clean electric energy through solar power generation.
The execution module of the PLC automatic control system 11 comprises a circulating water pump 111, an electromagnetic valve 112, a second spraying system 5 and a first spraying system 8.
The PLC control system comprises a water quality acquisition system, a PLC controller and an execution module, wherein the water quality acquisition system comprises a conductivity sensor, a COD sensor and NH 3 -N sensor, dissolved oxygen sensor, microbial sensor, organic matter detector, a/D converter; the water quality detection information is input into the PLC through the A/D converter;
conductivity sensor, COD sensor and NH 3 An N sensor, a dissolved oxygen sensor, a microbial sensor, and an organic matter detector are installed in the advanced oxidation-bioelectrochemical reaction chamber 10, and the organic matter detector is also installed in the soil filling chamber 9 through the sampling duct partition plate 91; the sensor and the detector are respectively connected with the A/D converter, and the soil and water quality detection information is transmitted to the PLC.
The PLC is connected with the execution module to complete the automatic and intelligent operation control of the solar photovoltaic driven advanced oxidation-bioelectrochemical soil pollution repair device, is connected with the management computer through the RS232 communication interface, is also connected with the man-machine dialogue device through the RS485 and is used for carrying out man-machine interaction dialogue treatment on the input and output information of the soil pollution repair device.
The PLC controller transmits signals to an execution module according to the detection information, and the execution module comprises a circulating water pump 111, an electromagnetic valve 112, an aeration device 4 and a spraying system; the circulating water pump 111 and the electromagnetic valve 112 are arranged on the reagent conveying pipeline, and the PLC is connected with the circulating water pump 111 and the electromagnetic valve 112 and used for controlling the conveying and spraying of the reagent; the PLC is also connected with an aeration device 4 and used for controlling the start and stop of the blast aerator and the aeration time and the aeration amount of the gas conveying pipeline of the biological filter bed.
The soil filling chamber 9 is filled with polluted soil, the concentration of organic matters in the soil is not lower than 100mg/kg, the sampling pore canal partition board 91 is arranged in the soil filling chamber 9, the first spraying system 8 is arranged above the soil filling chamber 9, the solution sprayed by the first spraying system 8 is a surfactant-chelating agent reinforced advanced oxidation repair agent, the components are surfactant, sodium persulfate, chelating agent, ferrous salt and pH regulator, the chelating agent is citric acid or sodium citrate, wherein the dosage of the nonionic surfactant polysorbate 80 (Tween 80) is 0.5-1 times of the total organic matters in the polluted soil, the molar ratio of the sodium persulfate, the sodium citrate, the ferrous salt and the pH regulator is 1-15:1-20:1-4, the working procedure of the first spraying system 8 is set through a PLC controller of the PLC automatic control system 11, and the additive amount and the adding time of the repair agent are controlled.
The biological filter bed 6 takes sand, broken stone, zeolite, haydite or plastics as filter materials, one side of the biological filter bed 6 is provided with an aeration device 4, the aeration device 4 comprises a blast aerator and an aeration pipeline 61 arranged at the bottom of the filter bed, the blast aerator is communicated with the aeration pipeline 61, and the aeration pipeline 61 is provided with aeration holes, so that dissolved oxygen required by microorganisms can be fully provided.
The solution sprayed by the second spraying system 5 comprises a carbon source, a nitrogen source, a phosphorus source, metal ions, nutrient elements necessary for microorganisms and microbial agents, wherein the spraying solution contains 0-120 g/L of the carbon source, 0-12 g/L of the nitrogen source, 0-6 g/L of the phosphorus source and 0.15-2.0 g of MgSO (MgSO) of the metal ions per liter of water 4 ·7H 2 O、10～20mg FeCl 3 、0.15～2.0g KH 2 PO 4 、0.06～1.2g CaCl 2 The method comprises the steps of carrying out a first treatment on the surface of the 0.8-5.5 ml/L of essential nutrient elements of microorganisms; and a proper amount of microbial agent is used for setting the working program of the spraying system 2 through a PLC controller of the PLC automatic control system 11, and controlling the additive amount and the additive time of the solution.
The carbon source of the solution sprayed by the second spraying system 5 is glucose, sucrose, sodium formate, sodium acetate and the like, and the ratio is 1:1:1 to 4:1:2:3; the nitrogen source is ammonium sulfate, ammonium chloride, etc.; the phosphorus source is disodium hydrogen phosphate, sodium dihydrogen phosphate and the like; the metal ion is K + 、Na + 、Ca 2+ 、Mg 2+ Etc.; the essential nutrient elements of the microorganism are microelements, vitamins, amino acids, etc.
The type of the soil pollutant repaired by the repairing device is organic pollutant, and the soil after repairing can be used as landscaping planting soil, wherein the organic pollutant comprises one or more of petroleum aromatic hydrocarbon, phenols, organochlorohydrocarbon and organophosphorus pesticide.
A method for bioelectrochemical soil pollution restoration device based on PLC control comprises the following steps:
step one: filling organic matter polluted soil into a soil filling chamber 9, starting a first spraying system 8 to spray surfactant-chelating agent reinforced advanced oxidation reagent, fully leaching the reagent into a polluted soil layer and oxidatively degrading organic pollutant, enabling the eluted organic matter and reacted solution to enter a bioelectrochemical reaction chamber 10 driven by solar energy photovoltaic, adsorbing residual organic pollutant by an anode electrode 102 in the reaction chamber and degrading the pollutant into micromolecules and CO by low voltage provided by a storage battery 3 2 And H 2 O. In the reaction process, the concentration of the organic matters in the soil filling chamber 9 and the bioelectrochemical reaction chamber 10 is detected by adopting an organic matter detector and is transmitted to a PLC (programmable logic controller) through an A/D (analog-to-digital) converter, when the concentration reaches a set limit value, the PLC starts an execution module, an electromagnetic valve 112 is automatically opened, a reaction solution is discharged to a reagent collecting tank through a water outlet pipeline, a circulating water pump 111 stops conveying a repairing reagent to the first spraying system 8, and the repairing reagent is stored in a reagent regulating tank;
step two: the PLC controller starts an execution module, the second spraying system 5 and the aeration device 4 controlled by the PLC controller work synchronously, the aeration device 4 is started to convey gas to the aeration pipeline 61 at the bottom of the biological filter bed 6 for aeration, meanwhile, the second spraying system 5 is started, spraying solution enters the restored soil layer through the biological filter bed 6, soil eluent is collected in the bioelectrochemical reaction chamber 10, and the anode electrode 102 in the reaction chamber continuously degrades residual organic matters through microorganisms attached by electrode biomembrane and low voltage provided by the storage battery 3. In the reaction process, a conductivity sensor, a COD sensor and NH are adopted 3 -N sensor, dissolved oxygen sensor, microbial sensorThe device and the organic matter detector detect the conductivity, COD and NH in the soil filling chamber 9 and the bioelectrochemical reaction chamber 10 3 The concentration of N, DO, BOD and organic matters is transmitted to a PLC (programmable logic controller) through an A/D converter, when the concentration reaches a set limit value, the PLC starts an execution module, automatically opens an electromagnetic valve 112 to enable reaction solution to be discharged to a solution collecting tank through an outlet pipeline, a circulating water pump 111 stops conveying microbial agents to a second spraying system 5, the microbial agents are stored in a solution regulating tank, and a blast aerator is closed to stop aeration;
step three: in the reaction process, the water quality acquisition system of the PLC control system is used for detecting the soil organic matters and the water quality information in real time, the detection information is transmitted to the PLC controller through the A/D converter, the PLC controller controls the execution module according to the concentration detection information, the circulating water pump 111, the electromagnetic valve 112, the first spraying system 8 and the working program of the second spraying system 5 are controlled through a circulating multi-stage mode, the circulating water pump 111 alternately and continuously conveys the surfactant-chelating agent enhanced advanced oxidation reagent to the soil filling chamber 9 and the biological filter bed 6 through the first spraying system 8 and the microbial solution through the second spraying system 5 respectively, and the leaching oxidation of the organic matters and the synergistic efficient degradation of microbial aerobe are continuously carried out, so that the complete decomposition and removal of the organic matters are realized.
In the embodiment 1-3, the biological filter bed 6 takes sand and broken stone as filter materials, the anode electrode 102 is made of an iron metal organic framework material, and the cathode electrode 103 is made of graphite rods; the voltage of solar photovoltaic driven bioelectrochemical soil remediation is 0V, soil pollutants are organic chlorohydrocarbons, and the concentration of the organic pollutants in the sampled and analyzed soil is 200mg/kg.
The spraying solution of the second spraying system 5 contains carbon source, nitrogen source and phosphorus source with concentration of 0g/L in each liter of water; metal ion MgSO 4 ·7H 2 O(0.12g/L)、KH 2 PO 4 (0.12g/L)、FeCl 3 (1.2mg/L)、CaCl 2 (0.06 g/L); and a proper amount of microbial agent, wherein the concentration of essential nutrient element vitamin of the microorganism is 0.6ml/L.
Example 1 was divided into 5 groups: (1) The spraying solution of the first spraying system 8 is surfactant Tween80, and the mass fraction of the solution is 4% (wt.);
(2) The spraying solution of the first spraying system 8 is mixed with an oxidant, and the molar ratio of sodium persulfate to sodium citrate to ferrous sulfate to organic matters is 1:15:5:1;
(3) The spraying solution of the first spraying system 8 is mixed with an oxidant, and the molar ratio of sodium persulfate to sodium citrate to ferrous sulfate to organic matters is 10:15:5:1, wherein the mass fraction of the solution is 4% (wt.);
(4) The spraying solution of the first spraying system 8 is mixed with an oxidant, and the molar ratio of sodium persulfate to sodium citrate to ferrous sulfate to organic matters is 15:15:5:1;
(5) The spraying solution of the first spraying system 8 is mixed with oxidant, sodium persulfate, sodium citrate, ferrous sulfate and organic matters in the molar ratio of 20:15:5:1, and the pH is regulated to 6-7 by using a pH regulator (1.0M/L).
Example 2
The three groups are: (1) The spraying solution of the first spraying system 8 is mixed with an oxidant, and the molar ratio of sodium persulfate to sodium citrate to ferrous sulfate to organic matters is 15:5:5:1;
(2) The spraying solution of the first spraying system 8 is mixed with an oxidant, and the molar ratio of sodium persulfate to sodium citrate to ferrous sulfate to organic matters is 15:10:5:1;
(3) The spraying solution of the first spraying system 8 is mixed with an oxidant, sodium persulfate, sodium citrate, ferrous sulfate and organic matters in a molar ratio of 15:20:5:1, and the pH is regulated to 6-7 by using a pH regulator (1.0M/L).
Example 3
Divided into two groups: (1) The spraying solution of the first spraying system 8 is mixed with an oxidant, and the molar ratio of sodium persulfate to sodium citrate to ferrous sulfate to organic matters is 15:15:10:1;
(2) The spraying solution of the first spraying system 8 is mixed with an oxidant, and the molar ratio of sodium persulfate to sodium citrate to ferrous sulfate to organic matters is 15:15:15:1; the pH was adjusted to 6 to 7 using a pH adjuster (1.0M/L).
In the biological filter bed 6 in the embodiments 4 to 6, sand and broken stone are used as filter materials, an anode electrode 102 is made of an iron metal organic framework material, and a cathode electrode 103 is made of a graphite rod; the voltage of solar photovoltaic driven bioelectrochemical soil remediation is 0V, soil pollutants are organic chlorohydrocarbons, and the concentration of the organic pollutants in the sampled and analyzed soil is 200mg/kg.
The spraying solution of the first spraying system 8 is a surfactant Tween80, the mass fraction of the solution is 4% (wt.), the mole ratio of sodium persulfate to sodium citrate to ferrous sulfate to organic matters is 15:15:5:1, and the pH is adjusted to 6-7 by using a pH regulator (1.0M/L).
Example 4
The spraying solution of the second spraying system 5 contains 60g/L of carbon source concentration per liter of water, wherein the ratio of glucose, sucrose, sodium formate and sodium acetate is 1:1:1:1; the nitrogen source concentration is 6g/L, and the phosphorus source concentration is 2.6g/L; metal ion MgSO 4 ·7H 2 O(1.2g/L)、KH 2 PO 4 (1.2g/L)、FeCl 3 (12mg/L)、CaCl 2 (0.6 g/L); and a proper amount of microbial agent, wherein the concentration of essential nutrient element vitamin of the microorganism is 2.2ml/L.
Example 5
The spraying solution of the second spraying system 5 contains 120g/L of carbon source concentration per liter of water, wherein the ratio of glucose, sucrose, sodium formate and sodium acetate is 4:1:2:3; the nitrogen source concentration is 12g/L, and the phosphorus source concentration is 6g/L; metal ion MgSO 4 ·7H 2 O(2.2g/L)、KH 2 PO 4 (2.2g/L)、FeCl 3 (22mg/L)、CaCl 2 (1.2 g/L); and a proper amount of microbial agent, wherein the concentration of essential nutrient element vitamin of the microorganism is 5.5ml/L.
Example 6
The spraying solution of the second spraying system 5 contains 150g/L of carbon source concentration per liter of water, wherein the ratio of glucose, sucrose, sodium formate and sodium acetate is 4:1:2:3; the nitrogen source concentration is 15g/L, and the phosphorus source concentration is 10g/L; metal ion MgSO 4 ·7H 2 O(2.5g/L)、KH 2 PO 4 (2.5g/L)、FeCl 3 (25mg/L)、CaCl 2 (1.5 g/L); and a proper amount of microbial agent, wherein the concentration of essential nutrient element vitamin of the microorganism is 8.0ml/L.
Examples 7 to 9
In the biological filter bed 6 in the embodiments 7 to 9, sand and broken stone are used as filter materials, an anode electrode 102 is made of an iron metal organic framework material, and a cathode electrode 103 is made of a graphite rod; the voltage of solar photovoltaic driven bioelectrochemical soil remediation is 2V, soil pollutants are organic chlorohydrocarbons, and the concentration of the organic pollutants in the sampled and analyzed soil is 200mg/kg.
The spraying solution of the first spraying system 8 is a surfactant Tween80, the mass fraction of the solution is 4% (wt.), the mole ratio of sodium persulfate to sodium citrate to ferrous sulfate to organic matters is 15:15:5:1, and the pH is adjusted to 6-7 by using a pH regulator (1.0M/L).
The spray solutions of the second spray system 5 in examples 7 to 9 are the same as in examples 4 to 6.
Example 10
The biological filter bed 6 takes sand, broken stone and zeolite as filter materials, an anode electrode 102 is made of titanium metal organic framework materials, and a cathode electrode 103 is made of graphite rods; the voltage of solar photovoltaic driven bioelectrochemical soil remediation is 2V, soil pollutants are organic chlorohydrocarbons, and the concentration of the organic pollutants in the sampled and analyzed soil is 200mg/kg.
The spraying solution of the first spraying system 8 is a surfactant Tween80, the mass fraction of the solution is 4% (wt.), the mole ratio of sodium persulfate to sodium citrate to ferrous sulfate to organic matters is 15:15:5:1, and the pH is adjusted to 6-7 by using a pH regulator (1.0M/L).
The spraying solution of the second spraying system 5 contains 150g/L of carbon source concentration per liter of water, wherein the ratio of glucose, sucrose, sodium formate and sodium acetate is 4:1:2:3; the nitrogen source concentration is 15g/L, and the phosphorus source concentration is 10g/L; metal ion MgSO 4 ·7H 2 O(2.5g/L)、KH 2 PO 4 (2.5g/L)、FeCl 3 (25mg/L)、CaCl 2 (1.5 g/L); and a proper amount of microbial agent, wherein the concentration of essential nutrient element vitamin of the microorganism is 5.5ml/L.
The specific settings of the examples are shown in Table 1.
Table 1 example design conditions
The average removal rate of organics for each example is shown in figure 3.
The invention has the beneficial effects that: (1) The soil organic matters are removed by adopting a surfactant-chelating agent reinforced advanced oxidation synergistic electric technology, meanwhile, the nano zero-valent iron 104 is arranged in the bioelectrochemical reaction chamber 10 at a position 5cm away from the anode, on one hand, the nano zero-valent iron 104 has high specific surface area and strong reactivity, can quickly activate and degrade the organic matters, and accelerates Fe in the reagent 2+ 、Fe 3+ Is to continuously supply Fe to the system 2+ Promote S 2 O 8 2- Activation to produce SO 4 -oxidative degradation of organics; on the other hand, the nano zero-valent iron 104 reduces the organic matters firstly, then carries out oxidation reaction, and utilizes the reduction and oxidation to cooperatively degrade the organic matters efficiently; (2) The electrode biomembrane is stimulated by using solar photovoltaic direct current, the degradation of the organic pollutants in the soil by microorganisms is enhanced, the electron transfer rate is accelerated by using the three-dimensional grid cell 101 through the adsorption and oxidation action of the porous electrode, the contact area of the organic pollutants in the soil and the electrode biomembrane is increased, and the high-efficiency degradation capability of the biological filter bed 6 on the pollutants is combined, so that a novel technology and a novel path for degrading the organic pollutants in the soil are finally formed; (3) The surfactant can obviously improve the solubility of organic matters adsorbed on the surface of the soil particle colloid and chelate Fe by utilizing the coupling treatment technology of surfactant and chelating agent reinforced advanced oxidation, nano zero-valent iron and bioelectrochemistry 2+ Continuous activation of persulfates to produce SO 4 Organic matter oxidative degradation to increase SO 4 The existence time of the-promotes the migration of the surfactant-chelating agent reinforced advanced oxidation solvent through the electric action, promotes the effective contact of the oxidant and the organic matters, and obviously improves the reaction rate.
Aiming at the defects of low efficiency, long time consumption, limited applicability and the like of the existing organic matter contaminated soil remediation technology, the invention provides the advanced oxidation-bioelectrochemical soil pollution remediation device and the advanced oxidation-bioelectrochemical soil pollution remediation method based on PLC control by taking the solar photovoltaic system as the electric driving force, which cooperatively couple the solar photovoltaic system, the advanced oxidation-bioelectrochemical and microbial organic matter contaminated soil remediation technology, can remarkably improve the degradation and remediation efficiency of organic pollutants in soil, and realize the automatic and intelligent operation control of organic matter contaminated soil remediation.
The invention cooperatively couples a solar photovoltaic system, advanced oxidation-bioelectrochemistry and microorganism organic matter polluted soil restoration technology, realizes automatic and intelligent operation control of organic matter polluted soil restoration through the PLC control system 11, has the advantages of simple structure, strong applicability, reasonable design, convenient operation control and high efficiency of soil restoration, realizes real-time monitoring and acquisition of soil information through the PLC controller, saves manpower, material resources and financial resources, and can generate better ecological benefit and economic benefit.
The invention and its embodiments have been described above by way of illustration and not limitation, and the invention is illustrated in the accompanying drawings and described in the drawings in which the actual structure is not limited thereto. Therefore, if one of ordinary skill in the art is informed by this disclosure, the structural mode and the embodiments similar to the technical scheme are not creatively designed without departing from the gist of the present invention.
Claims (9)
1. The utility model provides a bioelectrochemical soil pollution prosthetic devices's method based on PLC control, its device includes solar photovoltaic device, battery (3), biological filter bed (6), supporting layer (7), soil filling room (9), bioelectrochemical reaction room (10) and PLC automatic control system (11), solar photovoltaic device includes solar photovoltaic board (1) and photovoltaic board controller (2), and solar photovoltaic board (1) is connected with battery (3) through photovoltaic board controller (2), its characterized in that: a soil filling chamber (9) is arranged above the bioelectrochemical reaction chamber (10) through a supporting layer (7), and a biological filter bed (6) is arranged above the soil filling chamber (9) through the supporting layer (7);
a first spraying system (8) is arranged above the soil filling chamber (9), an aeration pipeline (61) is laid at the bottom of the biological filter bed (6), one end of the aeration pipeline (61) is connected with an aeration device (4), a second spraying system (5) is arranged above the biological filter bed (6), the input ends of the second spraying system (5) and the first spraying system (8) are respectively provided with a circulating water pump (111), and the input end of the circulating water pump (111) is connected with an electromagnetic valve (112);
a three-dimensional grid cell (101) is arranged in the bioelectrochemical reaction chamber (10), an anode electrode (102) and a cathode electrode (103) are arranged in the three-dimensional grid cell (101), and nano zero-valent iron (104) is arranged on one side of the anode electrode (102);
the output end of the storage battery (3) is connected with an aeration device (4), and the storage battery (3) is also connected with an anode electrode (102) and a cathode electrode (103) in the bioelectrochemical reaction chamber (10);
the execution module of the PLC automatic control system (11) comprises a circulating water pump (111), an electromagnetic valve (112), a second spraying system (5) and a first spraying system (8);
the method comprises the following steps:
step one: filling organic matter polluted soil into a soil filling chamber (9), starting a first spraying system (8) to spray a surfactant-chelating agent reinforced advanced oxidation reagent, fully leaching the reagent into a polluted soil layer and oxidatively degrading the organic pollutant, enabling the eluted organic matter and a reacted solution to enter a bioelectrochemical reaction chamber (10) driven by solar energy and photovoltaic, adsorbing the residual organic pollutant by an anode electrode (102) in the reaction chamber, and degrading the pollutant into micromolecules and CO by low voltage provided by a storage battery (3) 2 And H 2 In the reaction process, an organic matter detector is adopted to detect the concentration of organic matters in a soil filling chamber (9) and a bioelectrochemical reaction chamber (10), the concentration is transmitted to a PLC (programmable logic controller) through an A/D (analog-to-digital) converter, after the concentration reaches a set limit value, the PLC starts an execution module, an electromagnetic valve (112) is automatically opened, a reaction solution is discharged to a reagent collecting tank through a water outlet pipeline, a circulating water pump (111) stops conveying a repairing reagent to a first spraying system (8), and the repairing reagent is stored in a reagent regulating tank;
step two: the PLC controller starts an execution module, a second spraying system (5) controlled by the PLC controller and an aeration device (4) synchronously work, the aeration device (4) is started to convey gas to an aeration pipeline (61) at the bottom of the biological filter bed (6) for aeration, meanwhile, the second spraying system (5) is started, spraying solution enters a restored soil layer through the biological filter bed (6), and soil eluent is collected in the soil layerThe bioelectrochemical reaction chamber (10) is characterized in that an anode electrode (102) in the reaction chamber continuously degrades residual organic matters through microorganisms attached by electrode biomembrane and low voltage provided by a storage battery (3), and in the reaction process, a conductivity sensor, a COD sensor and NH are adopted 3 -N sensor, dissolved oxygen sensor, microorganism sensor, organic matter detector for detecting conductivity, COD, NH in soil filling chamber (9) and bioelectrochemical reaction chamber (10) 3 The concentration of N, DO, BOD and organic matters is transmitted to a PLC (programmable logic controller) through an A/D converter, when the concentration reaches a set limit value, the PLC starts an execution module, an electromagnetic valve (112) is automatically opened, a reaction solution is discharged to a solution collecting tank through a water outlet pipeline, a circulating water pump (111) stops delivering microbial agents to a second spraying system (5), the microbial agents are stored in a solution regulating tank, and a blast aerator is closed to stop aeration;
step three: in the reaction process, the water quality acquisition system of the PLC control system is used for detecting soil organic matters and water quality information in real time, the detection information is transmitted to the PLC controller through the A/D converter, the PLC controller controls the execution module according to the concentration detection information, the circulating water pump (111), the electromagnetic valve (112), the first spraying system (8) and the working program of the second spraying system (5) are controlled through a circulating multi-stage mode, the circulating water pump (111) is used for alternately and continuously conveying surfactant-chelating agent enhanced advanced oxidation reagent to the soil filling chamber (9) and the biological filter bed (6) through the first spraying system (8) and microorganism solution respectively, leaching oxidation of the organic matters and collaborative efficient degradation of microorganism aerobic are continuously carried out, and thorough decomposition and removal of the organic matters are realized.
2. The method of the bioelectrochemical soil pollution remediation device based on the PLC control of claim 1, wherein the method comprises the following steps: the PLC control system comprises a water quality acquisition system, a PLC controller and an execution module, wherein the water quality acquisition system comprises a conductivity sensor, a COD sensor and NH 3 -N sensor, dissolved oxygen sensor, microbial sensor, organic matter detector, a/D converter; the water quality detection information is input into the PLC through the A/D converter;
the PLC is connected with the execution module to complete the automatic and intelligent operation control of the solar photovoltaic driven advanced oxidation-bioelectrochemical soil pollution restoration device, the PLC is connected with the management computer through the RS232 communication interface, and the PLC is also connected with the man-machine interaction device through the RS485 for man-machine interaction to process the input and output information of the soil pollution restoration device.
3. The method of the bioelectrochemical soil pollution remediation device based on the PLC control of claim 1, wherein the method comprises the following steps: the solar photovoltaic device provides green clean electric energy through solar power generation.
4. The method of the bioelectrochemical soil pollution remediation device based on the PLC control of claim 1, wherein the method comprises the following steps: the first spraying system (8) and the second spraying system (5) are controlled by a circulating water pump (111) and a PLC automatic control system (11).
5. The method of the bioelectrochemical soil pollution remediation device based on the PLC control of claim 1, wherein the method comprises the following steps: the anode electrode (102) of the three-dimensional grid battery (101) is made of a conductive metal organic framework material, iron or a porous carbon material, and nano zero-valent iron (104) is arranged at a position 5cm away from the anode; the cathode electrode (103) is a graphite rod, titanium or stainless steel net, and the voltage range for driving the bioelectrochemical soil restoration is 0-2V.
6. The method of the bioelectrochemical soil pollution remediation device based on the PLC control of claim 1, wherein the method comprises the following steps: the soil filling chamber (9) is filled with polluted soil, the concentration of organic matters in the soil is not lower than 100mg/kg, the sampling pore canal partition board (91) is arranged in the soil filling chamber (9), the first spraying system (8) is arranged above the soil filling chamber (9), the solution sprayed by the first spraying system (8) is a surfactant-chelating agent reinforced advanced oxidation repair reagent, the components of the solution are surfactant, sodium persulfate, chelating agent, ferrous salt and pH regulator, the chelating agent is citric acid or sodium citrate, the dosage of the nonionic surfactant polysorbate 80 (Tween 80) is 0.5-1 times of the total organic matters in the polluted soil, the molar ratio of the sodium persulfate, the sodium citrate, the ferrous salt and the pH regulator is 1-15:1-20:1-4, the pH range is 6-7, and the working procedure of the first spraying system (8) is set through a PLC controller of the PLC automatic control system (11), and the repair reagent addition amount and the addition time are controlled.
7. The method of the bioelectrochemical soil pollution remediation device based on the PLC control of claim 1, wherein the method comprises the following steps: the biological filter bed (6) is characterized in that sand, broken stone, zeolite, ceramsite or plastic are used as filter materials, an aeration device (4) is arranged on one side of the biological filter bed (6), the aeration device (4) comprises a blast aerator and an aeration pipeline (61) arranged at the bottom of the filter bed, the blast aerator is communicated with the aeration pipeline (61), aeration holes are formed in the aeration pipeline (61), and dissolved oxygen required by microorganisms can be fully provided.
8. The method of the bioelectrochemical soil pollution remediation device based on the PLC control of claim 1, wherein the method comprises the following steps: the solution sprayed by the second spraying system (5) comprises carbon source, nitrogen source, phosphorus source, metal ions, nutrient elements necessary for microorganisms and microbial agents, wherein the spraying solution contains 0-120 g/L of carbon source, 0-12 g/L of nitrogen source, 0-6 g/L of phosphorus source and 0.15-2.0 g of MgSO (MgSO) in each liter of water 4 ·7H 2 O、10～20mg FeCl 3 、0.15～2.0g KH 2 PO 4 、0.06～1.2g CaCl 2 The method comprises the steps of carrying out a first treatment on the surface of the 0.8-5.5 ml/L of essential nutrient elements of microorganisms; and a proper amount of microbial agent is adopted, and the working program of the second spraying system (5) is set through a PLC controller of the PLC automatic control system (11), so that the additive amount and the additive time of the solution are controlled.
9. The method of the bioelectrochemical soil pollution remediation device based on the PLC control of claim 1, wherein the method comprises the following steps: the type of the soil pollutant repaired by the repairing device is organic pollutant, including one or more of petroleum aromatic hydrocarbon, phenols, organochlorohydrocarbon and organophosphorus pesticide.
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