CN110180886A - A kind of device and method of in-situ immobilization fluoride pollution soil - Google Patents
A kind of device and method of in-situ immobilization fluoride pollution soil Download PDFInfo
- Publication number
- CN110180886A CN110180886A CN201910605555.1A CN201910605555A CN110180886A CN 110180886 A CN110180886 A CN 110180886A CN 201910605555 A CN201910605555 A CN 201910605555A CN 110180886 A CN110180886 A CN 110180886A
- Authority
- CN
- China
- Prior art keywords
- situ immobilization
- electrode
- soil
- cathode
- fluorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002689 soil Substances 0.000 title claims abstract description 141
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 106
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 39
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000011737 fluorine Substances 0.000 claims abstract description 85
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 85
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 47
- 230000004888 barrier function Effects 0.000 claims abstract description 42
- 238000003860 storage Methods 0.000 claims abstract description 38
- 239000003792 electrolyte Substances 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 16
- 238000010828 elution Methods 0.000 claims abstract description 11
- 239000000356 contaminant Substances 0.000 claims abstract description 10
- 230000009471 action Effects 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 230000008439 repair process Effects 0.000 claims description 23
- 229910001220 stainless steel Inorganic materials 0.000 claims description 21
- 239000010935 stainless steel Substances 0.000 claims description 21
- 229910001111 Fine metal Inorganic materials 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000003480 eluent Substances 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 12
- 239000001632 sodium acetate Substances 0.000 claims description 12
- 235000017281 sodium acetate Nutrition 0.000 claims description 12
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910021536 Zeolite Inorganic materials 0.000 claims description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000010457 zeolite Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229920001661 Chitosan Polymers 0.000 claims description 8
- 238000005341 cation exchange Methods 0.000 claims description 8
- 230000008929 regeneration Effects 0.000 claims description 8
- 238000011069 regeneration method Methods 0.000 claims description 8
- 210000000988 bone and bone Anatomy 0.000 claims description 7
- 239000004323 potassium nitrate Substances 0.000 claims description 7
- 235000010333 potassium nitrate Nutrition 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 5
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 5
- 241001330002 Bambuseae Species 0.000 claims description 5
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 5
- 239000011425 bamboo Substances 0.000 claims description 5
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 5
- 239000003610 charcoal Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- 150000002603 lanthanum Chemical class 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 5
- 239000003011 anion exchange membrane Substances 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 13
- 230000005684 electric field Effects 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 3
- 238000000909 electrodialysis Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 12
- 238000005067 remediation Methods 0.000 description 10
- 230000001988 toxicity Effects 0.000 description 8
- 231100000419 toxicity Toxicity 0.000 description 8
- 208000004042 dental fluorosis Diseases 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000013589 supplement Substances 0.000 description 6
- 206010016818 Fluorosis Diseases 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 241000894007 species Species 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 201000010099 disease Diseases 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000005520 electrodynamics Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011066 ex-situ storage Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical group 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 230000003902 lesion Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004660 morphological change Effects 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000002686 phosphate fertilizer Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 238000009418 renovation Methods 0.000 description 2
- 239000004016 soil organic matter Substances 0.000 description 2
- 238000003900 soil pollution Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 208000002193 Pain Diseases 0.000 description 1
- 244000234609 Portulaca oleracea Species 0.000 description 1
- 235000001855 Portulaca oleracea Nutrition 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- -1 bone black Chemical compound 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- KMQAPZBMEMMKSS-UHFFFAOYSA-K calcium;magnesium;phosphate Chemical compound [Mg+2].[Ca+2].[O-]P([O-])([O-])=O KMQAPZBMEMMKSS-UHFFFAOYSA-K 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 210000003141 lower extremity Anatomy 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 208000016334 muscle symptom Diseases 0.000 description 1
- 201000000585 muscular atrophy Diseases 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
- B09C1/08—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
- B09C2101/00—In situ
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A kind of device and method of in-situ immobilization fluoride pollution soil use permeable reactive barrier combined electrical mechanical technology to carry out in-situ immobilization to fluoride pollution soil.Restorative procedure includes the steps that carrying out physical and chemical property determining to soil, the step of elution of upper soll layer fluorine is carried out using soil elution liquid, lay can in-situ immobilization electrode the step of, the step of continuous circulation loop of structure electrolyte is organized between electrolysis room and anolyte storage tank in situ, using action of low-voltage pulse power supply the step of two interpolar of yin-yang applies DC electric field.Fluorine ion under electric field action with negative electrical charge is mobile to anode chamber by electromigration and is adsorbed by permeable reactive barrier in anode chamber, fluorine is mobile to cathode chamber by electrodialysis with fluoride or other soluble ions simultaneously and is adsorbed by permeable reactive barrier in cathode chamber, electrode is taken out after the completion of repairing, i.e., the removal and reparation of fluorine contaminant in completion soil.
Description
Technical field
The invention belongs to the recovery technique field of fluoride pollution soil, specifically a kind of original position of fluoride pollution soil can seep
Transflection answers grid combined electrical mechanics restorative procedure.
Technical background
In recent years along with the fast development of industrial or agricultural and the increase of population, serious soil pollution is caused, wherein just
Including Fluorine Pollution In Soil.In Agricultural Activities, phosphate fertilizer is used for a long time and dirty filling will lead to Fluorine Pollution In Soil；Industrial production is living
In dynamic, burning of coal, make steel, aluminium processed and ceramics, glass, phosphate fertilizer production process in generated fluoro-gas and grit, lead to
Crossing the processes such as rainfall, leaching makes fluorine enter soil, will also result in Fluorine Pollution In Soil.Research shows that: excessive fluorine intake is to human body
Be it is harmful, will lead to fluorine poisoning.Endemic fluorosis abbreviation endemia fluorosis is that most wide one of endemic disease is distributed on the earth, early stage
Symptom is headache, pain in waist and lower extremities and den tal fluorosis, and with progression of the disease, nerve, muscle symptoms are aggravated, textured bone, muscular atrophy, sternly
It is detrimental to health again.In China, the distribution of the disease is also very extensive, and main pathogeny is high in water, food tealeaves and air
The fluorine of content, wherein again most wide with drinking water type endemic fluorosis distribution face.On June 12nd, 2018, national health health committee are public
Cloth " China's hygiene and health career development statistical communique in 2017 ".The bulletin is shown: China's endemic fluorosis is drunk water at present
Number 1115, type lesion county, lesion village number 75287,1410.7 ten thousand people of den tal fluorosis patient, 111.4 ten thousand people of fluorosis bone patients,
Form allows of no optimist, and Fluoride In Soils are exactly one of water and the important sources of food test quantity of fluoride in tea.
In addition to this, excessive fluorine will lead to soil aperture blocking in soil, be unfavorable for soil coagulation, moisture is not easy to seep
Thoroughly, to cause the deterioration of soil physico-chemical property.Be simultaneously from external source Fluorine Pollution In Soil can also cause iron, aluminum oxide or
The disintegration of nitrogen oxides promotes the soil organism solubilized, to influence the validity of potentially toxic element in soil.Therefore, it repairs
Multiple fluoride pollution soil, restores soil original function, has attracted increasing attention.
Currently, the approach for administering fluoride pollution soil in the prior art mainly uses chemical method, such as in acid soil
Lime is added or applies gypsum in alkaline soils to change the existing forms of fluorine in the soil, is passivated the fluorine in soil, is solid
It is fixed, to reduce its migration and bioavailability in the environment.Though this chemical fixation can reduce fluorine in soil
Toxicity, but fluoride can not be fundamentally removed, once environmental condition changes, fluorine may be reactivated, and be released
Come.
Electromotion repairing technique is a kind of novel soil restoring technology, it in contaminated soil mainly by applying low pressure
DC electric field, various the electro kinetic effects such as electromigration, electrodialysis and electrophoresis etc. generated using electric field, by pollutant from soil
In separate.The advantages of electrokinetics, is: removal efficiency is high, can in situ also can showering, especially suitable for hypotonic
Permeability soil, etc. smaller to soil interference.
Permeable reactive barrier technology permeable reactive barrier, PRB are a kind of groundwater remediation skill
Art, which will be placed in water flow downstream filled with active material inside the reaction grid with certain permeability, when sewage passes through
When reacting grid, go the pollutant in water removal that water is made to be purified by the effect of physics, chemistry or microorganism.This technology by
In having many advantages, such as that effect on environment is small, is easy maintenance, cheap, quickly grows, be employed successfully at present in recent years
Except various water bodies pollutant.In terms of soil pollution reparation, since the mobility of pollutant in the soil is far away from water body,
Therefore application of the PRB technology in soil remediation is limited.
CN105419804A disclosed on March 23rd, 2016 " a kind of renovation agent and a kind of fluoride pollution soil of fluoride pollution soil
The restorative procedure of earth " discloses a kind of fluoride pollution soil-repairing agent and a kind of fluoride pollution soil remediation method.This method is using modification
Fluorine in peat, calcium magnesium phosphate and calcium carbonate, calcium oxide or calcium hydroxide chemistry fixing soil, though fluorine in soil can be reduced
Toxicity, but can not fundamentally remove fluoride, once environmental condition changes, fluorine may be reactivated, release
Out.
" the chemistry of fluorides combined pollution place soil-plant connection of CN103736716A disclosed on April 23rd, 2014
Close restorative procedure " by chemistry-plant combined reparation fluorine combined contamination soil.Patent content shows that this method can effectively repair fluorine
Contaminated soil, but need first to carry out crushing and screening to contaminated soil particle, then grogs is placed in the polynary showering equipment of soil
In, mixing eluent is added, and by the way of ultrasound-enhanced and heating treatment, carry out continuous dystopy elution；Then again to washing
Soil inoculation purslane after de- applies the nutrient source buffer for being equal to soil quality 30%-40%, artificial to cultivate, plant growth
Soil remediation is realized after the completion.Substantially based on showering, soil particle needs broken, dystopy elution, addition plant for the reparation
Object repairs nutrient solution, and cost is excessively high, and the time is longer, and practicability is to be improved.
Therefore, how technology of Electrodynamics Renovation and permeable reactive barrier technology to be combined, it is to be repaired not moving
Under conditions of earth backing earth, the reparation of fluoride pollution soil is fast and efficiently carried out, to improve the reality of fluoride pollution soil restoring technology
It is this field urgent problem to be solved with property and validity.
Summary of the invention
In order to solve the above-mentioned technical problem, the present invention is by the way of permeable reactive barrier combined electrical mechanics, in original
Under the conditions of position, can efficiently, quickly finish the reparation of fluoride pollution soil, removal efficiency of flouride is up to 82% or more, greatly reduces into
This, has significant fluorine desorption repairing effect and practicability.
To realize the above-mentioned technical purpose, the technical scheme adopted by the invention is as follows: a kind of in-situ immobilization fluoride pollution soil
Device, including power supply, anolyte storage tank, catholyte storage tank and multiple original positions being laid in fluoride pollution soil
Electrode is repaired, the in-situ immobilization electrode includes circular bottom plate and the cylindrical support frame that is arranged in above circular bottom plate,
The circumferential direction of cylindrical support frame is enclosed equipped with stainless steel fine metal mesh, and being loaded on the inside of the stainless steel fine metal mesh has ion exchange
Film, the amberplex define the electrolysis room that an inside is used to accommodate electrolyte together with circular bottom plate,
The inside of the stainless steel fine metal mesh is also detachably provided with the permeable reactive barrier for adsorbing fluorine contaminant, the circle
A graphite stick electrode is vertically arranged at the center of shape bottom plate upwards, the height of the graphite stick electrode is not less than cylindrical shape
The height of support frame, and the top of graphite stick electrode is additionally provided with metal connection column；
Multiple in-situ immobilization electrodes include anode in-situ immobilization electrode and cathode in-situ immobilization electrode, multiple in-situ immobilizations
Electrode is distributed in fluoride pollution soil in concentric ring-shaped, and the in-situ immobilization polarity of electrode on same annulus is identical, adjacent
The in-situ immobilization polarity of electrode of annulus on the contrary, and multiple in-situ immobilization electrodes on each annulus along the circumferential direction of annulus where it
It is uniformly distributed, the metal connection column of the anode in-situ immobilization electrode is connected by the anode of conducting wire and power supply, and cathode is repaired in situ
The metal connection column of overlying electrode is connected by the cathode of conducting wire and power supply, and the power supply is action of low-voltage pulse DC power supply；
The anode in-situ immobilization electrode is internally provided with anode permeable reactive barrier, and be loaded yin in stainless steel fine metal mesh
Amberplex, electrolysis room pass through delivery hose and delivery pump and sun for accommodating anolyte, electrolysis room
Pole anolyte storage tank constitutes the continuous circulation loop of anolyte, and the cathode in-situ immobilization electrode is internally provided with yin
Pole permeable reactive barrier, be loaded in stainless steel fine metal mesh cation-exchange membrane, and electrolysis room is for accommodating catholyte
Liquid, electrolysis room are made up of the continuous circulation of catholyte delivery hose and delivery pump and catholyte storage tank
Circuit.
Further, the permeable reactive barrier passes through the multiple card slots being arranged on cylindrical support frame and is fixed on
The inside of stainless steel fine metal mesh.
Further, the delivery hose is provided with flow control valve.
Further, the power supply is solar DC power supply.
Further, at least one of potassium nitrate solution, ammonium hydroxide and the sodium acetate solution that the anolyte is；
The catholyte is at least one of potassium nitrate solution, acetic acid solution and citric acid solution.
Further, the filler in the anode permeable reactive barrier is that Modified Iron loads macropore phosphoramidic-resin
At least one of with modified lanthanum loading chitosan resin；Filler in the cathode permeable reactive barrier is modified lives
At least one of property aluminium oxide, bone black, zeolite and bamboo charcoal.
Further, be provided in the anolyte storage tank and catholyte storage tank to electrolyte into
The mixing component of row stirring.
Further, the graphite stick electrode is fixed on cylindrical support frame, and graphite stick electrode
Diameter is 2-20cm, is highly 20-50cm.
A kind of method of in-situ immobilization fluoride pollution soil, comprising the following steps:
Step 1: taking ammonium hydroxide, sodium hydroxide, sodium acetate, at least one of hydroxylamine hydrochloride and carboxymethyl chitosan are configured to dense
Degree is 0.08-0.12 mol/L fluorine eluent, is sprayed on the surface of fluoride pollution soil to be repaired, constantly stirs fluoride pollution to be repaired
Soil is not more than the upper soll layer of 20cm depth, makes the water content 20-35% of the upper soll layer；
Step 2: the fluorine to be repaired that multiple in-situ immobilization electrodes in prosthetic device are laid in step 1 by concentric ring-shaped is dirty
It contaminates in soil, the vertical depth of burying of control in-situ immobilization electrode in the soil is not less than 20cm；
Step 3: using delivery hose and delivery pump that the electrolysis room of step 2 Anodic in-situ immobilization electrode and anode is electric
The continuous circulation loop of anolyte is connected between solution liquid holding vessel, and controls the electrolysis of anode in-situ immobilization electrode
The input flow rate of indoor anolyte is consistently greater than output flow；
Step 4: using delivery hose and delivery pump that the electrolysis room of cathode in-situ immobilization electrode in step 2 and cathode is electric
The continuous circulation loop of catholyte is connected between solution liquid holding vessel, and controls the electrolysis of cathode in-situ immobilization electrode
The input flow rate of indoor catholyte is consistently greater than output flow；
Step 4: using delivery hose and delivery pump that the electrolysis room of cathode in-situ immobilization electrode in step 2 and cathode is electric
The continuous circulation loop of catholyte is connected between solution liquid holding vessel, and controls the electrolysis of cathode in-situ immobilization electrode
The input flow rate of indoor catholyte is consistently greater than output flow；
Step 5: the anode of the metal connection column of anode in-situ immobilization electrode and power supply is connected using conducting wire, by cathode original position
The cathode of the metal connection column and power supply of repairing electrode connects, and the output voltage intensity for adjusting power supply is 0.5-4V/cm, and is being controlled
Under the conditions of electrolyte in anolyte storage tank processed and catholyte storage tank constantly stirs, repair process 110- is carried out
130h, in repair process, adjusting the water content of upper soll layer using the fluorine eluent of step 1 configuration is always 20-35%, and every
20-30h replaces the anolyte in an anolyte storage tank and the catholyte in catholyte storage tank
Liquid removes prosthetic device, that is, completes the reparation of fluoride pollution soil later.
Further, after the completion of reparation, the permeable reactive barrier in in-situ immobilization electrode is removed, and wash using regeneration
De- liquid carries out zeolite regeneration to permeable reactive barrier, later, using chemical coagulation-sedimentation method and activated alumina absorption method pair
Gained elutes fluoride waste and carries out Combined Treatment, that is, completes the removal of fluorine contaminant.
The utility model has the advantages that
1, prosthetic device simple structure and reasonable design of the invention, using flexible is strong, and is easy to construction and installation.Wherein, it can seep
Transflection answer grid repair in situ in electrode detachable structure setting, make its internal adsorbent material fail or filler block
When, it can take out at any time and carry out zeolite regeneration or replacement, to improve the availability and remediation efficiency of device.
2, in electromotion repairing technique method, the phase, current value was obvious due to the reduction of soil intermediate ion concentration after repair
Decline, the electrodynamics removal efficiency in later period are only to repair the 20-30% of early period, and the low defect of remediation efficiency, of the invention repairs
Apparatus for coating replaces traditional constant voltage dc source using action of low-voltage pulse DC power supply, when current lead-through, pulse (peak value) electricity
Stream is equivalent to several times even tens times of conventional DC electric current, is strengthened by high-intensitive pulse (peak value) electric current and repairs effect
Fruit improves remediation efficiency.
3, prosthetic device of the invention are isolated using anion-exchange membrane by soil and anode electrolysis room, prevent anode electrolysis
The H of generation+Into soil；Soil and catholyte chamber are isolated using cation-exchange membrane, the OH for preventing catholyte from generating–
Into soil, electric energy is greatly saved in this mode, compared with prior art, can reduce energy consumption 10-30%.Meanwhile the present invention will
Fluorine eluent, which is added directly into soil, to be eluted, and while improving elution efficiency, further promotes the desorption of fluorine.Using this hair
After bright repair mode carries out the reparation of fluoride pollution soil, 10-20% is can be improved in the removal efficiency of fluorine in soil.
4, compared with prior art, the application uses in-situ remediation method, does not need after shifting contaminated soil excavation again
It is repaired, to significantly reduce rehabilitation cost, improves the applicability of technology.
5, the present invention is adsorbed electric field using built-in fluorine removal permeable reactive barrier and migrates the fluorine contaminant that comes, by electric power
Technology is combined with permeable reactive barrier technology organic assembling, greatly improves the removal efficiency of fluorine.Meanwhile the fluorine of use
Eluent, electrolyte (such as potassium nitrate, acetic acid etc.) and anions and canons exchange membrane are the repeatable absorption that recycles or degrade
Raw material, avoid the indwelling and enrichment of harmful substance in the soil in repair process, so as to avoid soil acid-base, reduce
Adverse effect of the repair process to soil.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of in-situ immobilization electrode in the present invention；
Fig. 2 is the structural schematic diagram of Anodic permeable reactive barrier of the present invention；
Fig. 3 is the structural schematic diagram of cathode permeable reactive barrier in the present invention；
Fig. 4 is the in-situ immobilization pole layout structural schematic diagram of embodiment 1 in the present invention；
Fig. 5 is the in-situ immobilization pole layout structural schematic diagram of embodiment 2 in the present invention；
Appended drawing reference: 1, power supply, 2, anolyte storage tank, 3, catholyte storage tank, 4, in-situ immobilization electrode, 401,
Circular bottom plate, 402, cylindrical support frame, 403, stainless steel fine metal mesh, 404, graphite stick electrode, 405, metal connection column,
5, anode permeable reactive barrier, 6, cathode permeable reactive barrier, 7, delivery hose, 8, card slot.
Specific embodiment
The present invention will be further described in detail combined with specific embodiments below:
A kind of device of in-situ immobilization fluoride pollution soil, including power supply 1, anolyte storage tank 2, catholyte storage tank
3 and multiple in-situ immobilization electrodes 4 being laid in fluoride pollution soil, the in-situ immobilization electrode 4 includes 401 He of circular bottom plate
The cylindrical support frame 402 of 401 top of circular bottom plate is set, is enclosed in the circumferential direction of cylindrical support frame 402 thin equipped with stainless steel
Metal mesh 403, the inside of the stainless steel fine metal mesh 403 are loaded and have amberplex, wherein stainless steel fine metal mesh 403 can
To protect amberplex not destroyed by the hard object in soil.The amberplex defines together with circular bottom plate 401
One inside is used to accommodate the electrolysis room of electrolyte, is also detachably arranged in the inside of the stainless steel fine metal mesh 403
There is the permeable reactive barrier for adsorbing fluorine contaminant, permeable reactive barrier is by being arranged on cylindrical support frame 402
Multiple card slots 8 be fixed on the inside of stainless steel fine metal mesh 403, be vertically arranged upwards at the center of the circular bottom plate 401
There are graphite stick electrode 404(diameter 2-20cm, a height 20-50cm, in use according to the area of fluoride pollution soil
It is specifically chosen with pollution level), which is fixed on cylindrical support frame 402, and its height is not less than circle
The height of tubular support frame 402, and the top of graphite stick electrode 404 is additionally provided with metal connection column 405.
Multiple in-situ immobilization electrodes 4 include anode in-situ immobilization electrode and cathode in-situ immobilization electrode, Duo Geyuan
Position is repaired electrode 4 and is distributed in fluoride pollution soil in concentric ring-shaped, the 4 polarity phase of in-situ immobilization electrode on same annulus
Together, adjacent rings 4 polarity of in-situ immobilization electrode on the contrary, and multiple in-situ immobilization electrodes 4 on each annulus where it
The circumferential direction of annulus is uniformly distributed, and the metal connection column 405 of the anode in-situ immobilization electrode is connected by the anode of conducting wire and power supply 1
It connects, the metal connection column 405 of cathode in-situ immobilization electrode is connect by conducting wire with the cathode of power supply 1, and the power supply 1 is low pressure
Pulse dc power can be used sun-generated electric power under illumination adequate condition and directly provide direct current.
The anode in-situ immobilization electrode 4 is internally provided with anode permeable reactive barrier 5, stainless steel fine metal mesh
Be loaded anion-exchange membrane in 403, the H that anion-exchange membrane prevents anode electrolysis from generating+Into soil, it is existing to reduce soil acidification
As, and allow negatively charged fluorine ion (F-, FeF6 3-Deng) enter anode chamber, the electrolysis room of anode in-situ immobilization electrode 4
For accommodating anolyte, electrolysis room constitutes sun by delivery hose 7 and delivery pump and anolyte storage tank 2
The continuous circulation loop of pole electrolyte.
The cathode in-situ immobilization electrode 4 is internally provided with cathode permeable reactive barrier 6, stainless steel fine metal mesh
Be loaded cation-exchange membrane in 403, the OH that cation-exchange membrane is used to that catholyte to be prevented to generate-Into soil, soil is reduced
Alkalize phenomenon, and allows positively charged fluorine complex ion (AlF2+、AlF2 +Deng) enter cathode chamber.The electricity of cathode in-situ immobilization electrode 4
Pole tank house is stored for accommodating catholyte, electrolysis room by delivery hose 7 and delivery pump and catholyte
The continuous circulation loop of the composition catholyte of tank 3.
In electrolyte cyclic process, delivery hose 7 and delivery pump are fixed using the flow control valve being arranged on delivery hose 7
Measure it is continual from anolyte storage tank to electrolysis room input electrolyte, also simultaneous quantitative uninterruptedly from electrolysis room to
Anolyte storage tank exports electrolyte, (by pumping the adjusting with flow control valve, it is ensured that the fluid infusion of electrolyte in electrolysis room
Amount be greater than drawing liquid amount, keep electrode chamber in there are a certain amount of electrolyte always), such anolyte storage tank and electrolysis room
Just constitute circulation loop.
Permeable reactive barrier (being embedded in in-situ immobilization electrode by card slot), permeable reactive barrier itself in device
For stainless steel frame structure, it is covered with thin stainless (steel) wire, inside is filled with defluoroing filling, and water energy passes freely through permeable reaction lattice
Grid, by while, fluorine by inner stuffing adsorb fix.What is filled in anode permeable reactive barrier is Modified Iron load macropore
Phosphoramidic-resin, or modified lanthanum loading chitosan resin or both certain proportion mixture.In cathode permeable reactive barrier
Filling is modified activated aluminum oxide or bone black or zeolite or bamboo charcoal or the former certain proportion mixture (method of modifying: defluorinating agent
Dipping modification is carried out with certain density zinc chloride or calcium chloride or potassium hydroxide).
Further, at least one of potassium nitrate solution, ammonium hydroxide and the sodium acetate solution that the anolyte is；
The catholyte is at least one of potassium nitrate solution, acetic acid solution and citric acid solution.
Further, it is provided in the anolyte storage tank 2 and catholyte storage tank 3 to electrolyte
The mixing component being stirred.Electrolyte is stirred evenly, concentration polarization can be reduced, and takes away the H of cathode and anode generation2And O2,
Reduce activation polarization, to reduce overpotential in favor of energy saving.
A kind of method of in-situ immobilization fluoride pollution soil, comprising the following steps:
Step 1: to fluoride pollution soil to be repaired carry out analysis of physical and chemical property (include: soil moisture content, soil pH, conductivity,
Cation exchange capacity (CEC), porosity of soil, soil particle diameter distribution, organic matter content in soil etc.), multi-point sampling measures Fluorine Pollution In Soil
Situation, including total fluorine content (alkali melts Fluoride ion selective electrode method), (continuous extraction+fluorine ion choosing such as fluorine fractions distribution
Select electrode method).
Step 2: according to the soil physico-chemical property that step 1 measures, soil fluoride and distribution, the existing forms of Fluoride In Soils
Deng configuring fluorine eluent, the fluorine eluent is by ammonium hydroxide, sodium hydroxide, sodium acetate, in hydroxylamine hydrochloride and carboxymethyl chitosan extremely
A kind of less to configure, concentration is 0.08-0.12 mol/L, and before reparation starts, it is dirty that fluorine eluent is sprayed on fluorine to be repaired
The surface for contaminating soil constantly stirs the upper soll layer that fluoride pollution soil to be repaired is not more than 20cm depth, makes the upper soll layer
Water content is 20-35%；
Step 3: the fluorine to be repaired that multiple in-situ immobilization electrodes in prosthetic device are laid in step 1 by concentric ring-shaped is dirty
It contaminates in soil, the vertical depth of burying of control in-situ immobilization electrode in the soil is not less than 20cm；
Step 4: using delivery hose and delivery pump that the electrolysis room of step 3 Anodic in-situ immobilization electrode and anode is electric
The continuous circulation loop of anolyte is connected between solution liquid holding vessel, and controls the electrolysis of anode in-situ immobilization electrode
The input flow rate of indoor anolyte is consistently greater than output flow；
Step 5: using delivery hose and delivery pump that the electrolysis room of cathode in-situ immobilization electrode in step 3 and cathode is electric
The continuous circulation loop of catholyte is connected between solution liquid holding vessel, and controls the electrolysis of cathode in-situ immobilization electrode
The input flow rate of indoor catholyte is consistently greater than output flow；
Step 6: using delivery hose and delivery pump that the electrolysis room of cathode in-situ immobilization electrode in step 3 and cathode is electric
The continuous circulation loop of catholyte is connected between solution liquid holding vessel, and controls the electrolysis of cathode in-situ immobilization electrode
The input flow rate of indoor catholyte is consistently greater than output flow；
Step 5: the anode of the metal connection column of anode in-situ immobilization electrode and power supply is connected using conducting wire, by cathode original position
The cathode of the metal connection column and power supply of repairing electrode connects, and the output voltage intensity for adjusting power supply is 0.5-4V/cm, and is being controlled
Under the conditions of electrolyte in anolyte storage tank processed and catholyte storage tank constantly stirs, repair process 110- is carried out
130h, in repair process, according to antecedent soil moisture situation, appropriateness supplements certain fluorine eluent, and the primary sun of every 20-30h replacement
The catholyte in anolyte and catholyte storage tank in the anolyte storage tank of pole, later, removal are repaired
Device completes the reparation of fluoride pollution soil.
Further, after the completion of reparation, the permeable reactive barrier in in-situ immobilization electrode is removed, and wash using regeneration
De- liquid carries out zeolite regeneration to permeable reactive barrier, later, using chemical coagulation-sedimentation method and activated alumina absorption method pair
Gained elutes fluoride waste and carries out Combined Treatment, that is, completes the removal of fluorine contaminant.
Restorative procedure combined electrical mechanical technology and permeable reactive barrier technology of the invention, can be in the original position of soil
Carry out repair process, abandoned traditional Ex-situ remediation method, soil need to be excavated, it is broken after be transferred to specific repair in slot
The troublesome operation repaired, simultaneously as Ex-situ remediation method can only once repair the fluoride pollution soil of about several hectograms, it is practical
Property is poor.The present invention uses the in-situ treatment method of soil, is remarkably improved the desorption effect of Fluorine Pollution In Soil object and repairs effect
Rate, good practical effect.
Embodiment 1
It needs during Aluminum Electrolysis Production using fluorine fluxing agent, so periphery farmland is easily by fluoride pollution.This programme chooses one block of electrolytic aluminium
1 square metre of factory periphery polluted agricultural land is as objective for implementation.
Firstly, carry out analysis of physical and chemical property to it, measuring soil pH is 8.3,17.5 g/kg of soil organic matter content,
Cation Exchange Capacity in Soils is 19.9 cmol/kg.Measuring total fluorine content is 1416.2 mg/kg, and wherein water-soluble state fluorine accounts for
66.3%, exchangeable species fluorine accounts for 7.3%, and iron oxygen reference state fluorine 3.9%, organically combine state fluorine accounts for 3.9%, and residual form fluorine is 18.6%；
Later, by the fluorine eluent of 0.1 mol/L (ammonia spirit of 0.1 mol/L, the sodium acetate solution of 0.1 mol/L, 0.1
The hydroxylamine hydrochloride solution of mol/L, the carboxymethyl chitosan solution that mass concentration is 0.5%, by 1:1:1:1 mixing group in equal volume
At) it is sprayed at contaminated soil surface, pollution of surface soil (0-20cm, the region are fluoride pollution main region) is stirred, makes 1 square
The surface layer rice contaminated soil 0-20cm moisture content is 30% or so.
Electrode is laid by concentric ring-shaped, as shown in figure 4, the in-situ immobilization electrode of high 20cm is repaired using radius 5cm
Multiple operation.It is arranged according to concentric ring-shaped, cathode is connect with anode by conducting wire, and positive and negative interpolar is arranged in action of low-voltage pulse power supply
Voltage gradient is 2 V/cm.Supplement electrolyte (sun when operation into the electrolysis room of in-situ immobilization electrode by 10 mL/min amounts
Pole supplements 0.1 mol/L sodium acetate solution, and cathode supplements 0.1 mol/L acetic acid solution), it is electric from in-situ immobilization by 5 mL/min amounts
Extract electrolyte in the electrolysis room of pole out, electrolyte is recycled in electrolysis room and anolyte storage tank.Every 24 is small
The acetic acid electrolyte being put into Shi Genghuan anolyte storage tank in sodium acetate electrolyte and catholyte storage tank.
What is filled in anode permeable reactive barrier is that Modified Iron load macropore phosphoramidic-resin and modified lanthanum load shell
The mixture of polysaccharide resins, ratio 1:1；The defluorinating agent filled in cathode permeable reactive barrier be modified activated aluminum oxide and
Bone black and zeolite and bamboo charcoal mixture, ratio 6:1:1:2.
After operation 120 hours, reparation is finished, and in-situ immobilization electrode is removed, to the permeable reaction in in-situ immobilization electrode
Grid carries out zeolite regeneration with regenerative elution liquid, and the fluoride waste after elution uses chemical coagulation-sedimentation method (CaCl2+ PAM poly- third
Acrylamide+PAC aluminium polychloride) and activated alumina absorption method Combined Treatment.
To the soil progress multi-point sampling detection and analysis after the above process is repaired, measuring total fluorine average content is 219.8
Mg/kg, removal rate 84.5%, while the fluorine contaminant morphologic change after reparation in soil, the strongest water-soluble state fluorine ratio of toxicity
It is reduced to 4.3%, the exchangeable species fluorine ratio that toxicity is taken second place is reduced to 1.8%, and ferrimanganic reference state fluorine ratio is reduced to 1.7%, organic
Reference state fluorine becomes 3.8%, and the fluorine after reparation in soil exists mostly in the form of residual form fluorine, and chemical activity and bio-toxicity are low,
The toxicity of soil and animals and plants is significantly reduced, soil is repaired.
Embodiment 2
The present embodiment chooses one piece of 1 square metre of electrolytic aluminium factory periphery polluted agricultural land as objective for implementation.
Firstly, carry out analysis of physical and chemical property to it, measuring soil pH is 8.2,17.2 g/kg of soil organic matter content,
Cation Exchange Capacity in Soils is 20.1 cmol/kg.Measuring total fluorine content is 1425.7 mg/kg, and wherein water-soluble state fluorine accounts for
65.1%, exchangeable species fluorine accounts for 8.5%, and iron oxygen reference state fluorine accounts for 3.7%, and organically combine state fluorine accounts for 3.8%, and residual form fluorine accounts for 18.9%.
Later, by the fluorine eluent of 0.1 mol/L (ammonia spirit of 0.1 mol/L, the sodium acetate solution of 0.1 mol/L,
The hydroxylamine hydrochloride solution of 0.1 mol/L, the carboxymethyl chitosan solution that mass concentration is 0.5%, by the volume ratio of 4:1:4:1
Mixing composition) it is sprayed at contaminated soil surface, pollution of surface soil (0-20cm, the region are fluoride pollution main region) is stirred,
Make the 1 square metre of surface layer contaminated soil 0-20cm moisture content 30% or so.
Electrode is laid by concentric ring-shaped (the present embodiment is specially quincunx), as shown in figure 5, using radius 10cm, it is high
The in-situ immobilization electrode of 20cm carries out repair.It to be arranged according to concentric ring-shaped, cathode is connect with anode by conducting wire,
It is 2 V/cm that positive and negative interpolar voltage gradient, which is arranged, in action of low-voltage pulse power supply.By 20 mL/min amounts to in-situ immobilization electrode when operation
Electrolyte is supplemented in electrolysis room, and (anode supplements 0.1 mol/L sodium acetate solution, and it is molten that cathode supplements 0.1 mol/L acetic acid
Liquid), extract electrolyte out from the electrolysis room of in-situ immobilization electrode by 10 mL/min amounts, electrolyte in electrolysis room and
It is recycled in anolyte storage tank.Sodium acetate electrolyte and cathode electricity are put into every 24 hours replacement anolyte storage tanks
Solve the acetic acid electrolyte in liquid holding vessel.
What is filled in anode permeable reactive barrier is that Modified Iron load macropore phosphoramidic-resin and modified lanthanum load shell
The mixture of polysaccharide resins, ratio 2:1；The defluorinating agent filled in cathode permeable reactive barrier be modified activated aluminum oxide and
Bone black and zeolite and bamboo charcoal mixture, ratio 5:2:1:2.
After operation 120 hours, reparation is finished, and in-situ immobilization electrode is removed, to the permeable reaction in in-situ immobilization electrode
Grid carries out zeolite regeneration with regenerative elution liquid, and the fluoride waste after elution uses chemical coagulation-sedimentation method (CaCl2+ PAM poly- third
Acrylamide+PAC aluminium polychloride) and activated alumina absorption method Combined Treatment.
Multi-point sampling detection and analysis are carried out to soil after reparation, measuring total fluorine average content is 256.4 mg/kg, is gone
Except rate is 82.01%.Fluorine contaminant morphologic change, the strongest water-soluble state fluorine ratio of toxicity are reduced in soil after repairing simultaneously
4.7%, the exchangeable species fluorine ratio that toxicity is taken second place is reduced to 2.1%, and ferrimanganic reference state fluorine ratio is reduced to 1.8%, organically combine state
Fluorine becomes 3.7%, and inert residual form fluorine ratio rises to 87.7%, and fluorine exists mostly in the form of residual form fluorine in soil after reparation,
Chemical activity and bio-toxicity are low, significantly reduce to the toxicity of soil and animals and plants, soil is repaired.
The above disclosure is just a few specific examples of the present application, it but is not intended to limit the scope of the present invention.
Anyone skilled in the art, the change and retouching done on the basis of the present invention, all should belong to guarantor of the invention
Protect range.
Claims (10)
1. a kind of device of in-situ immobilization fluoride pollution soil, it is characterised in that: including power supply (1), anolyte storage tank
(2), catholyte storage tank (3) and multiple in-situ immobilization electrodes (4) being laid in fluoride pollution soil, the original position is repaired
Overlying electrode (4) includes the cylindrical support frame (402) of circular bottom plate (401) and setting above circular bottom plate (401), in cylinder
The circumferential direction of shape support frame (402) is enclosed equipped with stainless steel fine metal mesh (403), is loaded on the inside of the stainless steel fine metal mesh (403)
There is amberplex, the amberplex and circular bottom plate (401) define an inside for accommodating electrolyte together
Electrolysis room, be also detachably provided with for adsorbing fluorine contaminant in the inside of the stainless steel fine metal mesh (403)
Permeable reactive barrier is vertically arranged with a graphite stick electrode (404) at the center of the circular bottom plate (401) upwards,
The height of the graphite stick electrode (404) is not less than the height of cylindrical support frame (402), and graphite stick electrode (404)
Top is additionally provided with metal connection column (405)；
Multiple in-situ immobilization electrodes (4) include anode in-situ immobilization electrode and cathode in-situ immobilization electrode, multiple original positions
It repairs electrode (4) to be distributed in fluoride pollution soil in concentric ring-shaped, in-situ immobilization electrode (4) polarity on same annulus
Identical, in-situ immobilization electrode (4) polarity of adjacent rings is on the contrary, and the equal edge of multiple in-situ immobilization electrodes (4) on each annulus
Circumferential direction of annulus is uniformly distributed where it, and the metal connection column (405) of the anode in-situ immobilization electrode passes through conducting wire and power supply
(1) anode connection, the metal connection column (405) of cathode in-situ immobilization electrode are connect by conducting wire with the cathode of power supply (1), institute
The power supply (1) stated is action of low-voltage pulse DC power supply；
The anode in-situ immobilization electrode (4) is internally provided with anode permeable reactive barrier (5), stainless steel fine metal mesh
(403) be loaded anion-exchange membrane in, and for accommodating anolyte, electrolysis room passes through delivery hose for electrolysis room
(7) and delivery pump and anolyte storage tank (2) constitute the continuous circulation loop of anolyte, the cathode in-situ immobilization
Electrode (4) is internally provided with cathode permeable reactive barrier (6), and be loaded cation exchange in stainless steel fine metal mesh (403)
Film, electrolysis room pass through delivery hose (7) and delivery pump and catholyte for accommodating catholyte, electrolysis room
The continuous circulation loop of liquid holding vessel (3) composition catholyte.
2. a kind of device of in-situ immobilization fluoride pollution soil according to claim 1, it is characterised in that: described is permeable
Reaction grid is fixed on stainless steel fine metal mesh (403) by the multiple card slots (8) being arranged on cylindrical support frame (402)
Inside.
3. a kind of device of in-situ immobilization fluoride pollution soil according to claim 1, it is characterised in that: the conveying is soft
Pipe (7) is provided with flow control valve.
4. a kind of device of in-situ immobilization fluoride pollution soil according to claim 1, it is characterised in that: the power supply
It (1) is solar DC power supply.
5. a kind of device of in-situ immobilization fluoride pollution soil according to claim 1, it is characterised in that: the anode electricity
At least one of potassium nitrate solution, ammonium hydroxide and the sodium acetate solution that solution liquid is；The catholyte be potassium nitrate solution,
At least one of acetic acid solution and citric acid solution.
6. a kind of device of in-situ immobilization fluoride pollution soil according to claim 1, it is characterised in that: the anode can seep
It is that Modified Iron loads in macropore phosphoramidic-resin and modified lanthanum loading chitosan resin that transflection, which answers the filler in grid (5),
It is at least one；Filler in the cathode permeable reactive barrier (6) is modified activated aluminum oxide, bone black, zeolite and bamboo
At least one of charcoal.
7. a kind of device of in-situ immobilization fluoride pollution soil according to claim 1, it is characterised in that: the anode electricity
The mixing component being stirred to electrolyte is provided in solution liquid holding vessel (2) and catholyte storage tank (3).
8. a kind of device of in-situ immobilization fluoride pollution soil according to claim 1, it is characterised in that: the graphite rod
Shape electrode (404) is fixed on cylindrical support frame (402), and the diameter of graphite stick electrode (404) is 2-20cm, high
Degree is 20-50cm.
9. a kind of method of in-situ immobilization fluoride pollution soil according to claim 1, which is characterized in that including following step
It is rapid:
Step 1: taking ammonium hydroxide, sodium hydroxide, sodium acetate, at least one of hydroxylamine hydrochloride and carboxymethyl chitosan are configured to dense
Degree is 0.08-0.12 mol/L fluorine eluent, is sprayed on the surface of fluoride pollution soil to be repaired, constantly stirs fluoride pollution to be repaired
Soil is not more than the upper soll layer of 20cm depth, makes the water content 20-35% of the upper soll layer；
Step 2: the fluorine to be repaired that multiple in-situ immobilization electrodes in prosthetic device are laid in step 1 by concentric ring-shaped is dirty
It contaminates in soil, the vertical depth of burying of control in-situ immobilization electrode in the soil is not less than 20cm；
Step 3: using delivery hose and delivery pump that the electrolysis room of step 2 Anodic in-situ immobilization electrode and anode is electric
The continuous circulation loop of anolyte is connected between solution liquid holding vessel, and controls the electrolysis of anode in-situ immobilization electrode
The input flow rate of indoor anolyte is consistently greater than output flow；
Step 4: using delivery hose and delivery pump that the electrolysis room of cathode in-situ immobilization electrode in step 2 and cathode is electric
The continuous circulation loop of catholyte is connected between solution liquid holding vessel, and controls the electrolysis of cathode in-situ immobilization electrode
The input flow rate of indoor catholyte is consistently greater than output flow；
Step 4: using delivery hose and delivery pump that the electrolysis room of cathode in-situ immobilization electrode in step 2 and cathode is electric
The continuous circulation loop of catholyte is connected between solution liquid holding vessel, and controls the electrolysis of cathode in-situ immobilization electrode
The input flow rate of indoor catholyte is consistently greater than output flow；
Step 5: the anode of the metal connection column of anode in-situ immobilization electrode and power supply is connected using conducting wire, by cathode original position
The cathode of the metal connection column and power supply of repairing electrode connects, and the output voltage intensity for adjusting power supply is 0.5-4V/cm, and is being controlled
Under the conditions of electrolyte in anolyte storage tank processed and catholyte storage tank constantly stirs, repair process 110- is carried out
130h, in repair process, adjusting the water content of upper soll layer using the fluorine eluent of step 1 configuration is always 20-35%, and every
20-30h replaces the anolyte in an anolyte storage tank and the catholyte in catholyte storage tank
Liquid removes prosthetic device, that is, completes the reparation of fluoride pollution soil later.
10. a kind of device of in-situ immobilization fluoride pollution soil according to claim 1, it is characterised in that: after the completion of reparation,
The permeable reactive barrier in in-situ immobilization electrode is removed, and permeable reactive barrier is eluted using regenerative elution liquid
Regeneration carries out Combined Treatment to gained elution fluoride waste using chemical coagulation-sedimentation method and activated alumina absorption method later,
Complete the removal of fluorine contaminant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910605555.1A CN110180886B (en) | 2019-07-05 | 2019-07-05 | Device and method for in-situ remediation of fluorine-contaminated soil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910605555.1A CN110180886B (en) | 2019-07-05 | 2019-07-05 | Device and method for in-situ remediation of fluorine-contaminated soil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110180886A true CN110180886A (en) | 2019-08-30 |
| CN110180886B CN110180886B (en) | 2021-03-02 |
Family
ID=67725107
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910605555.1A Expired - Fee Related CN110180886B (en) | 2019-07-05 | 2019-07-05 | Device and method for in-situ remediation of fluorine-contaminated soil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110180886B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110479757A (en) * | 2019-09-02 | 2019-11-22 | 河南工程学院 | A kind of the electro reclamation device and restorative procedure of Compound Heavy Metals soil |
| CN111375627A (en) * | 2019-10-09 | 2020-07-07 | 闻勤动力设备(上海)有限公司 | Device and method for restoring organic contaminated soil and underground water through pulse discharge |
| CN111389890A (en) * | 2020-03-31 | 2020-07-10 | 山东大学 | Dynamic in-situ repair particle induced polarization experimental device and method |
| CN112175623A (en) * | 2020-10-15 | 2021-01-05 | 森特士兴集团股份有限公司 | Stabilizer for repairing fluoride-contaminated soil and using method thereof |
| CN112371717A (en) * | 2020-10-22 | 2021-02-19 | 华东理工大学 | Method for reinforcing electrokinetic remediation of organic-heavy metal combined contaminated soil by chelating surfactant |
| CN114160565A (en) * | 2021-12-08 | 2022-03-11 | 江苏澳洋生态园林股份有限公司 | Electrochemical soil improvement system |
| CN114226436A (en) * | 2021-11-30 | 2022-03-25 | 浙江大学杭州国际科创中心 | Metal nanocrystalline modified composite electrode and preparation method and application thereof |
| CN114367533A (en) * | 2022-01-18 | 2022-04-19 | 陕西省土地工程建设集团有限责任公司 | Soil remediation system and method |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1899717A (en) * | 2006-07-07 | 2007-01-24 | 南开大学 | Process for united repairing heavy metal polluted soil by electric power and iron permeable reaction lattices |
| CN101786099A (en) * | 2010-02-03 | 2010-07-28 | 河南科技大学 | Electrodynamic method for removing fluorine contaminant in soil |
| KR20120131426A (en) * | 2011-05-25 | 2012-12-05 | 한국전기연구원 | Soil remediation system using electrokinetics |
| JP2014087750A (en) * | 2012-10-30 | 2014-05-15 | Mitsui Eng & Shipbuild Co Ltd | Electrodialyzer and electrodialytic method |
| CN104492796A (en) * | 2014-12-09 | 2015-04-08 | 江苏盖亚环境工程有限公司 | Electrokinetic remediation method of heavy metal contaminated soil |
| US20150151986A1 (en) * | 2013-03-18 | 2015-06-04 | Transglobal H2O, Llc. | Method and Apparatus for Conditioning Fresh and Saline Water |
| CN105057339A (en) * | 2015-07-24 | 2015-11-18 | 中国环境科学研究院 | Remedying method for removing chrome in contaminated soil of chromium slag site in situ |
| CN105798058A (en) * | 2016-05-27 | 2016-07-27 | 中国环境科学研究院 | Method for repairing hexachlorocyclohexane contaminated soil |
| CN106111693A (en) * | 2016-08-12 | 2016-11-16 | 中国环境科学研究院 | A kind of method of in-situ immobilization arsenic slag contaminated soil of site |
| CN205966754U (en) * | 2016-08-12 | 2017-02-22 | 中国环境科学研究院 | Arsenic slag contaminated sites soil electronic PRB prosthetic devices |
-
2019
- 2019-07-05 CN CN201910605555.1A patent/CN110180886B/en not_active Expired - Fee Related
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1899717A (en) * | 2006-07-07 | 2007-01-24 | 南开大学 | Process for united repairing heavy metal polluted soil by electric power and iron permeable reaction lattices |
| CN101786099A (en) * | 2010-02-03 | 2010-07-28 | 河南科技大学 | Electrodynamic method for removing fluorine contaminant in soil |
| KR20120131426A (en) * | 2011-05-25 | 2012-12-05 | 한국전기연구원 | Soil remediation system using electrokinetics |
| JP2014087750A (en) * | 2012-10-30 | 2014-05-15 | Mitsui Eng & Shipbuild Co Ltd | Electrodialyzer and electrodialytic method |
| US20150151986A1 (en) * | 2013-03-18 | 2015-06-04 | Transglobal H2O, Llc. | Method and Apparatus for Conditioning Fresh and Saline Water |
| CN104492796A (en) * | 2014-12-09 | 2015-04-08 | 江苏盖亚环境工程有限公司 | Electrokinetic remediation method of heavy metal contaminated soil |
| CN105057339A (en) * | 2015-07-24 | 2015-11-18 | 中国环境科学研究院 | Remedying method for removing chrome in contaminated soil of chromium slag site in situ |
| CN105798058A (en) * | 2016-05-27 | 2016-07-27 | 中国环境科学研究院 | Method for repairing hexachlorocyclohexane contaminated soil |
| CN106111693A (en) * | 2016-08-12 | 2016-11-16 | 中国环境科学研究院 | A kind of method of in-situ immobilization arsenic slag contaminated soil of site |
| CN205966754U (en) * | 2016-08-12 | 2017-02-22 | 中国环境科学研究院 | Arsenic slag contaminated sites soil electronic PRB prosthetic devices |
Non-Patent Citations (2)
| Title |
|---|
| MING ZHOU.ET: "An electrokinetic/activated alumina permeable reactive barrier-system for the treatment of fluorine-contaminated soil", 《CLEAN TECHNOLOGIES AND ENVIRONMENTAL POLICY》 * |
| 张瑞华等: "电动力和铁PRB技术联合修复铬（VI)污染土壤", 《环境科学》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110479757A (en) * | 2019-09-02 | 2019-11-22 | 河南工程学院 | A kind of the electro reclamation device and restorative procedure of Compound Heavy Metals soil |
| CN110479757B (en) * | 2019-09-02 | 2024-02-09 | 河南工程学院 | Electric restoration device and restoration method for composite heavy metal contaminated soil |
| CN111375627A (en) * | 2019-10-09 | 2020-07-07 | 闻勤动力设备(上海)有限公司 | Device and method for restoring organic contaminated soil and underground water through pulse discharge |
| CN111389890A (en) * | 2020-03-31 | 2020-07-10 | 山东大学 | Dynamic in-situ repair particle induced polarization experimental device and method |
| CN111389890B (en) * | 2020-03-31 | 2021-04-27 | 山东大学 | Dynamic in-situ repair particle induced polarization experimental device and method |
| CN112175623A (en) * | 2020-10-15 | 2021-01-05 | 森特士兴集团股份有限公司 | Stabilizer for repairing fluoride-contaminated soil and using method thereof |
| CN112371717A (en) * | 2020-10-22 | 2021-02-19 | 华东理工大学 | Method for reinforcing electrokinetic remediation of organic-heavy metal combined contaminated soil by chelating surfactant |
| CN114226436A (en) * | 2021-11-30 | 2022-03-25 | 浙江大学杭州国际科创中心 | Metal nanocrystalline modified composite electrode and preparation method and application thereof |
| CN114160565A (en) * | 2021-12-08 | 2022-03-11 | 江苏澳洋生态园林股份有限公司 | Electrochemical soil improvement system |
| CN114160565B (en) * | 2021-12-08 | 2022-11-15 | 江苏澳洋环境科技有限公司 | Electrochemical soil improvement system |
| CN114367533A (en) * | 2022-01-18 | 2022-04-19 | 陕西省土地工程建设集团有限责任公司 | Soil remediation system and method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110180886B (en) | 2021-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110180886A (en) | A kind of device and method of in-situ immobilization fluoride pollution soil | |
| CN107030101A (en) | A kind of method of utilization microbial association EK PRB restoration of soil polluted by heavy metal | |
| CN101786099B (en) | Electrodynamic method for removing fluorine contaminant in soil | |
| CN104174648B (en) | A kind of method of restoration of soil polluted by heavy metal and special equipment thereof | |
| CN104984994B (en) | Device and method for removing polychlorinated biphenyl in bottom mud through microorganism electrolytic tank | |
| CN103975788B (en) | Potted plant and the method for the microbiological fuel cell of in-situ immobilization is polluted for soil Cr | |
| CN103785677B (en) | Heavy-metal contaminated soil reparation and leacheate recycle integrated apparatus and method thereof | |
| CN1331619C (en) | Cathode acidifying electric power repairing process for heavy metal contaminated soil | |
| CN110420983B (en) | Method and system for combined leaching, adsorption and electrokinetic remediation of heavy metal contaminated soil | |
| CN205659980U (en) | Joint fenton oxidation strengthening biological of electric power migration restores reactor that phenol pollutes soil | |
| CN106424117B (en) | Mantoquita strengthens cathode electro reclamation heavy-metal contaminated soil device | |
| CN103240268B (en) | Two-dimensional inhomogeneous field experiment device for electrically repairing polluted soil | |
| CN107413837A (en) | Device and the application of oil heavy-metal composite pollution soil are repaired with electronic microbial association | |
| CN103286121B (en) | Two-dimensional inhomogeneous electric field experiment method used for electrokinetic restoration of polluted soil | |
| CN107900095B (en) | Self-generating current-rising wetland polluted soil remediation device and remediation method | |
| CN108326030A (en) | The heavy metal-polluted soil prosthetic device of convertible array-type electrode | |
| CN105665437A (en) | Device for repairing polluted soil by using electric power | |
| CN110883085A (en) | ERB combined remediation method and device for organic pesticide pollution | |
| CN109513741A (en) | Device and restorative procedure for repairing polluted soil | |
| CN116765112A (en) | Electrodynamic-osmotic reaction grid device | |
| CN106986501A (en) | A kind of method and device of electronic permeable reactive wall and artificial swamp coupling treatment of sewage water | |
| CN102863131A (en) | Method for removing heavy metals from municipal residual sludge | |
| CN107855353A (en) | A kind of plane leaching repairing method in situ of heavy-metal contaminated soil | |
| CN104876409A (en) | Device for removing heavy metals and polycyclic aromatic hydrocarbons in bottom sediment of river channels and method thereof | |
| CN208545167U (en) | Capacitive adsorption device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210302 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |