CN108273837A - A kind of calcium ion and pyrosulfurous acid radical ion mixture and its application - Google Patents
A kind of calcium ion and pyrosulfurous acid radical ion mixture and its application Download PDFInfo
- Publication number
- CN108273837A CN108273837A CN201810007439.5A CN201810007439A CN108273837A CN 108273837 A CN108273837 A CN 108273837A CN 201810007439 A CN201810007439 A CN 201810007439A CN 108273837 A CN108273837 A CN 108273837A
- Authority
- CN
- China
- Prior art keywords
- calcium
- contaminated soil
- pyrosulfurous acid
- calcium ion
- soil
- 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
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910001424 calcium ion Inorganic materials 0.000 title claims abstract description 45
- -1 pyrosulfurous acid radical ion Chemical class 0.000 title claims abstract description 20
- 239000000203 mixture Substances 0.000 title claims abstract description 17
- 239000002689 soil Substances 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229910009112 xH2O Inorganic materials 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 8
- 238000001556 precipitation Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000002910 solid waste Substances 0.000 claims abstract description 7
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 claims abstract description 5
- 235000010261 calcium sulphite Nutrition 0.000 claims abstract description 5
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 29
- 239000011575 calcium Substances 0.000 claims description 21
- 239000013049 sediment Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 230000004888 barrier function Effects 0.000 claims description 13
- 238000002347 injection Methods 0.000 claims description 13
- 239000007924 injection Substances 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- WBZKQQHYRPRKNJ-UHFFFAOYSA-N disulfurous acid Chemical compound OS(=O)S(O)(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000011065 in-situ storage Methods 0.000 claims description 8
- 230000008439 repair process Effects 0.000 claims description 8
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 7
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 5
- 229910004879 Na2S2O5 Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000002262 irrigation Effects 0.000 claims description 3
- 238000003973 irrigation Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229920001021 polysulfide Polymers 0.000 claims description 3
- 239000005077 polysulfide Substances 0.000 claims description 3
- 150000008117 polysulfides Polymers 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 230000033228 biological regulation Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 235000015424 sodium Nutrition 0.000 claims description 2
- 229940043430 calcium compound Drugs 0.000 claims 1
- 150000001674 calcium compounds Chemical class 0.000 claims 1
- 238000009738 saturating Methods 0.000 claims 1
- 239000002699 waste material Substances 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 5
- 239000011651 chromium Substances 0.000 description 33
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 14
- 229910052804 chromium Inorganic materials 0.000 description 14
- 230000006641 stabilisation Effects 0.000 description 12
- 238000011105 stabilization Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 5
- 238000005067 remediation Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000003673 groundwater Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 235000010262 sodium metabisulphite Nutrition 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000012502 risk assessment Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- SGIDZKQKQMFQNU-UHFFFAOYSA-N [dihydroxy(oxo)-$l^{6}-sulfanylidene]calcium Chemical compound OS(O)(=O)=[Ca] SGIDZKQKQMFQNU-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000010457 zeolite Substances 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
- B09C1/002—Reclamation of contaminated soil involving in-situ ground water treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/20—Agglomeration, binding or encapsulation of solid waste
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/06—Calcium compounds, e.g. lime
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
Landscapes
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention proposes a kind of calcium ion and pyrosulfurous acid radical ion mixture and its application.By calcium ions Ca2+With pyrosulfurous acid radical ion S2O5 2‑Solution mixed with heavy-metal contaminated soil or solid waste etc. under room temperature or low temperature, then heating makes S2O5 2‑Inferior sulfate radical SO is generated by thermal decomposition3 2‑, SO3 2‑With Ca2+Reaction generates calcium sulfite CaSO3·xH2O precipitations wrap up heavy-metal contaminated soil or solid waste particle.
Description
Technical field
The present invention relates to pollution control fields.
Background technology
Stabilization/curing technology be in municipal solid wastes disposal, contaminated soil and groundwater remediation most common technology it
One.Stabilisation refer to convert pollutant to not readily dissolve, the state and form of transfer ability or small toxicity, to reduce it to life
The harm of state system.Solidification refers to wrapping up pollutant, blocks its flyway.In recovery technique, two act on it is past
It is past to occur simultaneously, therefore the two is commonly refereed to as stabilization/curing technology.
In contaminated soil and groundwater remediation, stabilization/cure applications it is most be heavy-metal contaminated soil reparation, especially
It is the reparation of chromium-polluted soil and underground water, generally use reducing agent is by highly toxic Cr VI (Cr6+) it is reduced into hypotoxicity
Trivalent chromium (Cr3+), meanwhile, trivalent chromium generates the low-down Cr of solubility (OH) in neutral conditions3, realize to the steady of chromium
Fixed/curing process.
Stabilization/curing technology both can dystopy use, can also use in situ.
Generally use in chromium-polluted soil stabilization/curing process：Zero-valent Iron, ferrous sulfate (FeSO4), vulcanized sodium (Na2S)、
Calcium polysulfide (CaSx), sodium thiosulfate (Na2S2O3), sodium pyrosulfite (Na2S2O5), sodium sulfite (Na2SO3) etc. restore
Agent needs to retain a certain amount of reducing agent due to being difficult by the Cr VI Restore All in soil in treated soil.So
And under natural conditions due to rainwater and underground water wash away and the oxidation of oxygen in water, these reducing agents can be rushed
It walks or by oxidation deactivation.Detection finds that the concentration of Cr VI in underground water rebounds after leading to several months or even several years, here it is
So-called stabilization/cured long term stability problem.
Permeable reactive barrier (Permeable reactive barrier, PRB) technology is common in groundwater remediation
The filler of based technique for in-situ remediation, PRB is interior containing Zero-valent Iron, zeolite and the carbon source etc. for enhancing microbial activity, when contaminated
When lower water flows through PRB, substance in the pollutant and filler in water occur the physical-chemical reactions such as redox, adsorption precipitation and
Biological respinse is stopped in PRB, and the water of outflow PRB is made to be purified.When PRB technologies are used for the reparation of pollution of chromium underground water
When, face long term stability problem same as described above.
There are three types of the basic reasons for causing Cr VI stabilization/solidification long term stability problem：
(1) reducing agent is water-soluble, is easy to be washed away by underground water, such as：Ferrous sulfate, vulcanized sodium etc.；
(2) reducing agent is by oxygen in water oxidation deactivation, such as：Ferrous sulfate, sodium thiosulfate etc.；
(3) reducing agent is deposited object and is coated, and can not contact and react with the Cr VI of leaching, such as：Zero-valent scrap is held
Dissolved oxygen in Yi Yushui, which reacts, generates iron oxide precipitation, and iron filings are covered, make most of remaining iron filings that can not play
Effect.
Invention content
Present invention aim to address the problems of the prior art, to realize the present invention purpose and the technical solution adopted is that
It is such：
One, a kind of calcium ion and pyrosulfurous acid radical ion mixture, it is characterised in that:
Under room temperature or low temperature, calcium ion (Ca is prepared respectively2+) and pyrosulfurous acid root (S2O5 2-) solution；
Under room temperature or low temperature, by calcium ion (Ca2+) solution and pyrosulfurous acid root (S2O5 2-) solution mixing, obtain mixed liquor；
The mixed liquor is heated, S is made2O5 2-Inferior sulfate radical SO is generated by thermal decomposition3 2-, SO3 2-With Ca2+Reaction generates big
The calcium sulfite CaSO of amount3·xH2O sediments.
Further, the calcium ion (Ca2+) solution solute be selected from Ca (OH)2Or CaCl2；
Alternatively, calcium ion (the Ca2+) solution by calcium containing compound and acid reaction be made.The calcium containing compound is selected from
CaO、CaCO3Or Ca (OH)2, the acid is selected from HCl, HNO3。
Pyrosulfurous acid root (S2O5 2-) solution solute be selected from Na2S2O5。
Further, the calcium sulfite CaSO of generation is reacted3·xH2O precipitations have the characteristic of package solid particle.
Contain calcium ion (Ca it is worth noting that being prepared under room temperature or low temperature2+) and pyrosulfurous acid radical ion (S2O5 2-)
Mixed liquor, Ca2+With S2O5 2-Precipitation reaction does not occur.
When heating mixed liquor, S2O5 2-Inferior sulfate radical SO is generated by thermal decomposition3 2-, SO3 2-With Ca2+Reaction generates sulfurous acid
Calcium CaSO3·xH2O is precipitated, and there are one features for the sediment, i.e.,：It can crystallize and analyse in other solid phase surfaces first in forming process
Go out.This feature makes the sediment at least have positive application at several aspects as described later.
Two, the present invention discloses calcium ion and pyrosulfurous acid radical ion mixture is applied to the method for contaminated soil remediation：
Under room temperature or low temperature, mixed liquor is injected into contaminated soil, heats contaminated soil so that a large amount of sediment packets of generation
Wrap up in contaminated soil particle.
Further, before mixed liquor injection contaminated soil, contaminated soil is pre-processed using method chemically or physically.
Further, when in-situ immobilization, heating the mode of contaminated soil is, is inserted into electrode, electrified regulation in the soil.
Further, it when showering, needs in advance to dig out contaminated soil, after the completion of processing, soil is backfilled.
Further, the contaminated soil is hexavalent chromium polluted, and the method for the pretreatment contaminated soil is injection sulfuric acid
The reducing agent solutions such as ferrous iron, calcium polysulfide, vulcanized sodium, sodium sulfite, sodium thiosulfate, sodium pyrosulfite, zeroth order Nanoscale Iron.
It is worth noting that as previously mentioned, the characteristics of sediment is utilized in the technical program.The sediment will not picture
Other reducing agents are the same to wash away or is dissolved oxygen oxidation by underground water quickly.Further, since the sediment has in neutral conditions
Certain solubility is dissolved in water when there is a small amount of Cr VI to be leached from soil particle that is damaged or not wrapping
SO3 2-It can be restored again, avoid the rebound of hexavalent chromium concentration in water.When some areas because acid rain is serious, underground water pH drops
It is low, when Cr VI stripping quantity being caused to increase, because the solubility of sediment will rise rapidly with the reduction of pH value, to increase water
Middle SO3 2-Concentration, effectively the Cr VI of dissolution timely can be restored.In addition, just as the sediment is easy in tube wall
Upper crystallization is precipitated that block pipeline the same, also can blocking portion soil gap, reduce the water permeable ability of soil after stabilization/solidification,
Flowing through for underground water is prevented, to reduce the probability of polluted underground water.
Other than the reparation for chromium-polluted soil and underground water, this method can be additionally used in other heavy-metal contaminated soils
Solidification, only because of S2O5 2And SO3 2-The valence state of other heavy metals is not changed, therefore with only the package action of the sediment
With reduction soil permeability performance feature.
Three, the present invention discloses calcium ion and pyrosulfurous acid radical ion mixture is applied to the structure of permeable reactive barrier (PRB)
It builds：
The mixed liquor is uniformly mixed with the filler of structure PRB, the subsurface flow warp dug is inserted after heating and keeping the temperature
Irrigation canals and ditches in, overlying clay protection, to build permeable reactive barrier；
Four, the present invention discloses calcium ion and pyrosulfurous acid radical ion mixture repairing applied to permeable reactive barrier (PRB)
It is multiple：
It is for the permeable reactive barrier (PRB) of failure in a long time, mixed liquor injection permeable reactive barrier (PRB) is interior,
Permeable reactive barrier (PRB) disengaging water end (W.E.) is blocked with water fender simultaneously, does not allow solution to be lost in；It heats and keeps the temperature permeable reaction
Wall (PRB), repair are completed.
Five, the present invention discloses calcium ion and pyrosulfurous acid radical ion mixture is applied to the method for solid waste processing：
To some solid waste, such as：The sludge etc. that chromium slag, electroplating wastewater processing generate first carries out physically or chemically pre-
After processing, the mixed liquor is mixed with solid waste, heats and keep the temperature, finally filled.
The technique effect such as embodiment of the present invention.
Description of the drawings
Fig. 1 is the structural schematic diagram of embodiment 1.
In figure, the hexavalent chromium polluted soil of 1-, 2- injector wells, 3- collect well, 4- electrodes
Specific implementation mode
With reference to embodiment, the invention will be further described, but should not be construed the above-mentioned subject area of the present invention only
It is limited to following embodiments.Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and used
With means, various replacements and change are made, should all include within the scope of the present invention.
Embodiment 1：
In the present embodiment, in-situ immobilization is implemented in the way of attached drawing 1 to the underground water in certain pollution of chromium place.
Hexavalent chromium concentration is 685mg/kg in the place soil 1, and ferrous sulfate solution is passed through note using syringe pump first
It penetrates well 2 to inject in contaminated soil 1, to go back the Cr VI in native soil, until the concentration of Cr VI in well 3 is collected less than inspection in downstream
Survey limit.Then, using Ca (OH)2/CaCl2And Na2S2O5Preparation contains Ca2+And S2O5 2-Aqueous solution, which is passed through into injection
Well 2 injects in soil 1.Then, in the soil every 1.5 meters be inserted into an electrode 4, formed electrode matrix, piecemeal to soil into
Row heating, and 1 hour is kept the temperature, it can find that the injection resistance of solution dramatically increases at this time, the water percolating capacity being collected simultaneously in well 3 is also shown
It writes and reduces, illustrate CaSO3·xH2O sediments largely form and enclose part soil crack, and repair is completed.
Embodiment 2：
In the present embodiment, in-situ immobilization is implemented in the way of attached drawing 1 to the underground water in certain pollution of chromium place.
Hexavalent chromium concentration is 216mg/kg in the place soil 1, first by sodium pyrosulfite (Na2S2O5) solution use note
It penetrates pump to inject in contaminated soil 1 by injector well 2, to go back the Cr VI in native soil, until Cr VI in well 3 is collected in downstream
Concentration is limited less than detection.Then, it is reacted and is produced containing Ca with HCl using CaO2+The solution is injected soil by aqueous solution by injector well 2
In earth 1.Then, it being inserted into an electrode 4 every 1.2 meters in the soil, forms electrode matrix, piecemeal heats soil, and
Heat preservation 1 hour, can find that the injection resistance of solution dramatically increases, the water percolating capacity being collected simultaneously in well 3 also substantially reduces, and says at this time
The remaining S of bright first injection2O5 2-It decomposes in a heated condition and generates SO3 2-And the Ca further injected with second2+Reaction life
At CaSO3·xH2O sediments, the sediment enclose part soil crack, and repair is completed.
Embodiment 3：
In the present embodiment, in-situ immobilization is implemented in the way of attached drawing 1 to the underground water in certain pollution of chromium place.
Hexavalent chromium concentration is 61mg/kg in the place soil 1, dense according to Cr VI in space enrironment risk assessment soil 1
It spends exceeded.Underground water detection finds Cr VI, but not exceeded, for the environmental risk for reducing following, is carried out to the place preventative
It repairs.CaCO is used first3With HNO3Reaction is produced containing Ca2+Aqueous solution injects the solution in soil 1 by injector well 2.So
Afterwards, by sodium pyrosulfite (Na2S2O5) solution is injected by injector well 2 in contaminated soil 1 using syringe pump, until downstream is collected
The concentration of Cr VI is limited less than detection in well 3.Then, it is inserted into an electrode 4 every 5 meters in the soil, forms electrode matrix, point
Block heats soil, and keeps the temperature 1 hour, can find that the injection resistance of solution dramatically increases at this time, be collected simultaneously in well 3
Water percolating capacity also substantially reduces, and illustrates the S of the second injection2O5 2-It decomposes in a heated condition and generates SO3 2-And further with for the first time
The Ca of injection2+Reaction generates CaSO3·xH2O sediments, the sediment enclose part soil crack, and repair is completed.
Embodiment 4：
In the present embodiment, to the implementation showering of certain pollution of chromium place soil.
Hexavalent chromium concentration is 216mg/kg in the contaminated soil of site, is restored first with excess sodium metabisulfite solution
Processing, then again with CaCO3Reacted with HCl produce contain Ca2+Aqueous solution mixes, and is heated to 40~50 DEG C and keeps the temperature 1 hour, leaching
Go out experiment and Cr VI is not detected, is finally transported into the landfill isolation disposition of landfill area.
Embodiment 5：
In the present embodiment, the implementation dystopy risk management and control of certain pollution of chromium place soil is disposed.
Hexavalent chromium concentration is 38mg/kg in the contaminated soil of site, super according to space enrironment risk assessment hexavalent chromium concentration
Mark is implemented to dig clearly, using the risk management and control measure of strange land landfill after stabilisation to reduce environmental risk to the part soil.Clearly
The soil digged up is uniform with lime dry powder (CaO) and sodium pyrosulfite dry powder blend first, and then plus water stirs evenly.CaO
It meets water reaction and generates Ca (OH)2Solution, while discharging amount of heat and make S2O5 2-It decomposes and generates SO3 2-, SO3 2-Further with Ca2+Instead
CaSO should be generated3·xH2O precipitations are wrapped in outside soil particle.After waiting for natural air drying, which is transported to landfill area landfill
Isolation disposition.
Embodiment 6：
In the present embodiment, pollution of chromium underground water is repaired using present invention structure PRB (permeable reactive barrier).
By the rough sand of 1~2mm of diameter and use Ca (OH)2/CaCl2And Na2S2O5That prepares contains Ca2+And S2O5 2-Aqueous solution
It is uniformly mixed, is heated to 40~50 DEG C and keeps the temperature 1 hour, be then filled in the irrigation canals and ditches of the subsurface flow warp dug, overlying clay is protected
Shield.
Embodiment 7：
In the present embodiment, failed PRB is repaired using the present invention.
One cuts the PRB failures in a long time of mixture structure using coarse sand, iron, leads to the exceeded one times of left side of Cr VI in underground water
It is right.It will contain Ca using the present invention2+And S2O5 2-Aqueous solution injection PRB in, while by PRB disengaging water end (W.E.) blocked with water fender, no
Solution is allowed to be lost in.It inserts electrodes into PRB bodies, temperature is electrically heated to it and reaches 40~50 DEG C, keeps the temperature 1 hour, repairs work
It completes, removes the water fender of PRB disengaging water end (W.E.)s, check water outlet Cr VI, less than detection limit.
Embodiment 8：
In the present embodiment, stabilization/curing process is carried out to chromium slag using the present invention.
Chromium slag carries out Detoxified treatment with ferrous sulfate first, and Na is then added2S2O5 2-Aqueous solution is uniformly mixed, and is added again later
It is uniform to enter CaO dry powder blends.CaO meets water reaction and generates Ca (OH)2Solution, while discharging amount of heat and make S2O5 2-It decomposes and generates
SO3 2-, SO3 2-Further with Ca2+Reaction generates CaSO3·xH2O precipitations are wrapped in outside chromium slag particle.Maintenance is transported to after one day
Landfill yard landfill stabilization.
Claims (9)
1. a kind of calcium ion and pyrosulfurous acid radical ion mixture, it is characterised in that:
Under room temperature or low temperature, calcium ion (Ca is prepared respectively2+) and pyrosulfurous acid root (S2O5 2-) solution；
Under room temperature or low temperature, by calcium ion (Ca2+) solution and pyrosulfurous acid root (S2O5 2-) solution mixing, obtain mixed liquor；
The mixed liquor is heated, S is made2O5 2-Inferior sulfate radical SO is generated by thermal decomposition3 2-, SO3 2-With Ca2+Reaction generates a large amount of
Calcium sulfite CaSO3·xH2O sediments.
2. a kind of calcium ion according to claim 1 and pyrosulfurous acid radical ion mixture, it is characterised in that：
Calcium ion (the Ca2+) solution solute be selected from Ca (OH)2Or CaCl2；Alternatively, calcium ion (the Ca2+) solution is by containing
Calcium compound and acid reaction are made；The calcium containing compound is selected from CaO, CaCO3Or Ca (OH)2, the acid is selected from HCl, HNO3；
Pyrosulfurous acid root (S2O5 2-) solution solute be selected from Na2S2O5。
3. a kind of calcium ion according to claim 1 or 2 and pyrosulfurous acid radical ion mixture, it is characterised in that：
Calcium ion (the Ca2+) in, Ca2+Concentration range be 0.001~3.8mol/L
Pyrosulfurous acid root (the S2O5 2-) in solution, S2O5 2-Concentration range be 0.001~2.8mol/L
React the calcium sulfite CaSO generated3·xH2O precipitations have the characteristic of package solid particle.
4. a kind of calcium ion and pyrosulfurous acid radical ion mixture by described in 1~3 any one claim is applied to pollution
Soil in-situ reparation, it is characterised in that：Under room temperature or low temperature, mixed liquor is injected into contaminated soil, heats contaminated soil so that is raw
At a large amount of sediments wrap up contaminated soil particle.
5. application according to claim 4, it is characterised in that：Before mixed liquor injects contaminated soil, using chemically or physically
Method to contaminated soil pre-process.
6. application according to claim 5, it is characterised in that：When in-situ immobilization, heating the mode of contaminated soil is, in soil
Electrode, electrified regulation are inserted into earth.
When showering, needs in advance to dig out contaminated soil, after the completion of processing, soil is backfilled.
7. application according to claim 6, it is characterised in that：The contaminated soil is hexavalent chromium polluted, the pre- place
The method of reason contaminated soil is injection ferrous sulfate, calcium polysulfide, vulcanized sodium, sodium sulfite, sodium thiosulfate, pyrosulfurous acid
The reducing agent solutions such as sodium, zeroth order Nanoscale Iron.
8. a kind of calcium ion and pyrosulfurous acid radical ion mixture by described in 1~3 any one claim is applied to ooze
The structure of saturating reaction wall (PRB) or reparation, it is characterised in that：
Structure：The mixed liquor is uniformly mixed with the filler of structure PRB, the subsurface flow warp dug is inserted after heating and keeping the temperature
Irrigation canals and ditches in, overlying clay protection, to build permeable reactive barrier；
It repairs：It is for the permeable reactive barrier (PRB) of failure in a long time, mixed liquor injection permeable reactive barrier (PRB) is interior,
Permeable reactive barrier (PRB) disengaging water end (W.E.) is blocked with water fender simultaneously, does not allow solution to be lost in；It heats and keeps the temperature permeable reaction
Wall (PRB), repair are completed.
9. a kind of calcium ion and pyrosulfurous acid radical ion mixture by described in 1~3 any one claim is applied to solid
The processing of waste：After solid waste is first physically or chemically pre-processed, the mixed liquor is mixed with solid waste
Afterwards, it heats and keeps the temperature, then filled.
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| CN108273837B (en) | 2020-05-26 |
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