CN108273837B - Calcium ion and pyrosulfite ion mixture and application thereof - Google Patents
Calcium ion and pyrosulfite ion mixture and application thereof Download PDFInfo
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- CN108273837B CN108273837B CN201810007439.5A CN201810007439A CN108273837B CN 108273837 B CN108273837 B CN 108273837B CN 201810007439 A CN201810007439 A CN 201810007439A CN 108273837 B CN108273837 B CN 108273837B
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910001424 calcium ion Inorganic materials 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 150000002500 ions Chemical class 0.000 title description 3
- 239000002689 soil Substances 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims abstract description 15
- -1 metabisulfite ions Chemical class 0.000 claims abstract description 11
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 8
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 claims abstract description 6
- 235000010261 calcium sulphite Nutrition 0.000 claims abstract description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 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 32
- 239000011575 calcium Substances 0.000 claims description 30
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 30
- 238000005067 remediation Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 19
- 239000002244 precipitate Substances 0.000 claims description 15
- 230000004888 barrier function Effects 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000011790 ferrous sulphate Substances 0.000 claims description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 7
- 238000011065 in-situ storage Methods 0.000 claims description 7
- 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
- 230000008439 repair process Effects 0.000 claims description 7
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 7
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 229910004879 Na2S2O5 Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 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
- 239000013049 sediment Substances 0.000 claims description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 3
- 238000011049 filling 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
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 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
- 238000000053 physical method Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910009112 xH2O Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 5
- 238000001556 precipitation Methods 0.000 abstract description 5
- 239000002910 solid waste Substances 0.000 abstract description 4
- 239000011651 chromium Substances 0.000 description 15
- 239000003673 groundwater Substances 0.000 description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 13
- 238000002347 injection Methods 0.000 description 13
- 239000007924 injection Substances 0.000 description 13
- 229910052804 chromium Inorganic materials 0.000 description 12
- 230000006641 stabilisation Effects 0.000 description 10
- 238000011105 stabilization Methods 0.000 description 10
- 239000011734 sodium Substances 0.000 description 7
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000005516 engineering process 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
- 238000011066 ex-situ storage Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012502 risk assessment Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000009270 solid waste treatment Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 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
- 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 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 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
- 238000004090 dissolution Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000001617 migratory effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012954 risk control Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
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
- 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
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- 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 invention provides a mixture of calcium ions and metabisulfite ions and application thereof. Calcium ion Ca2+And metabisulfite ion S2O5 2‑The solution is mixed with heavy metal contaminated soil or solid waste at normal or low temperature, and then heated to S2O5 2‑Heated to decompose to produce sulfite SO3 2‑，SO3 2‑With Ca2+Reaction to generate calcium sulfite CaSO3·xH2The O precipitation wraps up heavy metal contaminated soil or solid waste particles.
Description
Technical Field
The invention relates to the field of pollution control.
Background
Stabilization/solidification technology is one of the most commonly used techniques in solid waste treatment disposal, contaminated soil and groundwater remediation. Stabilization refers to the conversion of a contaminant into a state and form that is not readily soluble, migratory or toxic, in order to reduce its harm to the ecosystem. Curing means to encapsulate the contaminants and block their migration pathways. In repair techniques, both actions tend to occur simultaneously, so both are often collectively referred to as stabilization/curing techniques.
In the remediation of contaminated soil and groundwater, the most widely used for stabilization/solidification is the remediation of heavy metal contaminated soil, particularly the remediation of chromium contaminated soil and groundwater, and highly toxic hexavalent chromium (Cr) is generally treated with a reducing agent6+) Reduced to trivalent chromium (Cr) with low toxicity3+) At the same time, trivalent chromium forms Cr (OH) with very low solubility under neutral conditions3The stabilization/solidification treatment of chromium is achieved.
The stabilization/curing technique can be used either ex situ or in situ.
The following are commonly used in the stabilization/solidification treatment of chromium-contaminated soils: zero-valent iron, ferrous sulfate (FeSO)4) Sulfur, sulfurDissolving sodium (Na)2S), calcium polysulfide (CaS)x) Sodium thiosulfate (Na)2S2O3) Sodium metabisulfite (Na)2S2O5) Sodium sulfite (Na)2SO3) And when the hexavalent chromium is used as a reducing agent, a certain amount of the reducing agent needs to be reserved in the treated soil because the hexavalent chromium in the soil is difficult to reduce completely. However, these reducing agents are naturally washed away or oxidatively ineffective due to rain and groundwater scouring and oxidation by dissolved oxygen in the water. Leading to a rebound of hexavalent chromium concentrations in the groundwater as detected after months or even years, a so-called stabilization/long term stability problem of solidification.
Permeable Reactive Barrier (PRB) technology is a common in-situ remediation technology in groundwater remediation, and the filler of PRB contains zero-valent iron, zeolite, and carbon source for enhancing microbial activity, so that when polluted groundwater flows through PRB, the pollutants in water and the substances in the filler undergo physicochemical and biological reactions such as oxidation reduction, adsorption precipitation, etc., and are blocked in PRB, so that the water flowing out of PRB is purified. The same long-term stability issues as described above are faced when PRB technology is used for remediation of chromium contaminated groundwater.
There are three fundamental reasons for hexavalent chromium stabilization/long-term stability of cure problems:
(1) reducing agents are water soluble and are easily washed away by groundwater, such as: ferrous sulfate, sodium sulfide, and the like;
(2) the reducing agent is oxidized and loses efficacy by dissolved oxygen in water, such as: ferrous sulfate, sodium thiosulfate, and the like;
(3) the reducing agent is coated by the precipitate and cannot be contacted with leached hexavalent chromium to react, such as: the zero-valent iron filings are easy to react with dissolved oxygen in water to generate iron oxide precipitate, and the iron filings are covered, so that most of the rest iron filings can not play a role.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and the technical scheme adopted for realizing the aim of the invention is as follows:
a calcium ion and pyrosulfite ion mixture is characterized in that:
respectively preparing calcium ions (Ca) at normal or low temperature2+) And pyrosulfite (S)2O5 2-) The solution of (1);
at normal or low temperature, calcium ion (Ca)2+) Solution and metabisulfite (S)2O5 2-) Mixing the solutions to obtain a mixed solution;
heating the mixture to S2O5 2-Heated to decompose to produce sulfite SO3 2-，SO3 2-With Ca2+A large amount of calcium sulfite CaSO is generated by the reaction3·xH2And (4) precipitating O.
Further, the calcium ion (Ca)2+) The solute of the solution is selected from Ca (OH)2Or CaCl2；
Alternatively, the calcium ion (Ca)2+) The solution is prepared by reacting a calcium-containing compound with an acid. The calcium-containing compound is selected from CaO and CaCO3Or Ca (OH)2The acid is selected from HCl and HNO3。
Metabisulfite (S)2O5 2-) The solute of the solution is selected from Na2S2O5。
Further, calcium sulfite CaSO generated by the reaction3·xH2The O-precipitate has the property of encapsulating solid particles.
It is worth mentioning that the calcium ion (Ca) is formulated at normal or low temperature2+) And metabisulfite ion (S)2O5 2-) Mixed solution of (2), Ca2+And S2O5 2-No precipitation reaction occurred.
When the mixed solution is heated, S2O5 2-Heated to decompose to produce sulfite SO3 2-，SO3 2-With Ca2+Reaction to generate calcium sulfite CaSO3·xH2O precipitation, which has one feature, namely: the crystal will be precipitated on the surface of other solid phase in the forming process. This feature makes the precipitate at least inSeveral aspects as described hereinafter have positive application.
The invention discloses a method for applying a mixture of calcium ions and metabisulfite ions to polluted soil remediation, which comprises the following steps:
and injecting the mixed solution into the polluted soil at normal temperature or low temperature, and heating the polluted soil to enable a large amount of generated precipitates to wrap the polluted soil particles.
Furthermore, before the mixed liquor is injected into the polluted soil, the polluted soil is pretreated by adopting a chemical or physical method.
Further, in the in-situ remediation, the contaminated soil is heated by inserting an electrode into the soil and heating the electrode by energization.
Furthermore, when the ex-situ remediation is carried out, the polluted soil needs to be dug out in advance, and after the treatment is completed, the soil is backfilled.
Further, the polluted soil is polluted by hexavalent chromium, and the method for pretreating the polluted soil is to inject reducing agent solutions such as ferrous sulfate, calcium polysulfide, sodium sulfide, sodium sulfite, sodium thiosulfate, sodium metabisulfite, zero-valent nano-iron and the like.
It is worth noting that, as mentioned above, the present solution makes use of the characteristics of the precipitate. The precipitate is not washed away by groundwater or oxidized by dissolved oxygen as quickly as other reductants. In addition, since the precipitate has a certain solubility under neutral conditions, when a small amount of hexavalent chromium is leached from damaged or uncoated soil particles, SO dissolved in water3 2-But also can reduce the chromium, thereby avoiding the rebound of the concentration of the hexavalent chromium in the water. When the pH value of underground water is reduced due to severe acid rain in some areas, SO that the dissolution amount of hexavalent chromium is increased, the solubility of precipitates can be rapidly increased along with the reduction of the pH value, SO that SO in water is increased3 2-The concentration of the chromium oxide can effectively and timely reduce the dissolved hexavalent chromium. In addition, just as the precipitate is easily crystallized on the pipe wall to separate out and block the pipeline, the precipitate can block part of soil gaps, reduce the water permeability of the stabilized/solidified soil, prevent the underground water from flowing through, and further reduce the probability of polluting the underground water.
In addition to for chromiumBesides the remediation of polluted soil and underground water, the method can also be used for the solidification of other heavy metal polluted soil, only because of S2O5 2And SO3 2-The valence state of other heavy metals is not changed, so that the wrapping effect of the precipitate is only utilized, and the characteristic of reducing the water permeability of the soil is utilized.
The invention discloses application of a calcium ion and metabisulfite ion mixture to construction of a Permeable Reactive Barrier (PRB):
uniformly mixing the mixed solution with a filler for constructing PRB, heating and insulating the mixed solution, filling the mixed solution into a trench through which dug underground water flows, and covering clay for protection to construct a permeable reactive barrier;
the invention discloses application of the mixture of calcium ions and metabisulfite ions to repair of permeable reactive walls (PRB):
for Permeable Reactive Barrier (PRB) which fails for a long time, the mixed solution is injected into the Permeable Reactive Barrier (PRB), and the water inlet end and the water outlet end of the Permeable Reactive Barrier (PRB) are plugged by a water baffle plate, so that the solution is prevented from losing; and heating and insulating the Permeable Reactive Barrier (PRB), and finishing the repair work.
The invention discloses a method for applying a mixture of calcium ions and metabisulfite ions to solid waste treatment, which comprises the following steps:
for some solid waste, such as: the method comprises the steps of firstly carrying out physical or chemical pretreatment on chromium slag, sludge generated by electroplating wastewater treatment and the like, mixing the mixed liquor with solid waste, heating and preserving heat, and finally carrying out landfill.
The technical effects of the invention are as in the embodiment.
Drawings
Fig. 1 is a schematic structural view of embodiment 1.
In the figure, 1-hexavalent chromium contaminated soil, 2-injection well, 3-collection well and 4-electrode
Detailed Description
The present invention is further illustrated by the following examples, but it should not be construed that the scope of the above-described subject matter is limited to the following examples. Various substitutions and alterations can be made without departing from the technical idea of the invention and the scope of the invention is covered by the present invention according to the common technical knowledge and the conventional means in the field.
Example 1:
in this example, the groundwater in a chromium contaminated site was subjected to in situ remediation in the manner shown in fig. 1.
The concentration of hexavalent chromium in the field soil 1 is 685mg/kg, firstly, a ferrous sulfate solution is injected into the polluted soil 1 through an injection well 2 by using an injection pump so as to reduce the hexavalent chromium in the soil until the concentration of the hexavalent chromium in a downstream collecting well 3 is lower than the detection limit. Then, Ca (OH) was used2/CaCl2And Na2S2O5Preparation of a composition containing Ca2+And S2O5 2-Is injected into the soil 1 through the injection well 2. Then, an electrode 4 is inserted into the soil every 1.5 meters to form an electrode matrix, the soil is heated in blocks and is kept warm for 1 hour, and at the moment, the injection resistance of the solution can be found to be remarkably increased, and the water seepage amount in the collecting well 3 is also remarkably reduced, which indicates that CaSO3·xH2And O precipitates are formed in a large quantity and seal partial soil gaps, and the repairing work is finished.
Example 2:
in this example, the groundwater in a chromium contaminated site was subjected to in situ remediation in the manner shown in fig. 1.
The concentration of hexavalent chromium in the field soil 1 is 216mg/kg, and sodium pyrosulfite (Na) is firstly added2S2O5) The solution is injected into the polluted soil 1 through the injection well 2 by using an injection pump to reduce hexavalent chromium in the soil until the concentration of the hexavalent chromium in the downstream collection well 3 is lower than the detection limit. Then, CaO reacts with HCl to prepare Ca2+An aqueous solution, which is injected into the soil 1 through the injection well 2. Then, one electrode 4 was inserted into the soil every 1.2 m to form an electrode matrix, the soil was heated in blocks and kept warm for 1 hour, at which time it was found that the injection resistance of the solution increased significantly and the water seepage in the collection well 3 also decreased significantly, indicating the residual S remaining from the first injection2O5 2-Decomposition under heating to produce SO3 2-And further with the second injected Ca2+Reaction to produce CaSO3·xH2And O, closing part of soil gaps by using the sediment, and finishing the repairing work.
Example 3:
in this example, the groundwater in a chromium contaminated site was subjected to in situ remediation in the manner shown in fig. 1.
The concentration of hexavalent chromium in the field soil 1 is 61mg/kg, and the concentration of hexavalent chromium in the field soil 1 exceeds the standard according to field environment risk assessment. And (4) detecting underground water to find hexavalent chromium, but the hexavalent chromium is not overproof, and performing preventive remediation on the site to reduce future environmental risks. First using CaCO3With HNO3Preparation of Ca-containing substance by reaction2+An aqueous solution, which is injected into the soil 1 through the injection well 2. Then, sodium metabisulfite (Na)2S2O5) The solution is injected into the contaminated soil 1 through the injection well 2 by using a syringe pump until the concentration of hexavalent chromium in the downstream collection well 3 is lower than the detection limit. Then, one electrode 4 was inserted every 5m into the soil to form an electrode matrix, the soil was heated in blocks and kept warm for 1 hour, at which time it was found that the injection resistance of the solution increased significantly and at the same time the amount of water seeped in the collection well 3 also decreased significantly, indicating that S was injected second2O5 2-Decomposition under heating to produce SO3 2-And further with the first injected Ca2+Reaction to produce CaSO3·xH2And O, closing part of soil gaps by using the sediment, and finishing the repairing work.
Example 4:
in this example, ex-situ remediation was performed on soil in a chromium-contaminated site.
The concentration of hexavalent chromium in the polluted soil of the site is 216mg/kg, and the hexavalent chromium is firstly reduced by using excessive sodium metabisulfite solution and then mixed with CaCO3Ca-containing compounds prepared by reaction with HCl2+And (3) mixing the aqueous solutions, heating to 40-50 ℃, preserving the heat for 1 hour, carrying out a leaching experiment to detect no hexavalent chromium, and finally carrying out landfill isolation treatment in a landfill area.
Example 5:
in this embodiment, the ectopic risk management and control of the soil in a certain chromium-contaminated site is handled.
The concentration of hexavalent chromium in the site-contaminated soil is 38mg/kg, the concentration of hexavalent chromium exceeds the standard according to site environment risk assessment, in order to reduce the environment risk, the soil is dug, and after stabilization, risk control measures of remote landfill are adopted. The dug soil is firstly mixed with lime dry powder (CaO) and sodium metabisulfite dry powder uniformly, and then water is added to stir uniformly. CaO reacts with water to generate Ca (OH)2Solution, while releasing a large amount of heat to make S2O5 2-Decomposition to SO3 2-，SO3 2-Further with Ca2+Reaction to produce CaSO3·xH2The O sediment is coated outside the soil particles. After natural air drying, the soil is transported to a landfill area for landfill and isolation treatment.
Example 6:
in this example, PRB (permeable reactive barrier) constructed by the method of the present invention was used to repair chromium-contaminated groundwater.
Mixing coarse sand with the diameter of 1-2 mm with Ca (OH)2/CaCl2And Na2S2O5Formulated Ca-containing2+And S2O5 2-Uniformly mixing the aqueous solution, heating to 40-50 ℃, preserving heat for 1 hour, filling the mixture into a trench through which dug underground water flows, and covering clay for protection.
Example 7:
in this embodiment, the failed PRB is repaired by using the present invention.
The PRB constructed by adopting the mixture of coarse sand and iron shavings is invalid in the years, so that the hexavalent chromium in the underground water exceeds the standard by about one time. The present invention can contain Ca2+And S2O5 2-The water solution is injected into the PRB, and the water inlet end and the water outlet end of the PRB are plugged by a water baffle plate, so that the solution is prevented from running off. Inserting an electrode into the PRB body, performing electric heating on the electrode to reach 40-50 ℃, preserving heat for 1 hour, completing the repair work, detaching a water baffle at the water inlet end and the water outlet end of the PRB, and checking that the discharged water is hexavalent chromium and is lower than the detection limit.
Example 8:
in this example, the present invention was used to stabilize/solidify chromium slag.
The chromium slag is firstly detoxified by ferrous sulfate and then added with Na2S2O5 2-The aqueous solution is mixed evenly, and then CaO dry powder is added and mixed evenly. CaO reacts with water to generate Ca (OH)2Solution, while releasing a large amount of heat to make S2O5 2-Decomposition to SO3 2-，SO3 2-Further with Ca2+Reaction to produce CaSO3·xH2The O precipitation is coated outside the chromium slag particles. And after curing for one day, transporting to a landfill site for landfill disposal.
Claims (7)
1. A method for applying a mixture of calcium ions and metabisulfite ions to soil remediation, comprising the steps of:
respectively preparing calcium ions (Ca) at normal or low temperature2+) And pyrosulfite (S)2O5 2-) The solution of (1);
at normal or low temperature, calcium ion (Ca)2+) Solution and metabisulfite (S)2O5 2-) Mixing the solutions to obtain a mixed solution for injecting the polluted soil;
heating the mixture to S2O5 2-Heated to decompose to produce sulfite SO3 2-， SO3 2-With Ca2+A large amount of calcium sulfite CaSO is generated by the reaction3·xH2O precipitate; the sediment is used for wrapping polluted soil particles.
2. A method of applying a mixture of calcium ions and metabisulfite ions for soil remediation according to claim 1, wherein said method comprises the steps of:
the calcium ion (Ca)2+) The solute of the solution is selected from Ca (OH)2Or CaCl2(ii) a Alternatively, the calcium ion (Ca)2+) The solution is prepared by reacting a calcium-containing compound with an acid; the calcium-containing compound is selected from CaO and CaCO3Or Ca (OH)2The acid is selected from HCl and HNO3；
Metabisulfite (S)2O5 2-) The solute of the solution is selected from Na2S2O5。
3. A method for applying a mixture of calcium ions and metabisulphite ions for soil remediation according to claim 1 or 2, wherein:
the calcium ion (Ca)2+) Middle, Ca2+The concentration range of (A) is 0.001-3.8 mol/L;
the metabisulfite (S)2O5 2-) In solution, S2O5 2-The concentration range of (A) is 0.001-2.8 mol/L
Calcium sulfite CaSO generated by reaction3·xH2The O-precipitate has the property of encapsulating solid particles.
4. A method of applying a mixture of calcium ions and metabisulfite ions for soil remediation according to claim 3, wherein said step of applying comprises: before the mixed liquid is injected into the polluted soil, the polluted soil is pretreated by adopting a chemical or physical method.
5. A method of applying a mixture of calcium ions and metabisulfite ions for soil remediation according to claim 4, wherein said method comprises the steps of: during in-situ remediation, the contaminated soil is heated by inserting an electrode into the soil and electrifying and heating;
when the ectopic restoration is carried out, the polluted soil needs to be dug out in advance, and the soil is backfilled after the treatment is finished.
6. A method of applying a mixture of calcium ions and metabisulfite ions for soil remediation according to claim 5, wherein said step of applying comprises: the polluted soil is polluted by hexavalent chromium, and the method for pretreating the polluted soil is to inject reducing agent solutions such as ferrous sulfate, calcium polysulfide, sodium sulfide, sodium sulfite, sodium thiosulfate, sodium metabisulfite, zero-valent nano-iron and the like.
7. A method of applying a mixture of calcium ions and metabisulfite ions to the construction or repair of a permeable reactive wall (PRB), characterized in that:
respectively preparing calcium ions (Ca) at normal or low temperature2+) And pyrosulfite (S)2O5 2-) The solution of (1);
at normal or low temperature, calcium ion (Ca)2+) Solution and metabisulfite (S)2O5 2-) Mixing the solutions to obtain a mixed solution for injecting the polluted soil;
construction: uniformly mixing the mixed solution with a filler for constructing a Permeable Reactive Barrier (PRB), heating and insulating the mixture, filling the mixture into a trench through which dug underground water flows, and covering clay for protection to construct the permeable reactive barrier;
repairing: for Permeable Reactive Barrier (PRB) which fails for a long time, the mixed solution is injected into the Permeable Reactive Barrier (PRB), and the water inlet end and the water outlet end of the Permeable Reactive Barrier (PRB) are plugged by a water baffle plate, so that the solution is prevented from losing; and heating and insulating the Permeable Reactive Barrier (PRB), and finishing the repair work.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10139926A (en) * | 1996-09-13 | 1998-05-26 | Sumitomo Rubber Ind Ltd | Discoloration inhibitor for deproteinized natural rubber latex, deproteinized natural rubber latex, and method for storing the same |
| CN103521513A (en) * | 2013-10-18 | 2014-01-22 | 中国科学院南京土壤研究所 | Leaching method of soil polluted by hexavalent chromium |
| CN104324938A (en) * | 2014-11-18 | 2015-02-04 | 青岛新天地环境保护有限责任公司 | Horizontal permeable reaction layer for soil remediation and soil remediating method |
| CN106424119A (en) * | 2016-10-28 | 2017-02-22 | 江苏省环境科学研究院 | Repair agent used for treating chromium-contaminated soil and use method of repair agent |
| CN106955888A (en) * | 2017-03-30 | 2017-07-18 | 北京高能时代环境技术股份有限公司 | The stabilization method of waste residue containing Cr, Cr contaminated soils or its combination |
| CN107486468A (en) * | 2017-08-15 | 2017-12-19 | 北京高能时代环境技术股份有限公司 | One kind is used for hexavalent chromium polluted soil heterotopic repairing method of microorganism |
-
2018
- 2018-01-04 CN CN201810007439.5A patent/CN108273837B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10139926A (en) * | 1996-09-13 | 1998-05-26 | Sumitomo Rubber Ind Ltd | Discoloration inhibitor for deproteinized natural rubber latex, deproteinized natural rubber latex, and method for storing the same |
| CN103521513A (en) * | 2013-10-18 | 2014-01-22 | 中国科学院南京土壤研究所 | Leaching method of soil polluted by hexavalent chromium |
| CN104324938A (en) * | 2014-11-18 | 2015-02-04 | 青岛新天地环境保护有限责任公司 | Horizontal permeable reaction layer for soil remediation and soil remediating method |
| CN106424119A (en) * | 2016-10-28 | 2017-02-22 | 江苏省环境科学研究院 | Repair agent used for treating chromium-contaminated soil and use method of repair agent |
| CN106955888A (en) * | 2017-03-30 | 2017-07-18 | 北京高能时代环境技术股份有限公司 | The stabilization method of waste residue containing Cr, Cr contaminated soils or its combination |
| CN107486468A (en) * | 2017-08-15 | 2017-12-19 | 北京高能时代环境技术股份有限公司 | One kind is used for hexavalent chromium polluted soil heterotopic repairing method of microorganism |
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