CN104841693A - Hexavalent chromium contaminated soil in-situ remediation method - Google Patents
Hexavalent chromium contaminated soil in-situ remediation method Download PDFInfo
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Abstract
The invention discloses a hexavalent chromium contaminated soil in-situ remediation method. The method comprises the following steps: dissolving a water-soluble sulfur-containing reagent into water, preparing 0.1-10 percent of a reducing agent, mixing chromium contaminated soil and the reducing agent in a reactor according to a mass ratio of the soil to the reducing agent being 3:1-1:5, stirring for 0.5-2 hours, and drying. Then, a stabilizer is added for treatment, so that the soil meets the environmental risk control requirement. The hexavalent chromium which is high in toxicity and easy to migrate and can be absorbed and utilized by plants in the soil is completely reduced and immobilized into trivalent chromium which is low in toxicity and difficult to migrate and can be utilized by plants, and bounce is difficultly caused. The in-situ remediation of the heavy metal hexavalent chromium contaminated soil is realized.
Description
Technical field
The present invention relates to a kind of hexavalent chromium polluted soil in-situ recovery technique, specifically, by water-soluble sulfur-bearing regent being configured to reducing agent, water-soluble phosphorus reagent being configured to stabilizing agent, by large for soil poisoning, can the hexavalent chrome reduction that absorbs by plant and utilize fix, realize the in-situ immobilization of hexavalent chromium polluted soil.
Background technology
China's heavy metal pollution of soil is serious." national Soil Pollution Investigation publication " shows, and national pollution of chromium exceeding standard rate is 1.1%, is one of eight kinds of main polluted heavy metals.The source of Chromium in Soil has a variety of, wherein endangers the most serious to mainly contain three aspects: 1) the random stacking of industrial waste and municipal refuse.It is reported, reform and opening-up is over 30 years, the chromium slag that China accumulates because of metallurgical and Chemical Manufacture is up to 6,000,000 tons, and increase with the output of annual 20 – 300,000 tons, the chromic wastes disposal facility that many factories have lacked, stack everywhere, cause leaching containing the Cr VI in chromium refuse, and pollute surrounding soil further.2) sewage irrigation and mud use, and sewage irrigation causes many irrigating region rice terrace water chromium concns to exceed standard.3) in agricultural tilling, the unreasonable fertilizer and agricultural chemicals etc. used containing chromium is also the hexavalent chromium polluted main cause of soil.
Cr VI is decided to be the mankind by international cancer research institution and determines carcinogenic substance, and ion concentration will be poisoning more than 0.1mg/L.Chromium to the toxic action of human body with variation of valence: large 100 times of chromic toxicity ratio trivalent chromium.Hexavalent chromium compound can be entered rapidly in cell by nonspecific anion channel on easyization diffusion and cell membrane, and trivalent chromium is more difficult permeate through cell membranes then.Therefore the toxicity of chromium is mainly manifested on hexavalent chromium compound.
The control of heavy metal pollution of soil and reparation problem have caused the extensive concern of governments at all levels and environmental worker.At present, hexavalent chromium polluted soil restoring technology mainly comprises following several:
(1) soil moved in improve the original method.Exactly contaminated soil is carried out digging, soil removal and replacement etc., by contaminated soil is buried, change fresh soil, thus reach the object alleviating harm.Repair one mu of contaminated land in this way and will spend unit up to a million, and contaminated soil still exists.In addition, the contaminated soil being buried in underground reducing environment excavates out and is exposed in air by soil moved in improve the original method, add trivalent chromium be oxidized to chromic may, staff is sucked and the exposure hazard be infected with increases.But because restorative procedure is simple, spended time is few, and this method of drinking poison to quench thirst is widely used at present.
(2) phytoremediation.Be there is by plantation heavy metal the plant of super accumulating capability, thus by the landfill in soil out.Research shows, Leersia Sw has good patience and purification function to Cr VI, and route is fluffy has well weakening and purification function to hexavalent chromium polluted.Leaf mustard surpasses to Cr VI that accumulation ability is maximum can reach 4100mg/kg.In addition, half Karma chrysanthemum and Paspalum distichum etc. also can purify the Cr VI in soil effectively.Usually, the time of phytoremediation at least needs more than 5 years, means that the time of falling into disuse of soil is at least 5 years, has influence on the production of grain and the income of peasant.In addition, the cost of phytoremediation is higher, and soil per ton reaches about 200 yuan, and the rehabilitation expense of every mu of soil is up to 8 ~ 100,000 yuan, and the rehabilitation cost of per hectare soil reaches 1.2 ~ 1.5 hundred million yuans.Local government and peasant are unaffordable.And, the super enriching plant of current discovery is all generally wild plant, there is larger technical difficulty in its seedling breeding, realize extensive seedling just more difficult, so use first booth breeding to be transplanted to the way of repairing district more now, this can increase rehabilitation cost and operation easier undoubtedly further.
(3) chemical leaching method.Adopt chemical agent as surfactant, mordant, complexing agent etc. the chromium in soil is leached out after carry out wastewater treatment again.This method not only cost is very high, far above phytoremediation, and brings into soil such as new pollutant such as surfactant, mordant etc., becomes new pollution sources.The physical arrangement of soil can be greatly affected.In addition, due to the chemical property that trivalent chromium is contrary with Cr VI, both are difficult to remove simultaneously; The while of removing chromic, the trivalent chromium in soil is activated, and is easily oxidized to Cr VI by series of biochemical reactions, cures the symptoms, not the disease.
(4) microorganism elution method.By adding microorganism species chromium to enrichment in soil, chromium is washed out.This mode not only cost is high, because microorganism leacheate is difficult to collect for large-area soil pollution, is in fact difficult to operation.
(5) electrochemical process.In soil, make water soluble hexavalent chromium ion enrichment to anode surface by the function of current, trivalent chromic ion is enriched to cathode surface.Remove the conditions such as the pH of Cr VI and trivalent chromium needs contrary, be difficult to reach and remove object simultaneously.In addition, this technology is also just groped in laboratory at present.Because function of current distance is too little, and actual contaminated land area is too large, and this technology is difficult to carry out in engineering, and no matter its high running cost is difficult to bear.
(6) chemical reduction method.Large 100 times of chromic toxicity ratio trivalent chromium, and be easily absorbed and used by plants, thus be accumulated in human body by food chain.By adding ferrous salt in contaminated soil, the reducing substances such as sulfide or organic matter makes water miscible hexavalent chromium be converted into the chromium hydroxide of trivalent and reduce its biologically active.But under the effect such as microorganism and acid rain, and when soil pH changes, chromium hydroxide easily changes solvable trivalent chromic ion into, thus is again oxidized to Cr VI by the manganese in soil, recovers toxicity.Therefore, simple electronation and add alkali solidification just cover hexavalent chromium polluted problem temporarily, momently.
In sum, how to develop practicable hexavalent chromium polluted soil restoring technology and become the bottleneck problem that the hexavalent chromium polluted control of following soil faces.
Summary of the invention
The technical issues that need to address of the present invention are just the defect overcoming prior art, a kind of hexavalent chromium polluted soil in-situ restorative procedure is provided, by in soil can the Cr VI that absorbs by plant and utilize through reduction be fixedly converted into the stable trivalent chromium of low toxicity, realize the in-situ immobilization of hexavalent chromium polluted soil.
For solving the problem, the present invention adopts following technical scheme:
Water-soluble sulfur-bearing regent is dissolved in the water, is mixed with the solution that mass concentration is 0.1 ~ 10%, obtains the reducing agent that hexavalent chromium polluted soil remediation is used; Water-soluble phosphorus reagent is dissolved in the water, is mixed with the solution that mass concentration is 0.1 ~ 10%, obtains the stabilizing agent that hexavalent chromium polluted soil remediation is used.According to soil: hexavalent chromium polluted soil mixes in reactor with reducing agent by reducing agent=3:1 ~ 1:5, stir 0.5 ~ 2 hour after dry process.After this, according to soil: stabilizing agent=3:1 ~ 1:5 by reduction after soil mix in reactor with stabilizing agent, stir 0.5 ~ 2 hour after drying process.Now soil is the stabilisation soil after removing Cr VI.
The present invention compared with prior art, has following feature:
(1) the present invention by the stable method of reduction by soil can the hexavalent chrome reduction that absorbs by plant and utilize be trivalent chromium, purification efficiency is up to 98%.
(2) trivalent chromium that the present invention generates is stablized, not affected by environment, is not easy again to change Cr VI into and produces secondary pollution.
(3) the present invention adopt reducing agent and stabilizing agent cheaper starting materials, be easy to get, and method of operating is simple, easy.
Detailed description of the invention
Enumerate 1 embodiment below, the present invention is further illustrated, but the present invention is not only limited to these embodiments.
Embodiment 1
Embodiment for object be certain chemical plant chromium slag leachate contaminated soil.Chromium in Soil content is content of 6-valence Cr ions is 5628.9mg/kg.Utilize the inventive method repairing hexavalent chromium polluted soil key step as follows:
1) 10 kilograms of sodium thiosulfate are dissolved in 90 kg of water, are configured to the reducing agent that mass concentration is 10%.
2) sodium hydrogen phosphate 10 kilograms is dissolved in 90 kg of water, is configured to the stabilizing agent that mass concentration is 10%.
3) 100 kilograms of hexavalent chromium polluted soil and 50 kilograms of reducing agents are fully uniformly mixed, mixing time 2 hours, the soil obtained carries out drying process;
4) by 100 kilograms through reduction treatment and dried soil and 50 kilograms of stabilizing agents be fully uniformly mixed, mixing time 2 hours, the soil obtained carry out drying process.
After completing above-mentioned steps, in soil, hexavalent chromium concentration is reduced to 1.5ppm by preprosthetic 350ppm, and in soil, Cr VI Leaching concentration is reduced to the detection limit (0.1ppm) of instrument below by 128ppm.
Embodiment 2
Embodiment for object be certain hexavalent chromium polluted soil.Chromium in Soil content is content of 6-valence Cr ions is 526.3mg/kg.Utilize the inventive method repairing hexavalent chromium polluted soil key step as follows:
1) 1 kilogram of vulcanized sodium is dissolved in 90 kg of water, is configured to the reducing agent that mass concentration is 0.1%.
2) phosphatase 11 kilogram is dissolved in 99 kg of water, is configured to the stabilizing agent that mass concentration is 0.1%.
3) 100 kilograms of hexavalent chromium polluted soil and 200 kilograms of reducing agents are fully uniformly mixed, mixing time 2 hours, the soil obtained carries out drying process;
4) by 100 kilograms through reduction treatment and dried soil and 300 kilograms of stabilizing agents be fully uniformly mixed, mixing time 2 hours, the soil obtained carry out drying process.
After completing above-mentioned steps, in soil, hexavalent chromium concentration is reduced to 1.3ppm by preprosthetic 86ppm, and in soil, Cr VI Leaching concentration is reduced to the detection limit (0.1ppm) of instrument below by 16.5ppm.
Embodiment 3
Embodiment for object be certain hexavalent chromium polluted soil.Chromium in Soil content is content of 6-valence Cr ions is 2572.4mg/kg.Utilize the inventive method repairing hexavalent chromium polluted soil key step as follows:
1) 5 kilograms of sodium thiosulfate and 5 kilograms of ferrous sulfites are dissolved in 90 kg of water, are configured to the reducing agent that mass concentration is 10%.
2) 5 kg of phosphoric acid sodium and 5 kg of phosphoric acid disodium hydrogens are dissolved in 190 kg of water, are configured to the stabilizing agent that mass concentration is 5%.
3) 100 kilograms of hexavalent chromium polluted soil and 50 kilograms of reducing agents are fully uniformly mixed, mixing time 2 hours, the soil obtained carries out drying process;
4) by 100 kilograms through reduction treatment and dried soil and 50 kilograms of stabilizing agents be fully uniformly mixed, mixing time 2 hours, the soil obtained carry out drying process.
After completing above-mentioned steps, in soil, hexavalent chromium concentration is reduced to 1.1ppm by preprosthetic 225ppm, and in soil, Cr VI Leaching concentration is reduced to the detection limit (0.1ppm) of instrument below by 106ppm.
Claims (6)
1. a hexavalent chromium polluted soil in-situ restorative procedure, is characterized in that, makes use sulfur-bearing regent and water-based phosphorus reagent complete in-situ immobilization to hexavalent chromium polluted soil.
2. the method for claim 1, comprises the following steps:
1), the preparation of reducing agent: water-soluble sulfur-bearing regent is dissolved in the water, is mixed with the solution that mass concentration is 0.1 ~ 10%, obtains the reducing agent that hexavalent chromium polluted soil remediation is used;
2), the preparation of stabilizing agent: water-soluble phosphorus reagent is dissolved in the water, is mixed with the solution that mass concentration is 0.1 ~ 10%, obtains the stabilizing agent that hexavalent chromium polluted soil remediation is used;
3), the reduction of hexavalent chromium polluted soil is fixed: according to soil: hexavalent chromium polluted soil mixes in reactor with reducing agent by the ratio of reducing agent=3:1 ~ 1:5, stir 0.5 ~ 2 hour after dry process; After this, according to soil: the soil after reduction mixes with stabilizing agent, stirs 0.5 ~ 2 hour by the ratio of stabilizing agent=3:1 ~ 1:5 in reactor, dry process;
4) the stabilisation soil after removing Cr VI is obtained.
3. hexavalent chromium polluted soil in-situ restorative procedure as claimed in claim 1, is characterized in that: described water-soluble sulfur-bearing regent is one or more in water miscible sulfide, polysulfide, sulphite, thiosulfate, dithionite, pyrosulfite and tetrathionate.
4. hexavalent chromium polluted soil in-situ restorative procedure as claimed in claim 1, is characterized in that: described water-soluble phosphorus reagent is one or more in phosphoric acid and water miscible phosphate, phosphite and pyrophosphate.
5. water-soluble sulfur-bearing regent as claimed in claim 3, is characterized in that: described water-soluble sulfide is potassium sulfide, vulcanized sodium, ammonium sulfide, NaHS and potassium bisulfide; Described water-soluble polysulfide is sodium polysulfide, potassium polysulfide and calcium polysulfide; Described water-soluble sulfite is sodium sulfite, potassium sulfite, ammonium sulfite, ferrous sulfite, sodium hydrogensulfite and potassium bisulfite; Described water-soluble thiosulfate is sodium thiosulfate, potassium thiosulfate and ATS (Ammonium thiosulphate); Described water-soluble dithionite are sodium dithionite, potassium hyposulfite and ammonium hyposulfite; Described water-soluble pyrosulfite is sodium pyrosulfite, potassium metabisulfite and ammonium pyrosulfite; Water-soluble tetrathionate is sodium tetrathionate, potassium tetrathionate and tetrathionic acid ammonium.
6. water-soluble phosphorus reagent as claimed in claim 4, is characterized in that: water-soluble phosphate is potassium dihydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium hydrogen phosphate, potassium phosphate and sodium phosphate; Water soluble phosphite is potassium phosphite and sodium phosphite; Water-soluble pyrophosphate is potassium pyrophosphate, sodium pyrophosphate.
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| CN105750323A (en) * | 2016-05-18 | 2016-07-13 | 山东省农业科学院农业资源与环境研究所 | Farmland chromium pollution remediation method under planting production condition |
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| CN105964679A (en) * | 2016-07-28 | 2016-09-28 | 云南民族大学 | Method for carbon reduction repair of chromium-contaminated soil with assistance of microwaves |
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| CN111318560A (en) * | 2020-01-17 | 2020-06-23 | 环保桥(湖南)生态环境工程股份有限公司 | Method for reducing leaching toxicity of acid chromium (VI) polluted site through RPSCP process |
| CN113182338A (en) * | 2021-04-25 | 2021-07-30 | 三明学院 | Method for restoring molybdenum-polluted soil by ultrasonic/oscillation-assisted chemical leaching |
| CN113399445A (en) * | 2021-07-14 | 2021-09-17 | 河北科技大学 | Method for efficiently leaching and repairing chromium-contaminated soil |
| CN116174464A (en) * | 2023-03-06 | 2023-05-30 | 核工业北京化工冶金研究院 | Secondary restoration stable solidification method for 'yellowing' chromium-polluted soil |
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