CN104070060A - Repair method of chromium-contaminated soil - Google Patents
Repair method of chromium-contaminated soil Download PDFInfo
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- CN104070060A CN104070060A CN201410278439.0A CN201410278439A CN104070060A CN 104070060 A CN104070060 A CN 104070060A CN 201410278439 A CN201410278439 A CN 201410278439A CN 104070060 A CN104070060 A CN 104070060A
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Abstract
The invention discloses a repair method of chromium-contaminated soil, which belongs to the technical field of environment engineering. The method comprises the following steps: reducing hexavalent chromium in the chromium-contaminated soil, removing trivalent chromium and performing sewage treatment. Ferrous sulfate is added into the chromium-contaminated soil, and the reaction environment is adjusted, so that the efficiency for reducing the hexavalent chromium in the chromium-contaminated soil into the trivalent chromium is improved, and conditions are provided for removing chromium; chromium in the soil is extracted by adopting disodium ethylenediamine tetraacetate, the removal rate of the chromium in the soil is increased by adopting microwave heating, and the reaction time is shortened; sodium sulphide is added into chromium sewage, and the reaction environment is adjusted, so that the settling efficiency of heavy metals in the sewage is improved; and additionally, the sewage is converted into disodium ethylenediamine tetraacetate solution, so that resource recovery and utilization are realized. According to the method, the hexavalent chromium is converted into the trivalent chromium to be treated, so that the environmental risk in the repair process is reduced; the chromium-contaminated soil is converted into chromium sewage for treatment, so that the treatment efficiency is improved, and the treatment effect is guaranteed; and the method has the characteristics of no secondary pollution, high efficiency, rapidity, high resource utilization rate and the like.
Description
Technical field
The invention discloses a kind of pollution of chromium soil restorative procedure, belong to field of environment engineering technology.
Background technology
At present, China is subject to nearly 2,000 ten thousand hectares of the cultivated area of the heavy metal pollutions such as chromium, it is estimated, the whole nation is annual because the grain of soil pollution reaches 1,200 ten thousand tons, and the direct economic loss causing exceedes 20,000,000,000 yuan.Along with the quickening of urbanization, process of industrialization, increasing soil suffers heavy metal pollution, and Urban strategy layout is readjusted, and a large amount of heavy metals is left over place urgent need and administered.Heavy metal pollution of soil has disguise, hysteresis quality and chronicity, is difficult to repair.Heavy metal can enter human body and harm humans is healthy by food chain, respiratory system and skin etc.; Meanwhile, heavy metal also can move and be exposed in underground water and atmosphere, destroys ecological environment.Heavy metal pollution soil must can develop again through repair process, due to " poison ground " the constantly exposure utilizing without reparation, country payes attention to the improvement of land pollution further, the appearance of " 12 " first ad hoc planning, indicates that China will go into overdrive to administer heavy metal pollution soil.
According to national Soil Pollution Investigation communique, pollution of chromium point position exceeding standard rate reaches 1.1%.The chromium of occurring in nature mainly occurs with trivalent and sexavalence simultaneously, trivalent chromium is a kind of trace element of needed by human, water-soluble Cr VI is listed in one of 8 of harm maximum kinds of chemical substances, Cr VI toxicity is generally more than 100 times of trivalent chromium toxicity, be one of internationally recognized 3 kinds of carcinogenic metal objects, be also one of 129 kinds of generally acknowledged priority pollutants of U.S. EPA simultaneously.Chromium is that to the mankind's threat it can not be decomposed by microorganism, can pass through food chain enrichment in vivo.
At present, mainly comprise microorganism removal method (China Patent Publication No. CN201210355258.4 for the recovery technique of pollution of chromium soil, open day on September 21st, 2012, denomination of invention " a kind of repairing method of microorganism of basic chromium contaminated soil "), chemical method (medicament washing, thermal decomposition etc.) (China Patent Publication No. CN201310493630.2, open day on October 18th, 2013, denomination of invention " ELUTION METHOD of hexavalent chromium polluted soil "), Physical (electrical method, solidification and stabilization etc.) (China Patent Publication No. CN201110360190.4, open day on November 15th, 2011, denomination of invention " nano zero valence iron-electromagnetism rake renovation of heavy metal polluted soil with combined/mud technique ") and plant extract (China Patent Publication No. CN200910173646.9, open day on September 8th, 2009, denomination of invention " nano zero valence iron-electromagnetism rake renovation of heavy metal polluted soil with combined/mud technique "), a large amount of methods is also in the laboratory research stage, scene is difficult to carry out, simultaneously, existing pollution of chromium soil treatment technology technique is relatively backward, cause pollution of chromium soil remediation efficiency low, cost is high, secondary pollution and environmental risk are large.
Summary of the invention
For above-mentioned existing problems, the object of the present invention is to provide that a kind of remediation efficiency is high, treatment effect good, non-secondary pollution and the high pollution of chromium soil restorative procedure of recycling rate.
To achieve these goals, its technical solution is:
A kind of pollution of chromium soil restorative procedure, carries out according to following steps:
1 one kinds of pollution of chromium soil restorative procedures, is characterized in that: described restorative procedure carries out according to following steps:
A) determine total chromium, Cr VI and chromic concentration in pollution of chromium soil, and calculate total chromium, Cr VI and chromic content in pollution of chromium soil;
B) by pollution of chromium soil with water in mass ratio for 1/5-1/10 mixes, formation mud;
C) in the mud forming through step B, add NaOH or hydrochloric acid, regulating the pH value of mud is 7-9;
D) in the mud after step C regulates pH value, add ferrous sulfate, in ferrous sulfate and pollution of chromium soil, chromic mol ratio is 3:1, uniform stirring mud 10-20 minute;
E) in the mud after step D stirs, add disodium ethylene diamine tetraacetate, in disodium ethylene diamine tetraacetate and pollution of chromium soil, the mol ratio of total chromium is 3:2, mixes and is placed in high-temperature resistant container;
F) high-temperature resistant container through step e is placed in to micro-wave oven, adjusting microwave power is 500w-900w, keeps 30 seconds-1 minute, by quick the chromium ion that is adsorbed in pollution of chromium soil particle surface, fully desorb;
G) take out high-temperature resistant container, cooling after, mud that will be after desorb imports in centrifuge and carries out Separation of Solid and Liquid, the solid obtaining is clean soil after treatment, collects the sewage after Separation of Solid and Liquid;
H) in the sewage of collecting through step G, add NaOH or hydrochloric acid, adjusting pH value of sewage water is 8-10;
I) to add vulcanized sodium in step H sewage after treatment, in vulcanized sodium and sewage, the mol ratio of ethylenediamine tetra-acetic acid is 1:1, stirs after 3 minutes and leaves standstill 10 minutes;
J) will filter through step I sewage after treatment.
Described water is the one of running water or river.
Described high-temperature resistant container is made up of PET resin or polyester material.
Owing to having adopted above technical scheme, a kind of pollution of chromium soil restorative procedure of the present invention, adopt ferrous sulfate as reducing agent, adjusting reaction environment is alkalescent, improve hexavalent chrome reduction in pollution of chromium soil and become chromic efficiency, for the removal of chromium provides condition, simultaneously, Cr VI in Polluted Soil is converted into trivalent chromium to be processed, reduce the environmental risk in repair process, adopt disodium ethylene diamine tetraacetate to extract the chromium in soil, high-efficiency environment friendly, improved the clearance of Chromium in Soil by heating using microwave, shorten the reaction time, soil after centrifugal treating is clean soil, in the chromium sewage after centrifugal, add vulcanized sodium, and regulator solution is alkalescence, improve the deposition efficiency of Chromium in Sewage, chromium has been realized recovery, sewage is converted into disodium ethylene diamine tetra-acetic acid solution simultaneously, realize resource secondary utilization, save pollution of chromium soil processing cost.Chromium-polluted soil is converted into chromium sewage disposal by the method, improved treatment effeciency, ensured treatment effect, has non-secondary pollution, efficient quick and resource utilization high.
Detailed description of the invention
A kind of pollution of chromium soil restorative procedure, described method is carried out according to following steps:
A) determine total chromium, Cr VI and chromic concentration in pollution of chromium soil, and calculate total chromium, Cr VI and chromic content in pollution of chromium soil.
B) by pollution of chromium soil with water in mass ratio for 1/5-1/10 mixes, formation mud, water be running water or with water in one.
C) in the mud forming through step B, add NaOH or hydrochloric acid, regulating the pH value of mud is 7-9, for chromic reduction in soil provides alkaline environment.
D) in the mud after step C regulates pH value, add ferrous sulfate, in ferrous sulfate and pollution of chromium soil, chromic mol ratio is 3:1, uniform stirring mud 10-20 minute, in contaminated soil, Cr VI is converted into hypotoxic trivalent chromium under the effect of reducing agent ferrous sulfate, on the one hand, easily and disodium ethylene diamine tetraacetate generation complex reaction and being removed, on the other hand, hypotoxic trivalent chromium has reduced the environmental risk in the native processing procedure of pollution of chromium to chromic chemical combination ion.
E) in the mud after step D stirs, add disodium ethylene diamine tetraacetate, in disodium ethylene diamine tetraacetate and pollution of chromium soil, the mol ratio of total chromium is 3:2, mix and be placed in high-temperature resistant container, disodium ethylene diamine tetraacetate can form soluble chelating thing with the trivalent chromium in Polluted Soil by ion exchange and be dissolved in solution, realize the removal of chromium in pollution of chromium soil, in disodium ethylene diamine tetraacetate and pollution of chromium soil, the mol ratio of chromium is 3:2, mix and be placed in high-temperature resistant container, high-temperature resistant container is made up of PET resin or polyester material, can high temperature resistantly reach 200 DEG C, guarantee the security of heating process.
F) high-temperature resistant container is placed in to micro-wave oven, adjusting microwave power is 500w-900w, keep 30 seconds-1 minute, by quick the chromium ion that is adsorbed in pollution of chromium soil particle surface, fully desorb, microwave on the one hand can spoiled soil structure, increase the stripping of chromium, improve on the one hand the reaction speed of chromium and disodium ethylene diamine tetraacetate by Fast Heating.
G) take out high-temperature resistant container, cooling after, mud that will be after desorb imports in centrifuge and carries out Separation of Solid and Liquid, the solid obtaining is clean soil after treatment, collect the sewage after Separation of Solid and Liquid, centrifugation has improved efficiency, and the solid obtaining is clean soil after treatment.
H) in the sewage of collecting through step G, add NaOH or hydrochloric acid, adjusting pH value of sewage water is 8-10;
I) to add vulcanized sodium in step H sewage after treatment, employing adds vulcanized sodium to generate the method for sulfide precipitation, can remove Chromium in Sewage, simultaneously, chromium sewage solution is converted into disodium ethylene diamine tetra-acetic acid solution, recoverable, in vulcanized sodium and sewage, the mol ratio of ethylenediamine tetra-acetic acid is 1:1, stirs after 3 minutes and leaves standstill 10 minutes.
J) will filter through step I sewage after treatment, in filter residue, contain the chromium of high-load, recoverable, filtrate is disodium ethylene diamine tetra-acetic acid solution, also recoverable.
case study on implementation
Describe in further detail below in conjunction with relevant case study on implementation:
case study on implementation 1
Obtaining total chromium, Cr VI and chromic concentration in pollution of chromium soil by chemical analysis is respectively: 3547mg/kg, 1213mg/kg, 2334mg/kg, calculate total chromium, Cr VI and trivalent chromium content in 100kg pollution of chromium soil and be respectively 354.7g, 121.3g, 233.4g, 6.82,2.33,4.48 moles.In 100kg pollution of chromium soil, add running water 500kg, after stirring, form mud, in mud, add NaOH, making mud pH value is 7, add wherein again ferrous sulfate, in ferrous sulfate and pollution of chromium soil, chromic mol ratio is 3:1, after uniform stirring mud 10 minutes, add disodium ethylene diamine tetraacetate, in disodium ethylene diamine tetraacetate and pollution of chromium soil, the mol ratio of total chromium is 3:2, mix and be placed in PET resin plastic magazine, plastic casing is placed in to micro-wave oven, adjusting microwave power is 500w, keep 1 minute, take out plastic casing, after cooling, mud is imported and in centrifuge, carries out Separation of Solid and Liquid, the solid obtaining is clean soil after treatment, after testing, reach our soil environment quality primary standard.In the chromium sewage after centrifugal, add NaOH, regulating pH value of sewage water is 8, adds wherein vulcanized sodium, in vulcanized sodium and sewage, the mol ratio of ethylenediamine tetra-acetic acid is 1:1, stir after 3 minutes and leave standstill 10 minutes, sewage is filtered, filter residue and filtrate are recycled respectively.
case study on implementation 2
Obtaining total chromium, Cr VI and chromic concentration in pollution of chromium soil by chemical analysis is respectively: 3547mg/kg, 1213mg/kg, 2334mg/kg, calculate total chromium, Cr VI and trivalent chromium content in 100kg pollution of chromium soil and be respectively 354.7g, 121.3g, 233.4g, 6.82,2.33,4.48 moles.In 100kg pollution of chromium soil, add river 800kg, after stirring, form mud, in mud, add hydrochloric acid, making mud pH value is 8, add wherein again ferrous sulfate, in ferrous sulfate and pollution of chromium soil, chromic mol ratio is 3:1, after uniform stirring mud 15 minutes, add disodium ethylene diamine tetraacetate, in disodium ethylene diamine tetraacetate and pollution of chromium soil, the mol ratio of total chromium is 3:2, mix and be placed in polyester plastics box, plastic casing is placed in to micro-wave oven, adjusting microwave power is 700w, keep 45 seconds, take out plastic casing, after cooling, mud is imported and in centrifuge, carries out Separation of Solid and Liquid, the solid obtaining is clean soil after treatment, after testing, reach our soil environment quality primary standard.In the chromium sewage after centrifugal, add NaOH, regulating pH value of sewage water is 9, adds wherein vulcanized sodium, in vulcanized sodium and sewage, the mol ratio of ethylenediamine tetra-acetic acid is 1:1, stir after 3 minutes and leave standstill 10 minutes, sewage is filtered, filter residue and filtrate are recycled respectively.
case study on implementation 3
Obtaining total chromium, Cr VI and chromic concentration in pollution of chromium soil by chemical analysis is respectively: 3547mg/kg, 1213mg/kg, 2334mg/kg, calculate total chromium, Cr VI and trivalent chromium content in 100kg pollution of chromium soil and be respectively 354.7g, 121.3g, 233.4g, 6.82,2.33,4.48 moles.In 100kg pollution of chromium soil, add running water 1000kg, after stirring, form mud, in mud, add NaOH, making mud pH value is 9, add wherein again ferrous sulfate, in ferrous sulfate and pollution of chromium soil, chromic mol ratio is 3:1, after uniform stirring mud 20 minutes, add disodium ethylene diamine tetraacetate, in disodium ethylene diamine tetraacetate and pollution of chromium soil, the mol ratio of total chromium is 3:2, mix and be placed in PET resin plastic magazine, plastic casing is placed in to micro-wave oven, adjusting microwave power is 900w, keep 30 seconds, take out plastic casing, after cooling, mud is imported and in centrifuge, carries out Separation of Solid and Liquid, the solid obtaining is clean soil after treatment, after testing, reach our soil environment quality primary standard.In the chromium sewage after centrifugal, add NaOH, regulating pH value of sewage water is 10, adds wherein vulcanized sodium, in vulcanized sodium and sewage, the mol ratio of ethylenediamine tetra-acetic acid is 1:1, stir after 3 minutes and leave standstill 10 minutes, sewage is filtered, filter residue and filtrate are recycled respectively.
Claims (3)
1. a pollution of chromium soil restorative procedure, is characterized in that: described restorative procedure carries out according to following steps:
A) determine total chromium, Cr VI and chromic concentration in pollution of chromium soil, and calculate total chromium, Cr VI and chromic content in pollution of chromium soil;
B) by pollution of chromium soil with water in mass ratio for 1/5-1/10 mixes, formation mud;
C) in the mud forming through step B, add NaOH or hydrochloric acid, regulating the pH value of mud is 7-9;
D) in the mud after step C regulates pH value, add ferrous sulfate, in ferrous sulfate and pollution of chromium soil, chromic mol ratio is 3:1, uniform stirring mud 10-20 minute;
E) in the mud after step D stirs, add disodium ethylene diamine tetraacetate, in disodium ethylene diamine tetraacetate and pollution of chromium soil, the mol ratio of total chromium is 3:2, mixes and is placed in high-temperature resistant container;
F) high-temperature resistant container is placed in to micro-wave oven, adjusting microwave power is 500w-900w, keeps 30 seconds-1 minute, by quick the chromium ion that is adsorbed in pollution of chromium soil particle surface, fully desorb;
G) take out high-temperature resistant container, cooling after, mud that will be after desorb imports in centrifuge and carries out Separation of Solid and Liquid, the solid obtaining is clean soil after treatment, collects the sewage after Separation of Solid and Liquid;
H) in the sewage of collecting through step G, add NaOH or hydrochloric acid, adjusting pH value of sewage water is 8-10;
I) to add vulcanized sodium in step H sewage after treatment, in vulcanized sodium and sewage, the mol ratio of ethylenediamine tetra-acetic acid is 1:1, stirs after 3 minutes and leaves standstill 10 minutes;
J) will filter through step I sewage after treatment.
2. a kind of pollution of chromium soil restorative procedure as claimed in claim 1, is characterized in that: described water is the one of running water or river.
3. a kind of pollution of chromium soil restorative procedure as claimed in claim 1, is characterized in that: described high-temperature resistant container is made up of PET resin or polyester material.
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Cited By (12)
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| CN104438312A (en) * | 2014-11-14 | 2015-03-25 | 华中科技大学 | Restoration method of severely combined pollution site |
| CN104610973A (en) * | 2014-12-11 | 2015-05-13 | 桑德环境资源股份有限公司 | Chromium-polluted soil restoration leaching agent and chromium-polluted soil restoration method |
| CN105127190A (en) * | 2015-08-11 | 2015-12-09 | 青海省环境科学研究设计院 | Method for repairing hexavalent chromium in chromium polluted soil |
| CN105149334A (en) * | 2015-10-12 | 2015-12-16 | 山东师范大学 | Oxidation-chelation leaching combined remediation method for Cr-contaminated soil |
| CN105349152A (en) * | 2015-12-18 | 2016-02-24 | 南京大学 | Passivator for alkaline soil and application of passivator |
| CN105499262A (en) * | 2016-01-22 | 2016-04-20 | 户园凌 | Alkaline chromium-contaminated soil solidifying, stabilizing and repairing method |
| CN105542775A (en) * | 2015-12-18 | 2016-05-04 | 南京大学 | Passivating agent for weakly acidic cadmium contaminated soil and application thereof |
| CN106335940A (en) * | 2016-09-28 | 2017-01-18 | 江苏华兴电气科技有限公司 | Mechanical filter for filtering industrial sewage |
| CN109940038A (en) * | 2019-04-09 | 2019-06-28 | 河北科技大学 | A kind of organic matter and hexavalent chromium combined contamination soil repair reactor and its restorative procedure |
| CN111659726A (en) * | 2020-06-29 | 2020-09-15 | 西南大学 | Ectopic remediation method for chromium-contaminated soil |
| CN112958606A (en) * | 2021-02-03 | 2021-06-15 | 中环国投(重庆)环保产业开发有限公司 | Remediation method for organic contaminated soil |
| CN113617822A (en) * | 2021-08-24 | 2021-11-09 | 江苏省环境科学研究院 | Heavy metal polluted foundation soil restoration and safe recycling method |
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| CN104438312A (en) * | 2014-11-14 | 2015-03-25 | 华中科技大学 | Restoration method of severely combined pollution site |
| CN104610973A (en) * | 2014-12-11 | 2015-05-13 | 桑德环境资源股份有限公司 | Chromium-polluted soil restoration leaching agent and chromium-polluted soil restoration method |
| CN104610973B (en) * | 2014-12-11 | 2018-10-09 | 桑德环境资源股份有限公司 | Repair the eluent and method of chromium-polluted soil |
| CN105127190A (en) * | 2015-08-11 | 2015-12-09 | 青海省环境科学研究设计院 | Method for repairing hexavalent chromium in chromium polluted soil |
| CN105149334B (en) * | 2015-10-12 | 2018-05-04 | 山东师范大学 | A kind of oxidation of chromium-polluted soil-chelating elution combined remediation method |
| CN105149334A (en) * | 2015-10-12 | 2015-12-16 | 山东师范大学 | Oxidation-chelation leaching combined remediation method for Cr-contaminated soil |
| CN105349152A (en) * | 2015-12-18 | 2016-02-24 | 南京大学 | Passivator for alkaline soil and application of passivator |
| CN105542775A (en) * | 2015-12-18 | 2016-05-04 | 南京大学 | Passivating agent for weakly acidic cadmium contaminated soil and application thereof |
| CN105542775B (en) * | 2015-12-18 | 2019-02-22 | 南京大学 | A kind of passivator and its application for faintly acid cadmium pollution soil |
| CN105499262B (en) * | 2016-01-22 | 2018-08-31 | 户园凌 | A kind of basic chromium Polluted Soil consolidates steady restorative procedure |
| CN105499262A (en) * | 2016-01-22 | 2016-04-20 | 户园凌 | Alkaline chromium-contaminated soil solidifying, stabilizing and repairing method |
| CN106335940A (en) * | 2016-09-28 | 2017-01-18 | 江苏华兴电气科技有限公司 | Mechanical filter for filtering industrial sewage |
| CN109940038A (en) * | 2019-04-09 | 2019-06-28 | 河北科技大学 | A kind of organic matter and hexavalent chromium combined contamination soil repair reactor and its restorative procedure |
| CN111659726A (en) * | 2020-06-29 | 2020-09-15 | 西南大学 | Ectopic remediation method for chromium-contaminated soil |
| CN112958606A (en) * | 2021-02-03 | 2021-06-15 | 中环国投(重庆)环保产业开发有限公司 | Remediation method for organic contaminated soil |
| CN113617822A (en) * | 2021-08-24 | 2021-11-09 | 江苏省环境科学研究院 | Heavy metal polluted foundation soil restoration and safe recycling method |
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