CN104923557A - Cyanide contaminated soil restoring method - Google Patents
Cyanide contaminated soil restoring method Download PDFInfo
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Abstract
The invention discloses a cyanide contaminated soil restoring method. The method is used for processing heavily-contaminated soil with cyanide as the specific pollutant, and meanwhile the contaminated soil contains copper and other heavy metal. In the method, the heavy metal cyano complex, thiocyanate and other reducing substances in the soil are broken through the oxidizability of ozone and hydrogen peroxide. The pH value of the soil can be restored through a pH value restoring agent, finally restoration is conducted through the hydrogen peroxide, and a reaction system tends to be stable while the pollutant is processed; through the restoration of the method, a good restoration effect is achieved for copper and other heavy metal. The soil reaches the B-level standard in Standard of Soil Quality Assessment for Exhibition Sites after being restored and can be used as a class-II soil resource. The method is good in restoration effect of the cyanide heavily-contaminated soil, adopts environment-friendly agents so that no secondary pollution can be caused to the soil, is low in restoration cost, short in restoration cycle and suitable for application and popularization, and has certain environment benefits.
Description
Technical field
The invention belongs to environmental protection and process for comprehensively treating field, relate to soil restoring technology, mainly for the soil of cyanide pollution, relate to a kind of cyanide polluted soil restorative procedure.
Background technology
Advance rapidly in industrialized process in China, the environment that we depend on for existence receives serious destruction, and Soil Environmental Pollution problem is more and more serious, and soil pollution accident emerges in an endless stream.More common pollutant kind has cyanide and heavy metal, and the industrialized regions of other use cyanides such as gold mine and plating exists the contaminated site of larger area, and seriously polluted.And the secondary pollution source become by the soil of cyanide pollution in environment.At present, the technology for soil remediation mainly contains solidification-stabilizing method, phytoremediation technology and technology of Electrodynamics Renovation etc.
Solidification-stabilizing method is the common method of contaminated soil remediation, is to be mixed with certain curing agent by contaminated soil, is fixed by curing agent, makes pollutant environmental transport and transfer no longer towards periphery.But solidification-stabilization method can only be applicable to the soil remediation of slight pollution, for the soil of serious pollution, solidification-stabilization method solidification effect is poor, and cost is high, also can cause secondary pollution.
Electric repairing technique is the electrodynamics according to ion and electrodialysis principle, uses direct current, process soil, this is that the shortcoming of technology exists acidic region exactly, and cyanide easily produces hydrogen cyanide volatilization in acid condition, harm is comparatively large, and cyanide reparation aspect research is less.
Phytoremediation technology have suit measures to local conditions, advantage that soil exempts from disturbance, but phytoremediation excessive cycle, cyanide is as having highly toxic chemical substance, and the soil of serious pollution has a strong impact on plant growth.
Along with the progressively raising of environmental requirement; the reparation demand of cyanide polluted soil is day by day urgent, gold industry and other use the industry of cyanides need badly a kind of simultaneously to cyanide, rhodanate, heavy metal treatment effect is good, non-secondary pollution, processing cost are low soil remediation method to meet environmental protection requirement.
Summary of the invention
The object of the invention is to be to provide a kind of cyanide polluted soil restorative procedure, the method is the soil of the serious pollution of cyanide for the treatment of characteristic contamination, contains the heavy metals such as copper in this contaminated soil simultaneously.The method utilizes the oxidisability of ozone and hydrogen peroxide, the heavy metal cyano complex in spoiled soil, rhodanate and other reducing substanceses.PH value renovation agent can the pH value of rehabilitating soil, and finally utilize hydrogen peroxide reparation, while process pollutant, make reaction system be tending towards stable state, through the reparation of this method, the heavy metals such as copper have good repairing effect.After repairing, soil reaches the B grade standard in " exhibition land used evaluation criteria of soil environment quality (provisional) ", can be used as II class land resource to use, this method is effective to cyanide serious pollution soil remediation, and environment for use friendly medicament, can not cause secondary pollution to soil, and rehabilitation cost is low, repairing efficiency is short, there is certain environmental benefit, be applicable to promoting the use of.
The present invention includes following steps:
Step one: the collection of sample and pretreatment
Gather by the soil of cyanide pollution, process of sieving after rejecting root system of plant and chad, mixing, sealing is placed for subsequent use;
Step 2: preparation slurry liquid
By certain Tu Shui than precise pedotheque and water, be made into slurry liquid, be placed in the first tank diameter, stir 5min ~ 10min, make pollutant dispersal events in water, when adsorption by soil buffer capacity is stronger, suitably can increase mixing time, fully discharge in water to pollutant, reach stable state.
Step 3: ozone reparation
The slurry liquid of configuration enters ozone reactor reparation, and the pH of slurry liquid should maintain 7 ~ 11.Ozone amount is determined according to the actual pollutant load of soil, and ozone usage should be more than or equal to two times of cyanide and rhodanate total amount, and oxidization time adjusts according to ozone concentration.Aeration mode is bottom aeration, distribution device comprises aeration head, aeration tube etc., and in ozone reactor, ozone and the abundant catalytic oxidation of slurry liquid, can destroy cyanide, rhodanate and other reducing substanceses are also destroyed simultaneously, and the heavy metals such as copper exist with sedimentary form.Air or liquid oxygen can be adopted to produce ozone as raw material electric discharge for the generation of ozone and additive method produces ozone.The material of ozone reparation reactor is the closed container of the material of resistance to ozone corrosion, and as 316 stainless steels, 304 stainless steels, closure is good simultaneously, and tail gas, to tail gas comprehensive utilization section recycling, can improve ozone utilization ratio, save tail gas breaking plant simultaneously.
Step 4: pH value reparation
After ozone reparation completes, slurry liquid enters the second tank diameter and carries out pH value reparation, general cyanide pollution feature soil has certain pH value buffer capacity, and add pH value renovation agent and ensure that pH value maintains 7 ~ 8.5, pH value renovation agent comprises NaOH, sodium acid carbonate and sulfuric acid.
Step 5: hydrogen peroxide reparation
PH value is after repairing, pollutant load in slurry liquid has certain fluctuation, adds hydrogen peroxide reparation in the second tank diameter, makes slurry liquid reaction system be tending towards stable state while removing pollutant, need if desired to add certain copper sulphate as catalyst, reaction time 0.5h ~ 2h.
Step 6: Separation of Solid and Liquid
Separation of Solid and Liquid is carried out after step 5 process, solid-liquid separating method can adopt natural sedimentation, filtration or filter-pressing method, or several method associating, B grade standard during gained soil can reach " exhibition land used evaluation criteria of soil environment quality (provisional) ", can be used as the land resource recyclings such as venue land used, commercial land.
Step 7: tail gas fully utilizes
Clear liquid after Separation of Solid and Liquid enters tail gas comprehensive utilization device advanced treating, and tail gas comprehensive utilization device adopts tank diameter or ozone reactor.Pass into the tail gas that ozone repairs section generation, improve waste gas utilization rate, reduce breaking plant simultaneously.Aeration mode is bottom aeration, and distribution device comprises aeration head, aeration tube and perforated pipe aerating regulation, and advanced treating liquid can return step 2 and recycle or qualified discharge.
Beneficial effect of the present invention:
The present invention can remove cyanide, rhodanate in soil, cuts down the harm of various heavy simultaneously, and repairing effect is good.Ozone in tail gas and pollutant react further, can improve the high and treatment effect of ozone utilization ratio, make the ozone in tail gas realize qualified discharge, save tail gas breaking plant simultaneously.Waste water after this PROCESS FOR TREATMENT can return the technological process of production and recycle or qualified discharge.The method is stablized cyanide polluted soil repairing effect, and environment for use friendly medicament can not cause secondary pollution to soil, and repairing efficiency is short, and the soil after reparation can be used as Land_use change resource, has environmental benefit.
Detailed description of the invention
The present invention includes following steps:
Step one: the collection of sample and pretreatment
Gather by the soil of cyanide pollution, process of sieving after rejecting root system of plant and chad, mixing, sealing is placed for subsequent use;
Step 2: preparation slurry liquid
By certain Tu Shui than precise pedotheque and water, be made into slurry liquid, be placed in the first tank diameter, stir 5min ~ 10min, make pollutant dispersal events in water, when adsorption by soil buffer capacity is stronger, suitably can increase mixing time, fully discharge in water to pollutant, reach stable state.
Step 3: ozone reparation
The slurry liquid of configuration enters ozone reactor reparation, and the pH of slurry liquid should maintain 7 ~ 11.Ozone amount is determined according to the actual pollutant load of soil, and ozone usage should be more than or equal to two times of cyanide and rhodanate total amount, and oxidization time adjusts according to ozone concentration.Aeration mode is bottom aeration, distribution device comprises aeration head, aeration tube etc., and in ozone reactor, ozone and the abundant catalytic oxidation of slurry liquid, can destroy cyanide, rhodanate and other reducing substanceses are also destroyed simultaneously, and the heavy metals such as copper exist with sedimentary form.Air or liquid oxygen can be adopted to produce ozone as raw material electric discharge for the generation of ozone and additive method produces ozone.The material of ozone reparation reactor is the closed container of the material of resistance to ozone corrosion, and as 316 stainless steels, 304 stainless steels, closure is good simultaneously, and tail gas, to tail gas comprehensive utilization section recycling, can improve ozone utilization ratio, save tail gas breaking plant simultaneously.
Step 4: pH value reparation
After ozone reparation completes, slurry liquid enters the second tank diameter and carries out pH value reparation, general cyanide pollution feature soil has certain pH value buffer capacity, and add pH value renovation agent and ensure that pH value maintains 7 ~ 8.5, pH value renovation agent comprises NaOH, sodium acid carbonate and sulfuric acid.
Step 5: hydrogen peroxide reparation
PH value is after repairing, pollutant load in slurry liquid has certain fluctuation, adds hydrogen peroxide reparation in the second tank diameter, makes slurry liquid reaction system be tending towards stable state while removing pollutant, need if desired to add certain copper sulphate as catalyst, reaction time 0.5h ~ 2h.
Step 6: Separation of Solid and Liquid
Separation of Solid and Liquid is carried out after step 5 process, solid-liquid separating method can adopt natural sedimentation, filtration or filter-pressing method, or several method associating, B grade standard during gained soil can reach " exhibition land used evaluation criteria of soil environment quality (provisional) ", can be used as the land resource recyclings such as venue land used, commercial land.
Step 7: tail gas fully utilizes
Clear liquid after Separation of Solid and Liquid enters tail gas comprehensive utilization device advanced treating, and tail gas comprehensive utilization device adopts tank diameter or ozone reactor.Pass into the tail gas that ozone repairs section generation, improve waste gas utilization rate, reduce breaking plant simultaneously.Aeration mode is bottom aeration, and distribution device comprises aeration head, aeration tube and perforated pipe aerating regulation, and advanced treating liquid can return step 2 and recycle or qualified discharge.
Specific embodiment 1:
Gather by the soil of cyanide pollution as pending soil, process of sieving after rejecting the impurity such as root system of plant and chad, mixing, sampling.The content of the cyanide of this soil surpasses 608mg/kg by analysis, and the content of rhodanate is 144mg/kg.Carry out toxicity discriminating to it, its major pollutants are cyanide, heavy metal, and major pollutants are composed as follows:
Table 1 cyanide polluted soil leaching characteristic identification result
Note: pH value dimensionless.
According to the relevant limit value regulation in " hazardous waste judging standard leaching characteristic identification " (GB 50853-2007), the concentration of cyanide is seriously higher than 5mg/L, so this soil has Leaching feature.Preferably, get 1kg soil, 1kg water, be mixed with slurry liquid 1. according to soil and water quality than for 1:1, stir 10min, filter and carry out pollutant levels analysis to its filtrate, analysis result sees the following form:
Table 2 analysis detects table
Note: pH value dimensionless.
Slurry liquid 1. throughput is 0.4m
3/ h, ozone concentration is 5.0g/m
3, the reaction time is 44min, and the dosage of ozone is 1.46kg/t, and pH value in reaction is 9.84, and after ozone is repaired, it is 8.75, CN that analysis pH value is carried out in filtration
tconcentration is 2.15mg/L.
After ozone is repaired, cyanide clearance is more than 97%, and the clearance of heavy metal copper is more than 98%, ozone reparation is a process consuming basicity, though pH value declines to some extent, but relative basicity is higher, and toxicity leaches result and shows to exist in this soil to consume H in a large number
+material, have certain pH value buffer capacity, this test carries out pH value adjustment by the concentrated sulfuric acid to it, adds the concentrated sulfuric acid of 1.2ml/kg, reaction 30min after, though pH still presents ascendant trend slowly, comparatively stable, pH is about 8.0.Due to pH value change, there is certain fluctuation in reaction system pollutant levels, needs to be further processed it, preferably, employing hydrogen peroxide is repaired, and the consumption of hydrogen peroxide is 6ml/kg, and the reaction time is 30min, adopts the mode of filtering to carry out Separation of Solid and Liquid to it, analyze liquid, pH value is 8.03, CN
tconcentration is 0.42mg/L.Clear liquid carries out tail gas comprehensive utilization process, and after process, concentration of cyanide is 0.26mg/L, returns and recycles or qualified discharge.
After Separation of Solid and Liquid, analyze solid, the content of cyanide is 5mg/kg, and lower than the B grade standard 8mg/kg in " exhibition land used evaluation criteria of soil environment quality (provisional) ", other heavy metal contaminants all can reach the A grade standard in standard.Carry out toxicity to it and leach discriminating and pollutant levels analysis, the content of pollutant is lower than the relevant limit value regulation in " hazardous waste judging standard leaching characteristic identification " (GB50853-2007), and this soil does not have Leaching feature.Identification result sees the following form:
Table 3 processes rear soil leaching characteristic identification result
Note: pH value dimensionless.
Claims (3)
1. a cyanide polluted soil restorative procedure, comprises the following steps:
Step one: the collection of sample and pretreatment
Gather by the soil of cyanide pollution, process of sieving after rejecting root system of plant and chad, mixing, sealing is placed for subsequent use;
Step 2: preparation slurry liquid
Pedotheque and water are made into slurry liquid, are placed in the first tank diameter, stir 5min ~ 10min, make pollutant dispersal events in water, when adsorption by soil buffer capacity is stronger, suitably can increase mixing time, fully discharge in water to pollutant, reach stable state;
Step 3: ozone reparation
The slurry liquid of configuration enters ozone reactor reparation, and the pH of slurry liquid maintains 7 ~ 11; Ozone amount is determined according to the actual pollutant load of soil, and ozone usage should be more than or equal to two times of cyanide and rhodanate total amount, and oxidization time adjusts according to ozone concentration; Aeration mode is bottom aeration;
Step 4: pH value reparation
After ozone reparation completes, slurry liquid enters the second tank diameter and carries out pH value reparation, and general cyanide pollution feature soil has certain pH value buffer capacity, adds pH value renovation agent and ensures that pH value maintains 7 ~ 8.5;
Step 5: hydrogen peroxide reparation
PH value is after repairing, pollutant load in slurry liquid has certain fluctuation, adds hydrogen peroxide reparation in the second tank diameter, makes slurry liquid reaction system be tending towards stable state while removing pollutant, need if desired to add certain copper sulphate as catalyst, the reaction time is 0.5h ~ 2h;
Step 6: Separation of Solid and Liquid
Carry out Separation of Solid and Liquid after step 5 process, the B grade standard during gained soil can reach " exhibition land used evaluation criteria of soil environment quality (provisional) ", can be used as the land resource recycling of venue land used, commercial land;
Step 7: tail gas fully utilizes
Clear liquid after Separation of Solid and Liquid enters tail gas comprehensive utilization device and carries out advanced treating, and tail gas comprehensive utilization device adopts tank diameter or ozone reactor; Pass into the tail gas that ozone repairs section generation, improve waste gas utilization rate, reduce breaking plant simultaneously; Aeration mode is bottom aeration; Advanced treating liquid can return step 2 and recycle or qualified discharge.
2. a kind of cyanide polluted soil restorative procedure according to claim 1, it is characterized in that: in described step 4, pH renovation agent is NaOH, sodium acid carbonate and sulfuric acid.
3. a kind of cyanide polluted soil restorative procedure according to claim 1, it is characterized in that: in described step 6, the method for Separation of Solid and Liquid is natural sedimentation, filtration or filter-pressing method, or the associating of wherein several method.
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Cited By (10)
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| CN105414162A (en) * | 2015-11-18 | 2016-03-23 | 中科鼎实环境工程有限公司 | Method for repairing cyanide-polluted soil by physical heat analysis technology |
| CN106216385A (en) * | 2016-07-27 | 2016-12-14 | 湖南恒凯环保科技投资有限公司 | A kind of contact break stabilisation restorative procedure of heavy-metal contaminated soil |
| CN106350072A (en) * | 2016-08-05 | 2017-01-25 | 太仓市粮满仓土肥服务专业合作社 | Soil remediation agent |
| CN106623389A (en) * | 2016-12-06 | 2017-05-10 | 天津华勘环保科技有限公司 | Remediation method for cyanide contaminated soil |
| CN106734144A (en) * | 2016-12-10 | 2017-05-31 | 云南大地绿坤环保科技有限公司 | A kind of method of contaminated soil containing cyanogen and underground water in-situ immobilization |
| CN107363084A (en) * | 2017-08-18 | 2017-11-21 | 上海憬图环境工程有限公司 | A kind of Organic Pollution arable soil wet method improvement prosthetic device and technique |
| CN109201726A (en) * | 2018-08-28 | 2019-01-15 | 中石化（洛阳）科技有限公司 | A kind of restorative procedure of cyanide polluted soil |
| CN109396167A (en) * | 2018-12-06 | 2019-03-01 | 天津华勘环保科技有限公司 | One kind soil repair system containing cyanogen and restorative procedure |
| CN110782144A (en) * | 2019-10-16 | 2020-02-11 | 上海康恒环境修复有限公司 | Evaluation method for heavy metal contaminated soil solidification/stabilization remediation effect |
| CN112775173A (en) * | 2020-11-30 | 2021-05-11 | 长沙工研院环保有限公司 | Method for restoring soil and underground water polluted by cyanide by in-situ leaching-ventilation enhanced microorganisms |
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| CN106216385A (en) * | 2016-07-27 | 2016-12-14 | 湖南恒凯环保科技投资有限公司 | A kind of contact break stabilisation restorative procedure of heavy-metal contaminated soil |
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| CN106734144A (en) * | 2016-12-10 | 2017-05-31 | 云南大地绿坤环保科技有限公司 | A kind of method of contaminated soil containing cyanogen and underground water in-situ immobilization |
| CN107363084A (en) * | 2017-08-18 | 2017-11-21 | 上海憬图环境工程有限公司 | A kind of Organic Pollution arable soil wet method improvement prosthetic device and technique |
| CN109201726A (en) * | 2018-08-28 | 2019-01-15 | 中石化（洛阳）科技有限公司 | A kind of restorative procedure of cyanide polluted soil |
| CN109396167A (en) * | 2018-12-06 | 2019-03-01 | 天津华勘环保科技有限公司 | One kind soil repair system containing cyanogen and restorative procedure |
| CN110782144A (en) * | 2019-10-16 | 2020-02-11 | 上海康恒环境修复有限公司 | Evaluation method for heavy metal contaminated soil solidification/stabilization remediation effect |
| CN110782144B (en) * | 2019-10-16 | 2023-08-08 | 上海康恒环境修复有限公司 | Evaluation method for solidification/stabilization restoration effect of heavy metal contaminated soil |
| CN112775173A (en) * | 2020-11-30 | 2021-05-11 | 长沙工研院环保有限公司 | Method for restoring soil and underground water polluted by cyanide by in-situ leaching-ventilation enhanced microorganisms |
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