CN111575011B - Heavy metal contaminated soil composite remediation agent and application method thereof - Google Patents
Heavy metal contaminated soil composite remediation agent and application method thereof Download PDFInfo
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- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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Abstract
The invention discloses a composite remediation agent for heavy metal contaminated soil and an application method thereof, belonging to the field of remediation of heavy metal contaminated soil, wherein the composite remediation agent comprises the following components in parts by weight: 25-40 parts of iron series medicament, 5-15 parts of sulfur series medicament and 40-60 parts of calcium series medicament; 5-10 parts of organic matters; the organic matter is selected from fulvic acid, fulvic acid and at least one of fulvic acid and fulvic acid. The medicament provided by the invention can adjust the dosage and the component ratio of each medicament according to the heavy metal content of the soil, and can be widely applied to different types of polluted soil. The invention has good repairing effect on the heavy metal composite polluted soil such as cadmium, lead, zinc, arsenic and the like, has long-term stability, short repairing time, flexible medicament proportioning and small dosage and saves the treatment cost.
Description
Technical Field
The invention belongs to the technical field of remediation of heavy metal contaminated soil, and particularly relates to a composite remediation agent for heavy metal contaminated soil and an application method thereof.
Background
Soil pollution can be divided into various types such as heavy metal pollution, pesticide pollution, organic matter pollution and the like. Relevant data show that at present, the most serious pollution in China is heavy metal pollution, the main pollutants are cadmium, arsenic, chromium, lead and the like, and more than half of the pollution is caused by the emission of industrial three wastes.
The existing common repair technologies for heavy metal contaminated soil include soil improvement method, electric repair technology, solidification/stabilization, soil leaching method, bioremediation technology and the like. The soil improvement method needs to consume a large amount of capital, manpower and material resources, and has the defects of land occupation, leakage, environmental pollution and the like in the soil change process; the electric restoration technology is economical and reasonable, but is easy to cause secondary soil pollution and has poor effect on sandy soil with high permeability and poor conductivity; the subsequent mud-water separation of the soil leaching method is difficult, the sewage treatment difficulty is high, the soil structure is damaged, and the resource recycling is not suitable; the bioremediation technology has long restoration period, the growth speed of the hyper-enriched plants is slow, the biomass of microorganisms is small, and the subsequent treatment is needed, so that the application requirement of large-scale engineering restoration is difficult to meet; the solidification/stabilization is to add a curing agent, an organic matter, a chemical reagent, natural minerals and the like into the soil to change the physical and chemical properties of the soil such as pH value, Eh and the like, and reduce the biological effectiveness of pollutants through the actions of oxidation, reduction, precipitation, adsorption, inhibition, complexation, chelation and the like, so as to finally achieve the aim of restoring the polluted soil. However, the existing soil remediation agents have the defects of high price, large dosage, high treatment cost, low treatment efficiency, incapability of ensuring long-term safety and the like.
Disclosure of Invention
The invention aims to overcome the defects in the background technology and provide a composite remediation agent for heavy metal contaminated soil and an application method thereof.
The technical scheme provided by the invention is as follows:
the invention relates to a composite remediation agent for heavy metal contaminated soil, which comprises the following components in parts by weight:
25-40 parts of iron series medicament, 5-15 parts of sulfur series medicament and 40-60 parts of calcium series medicament; 5-10 parts of organic matters;
the organic matter is selected from fulvic acid, fulvic acid and at least one of fulvic acid and fulvic acid.
The repairing agent consists of an iron-series agent, a sulfur-series agent, a calcium-series agent and an organic matter, wherein the calcium-series agent can change the pH value and the cation exchange capacity of soil, promote heavy metals to form oxide precipitates, effectively reduce the exchange state content of the heavy metals and form a strength matrix to fix the heavy metals so that the heavy metals are not easy to leach; the iron series medicament is a stronger reducing agent, can change the oxidation-reduction potential and the heavy metal valence state of the soil, reduce the heavy metal toxicity; part of calcium-based and iron-based compounds generated in the repair process are porous molecular structures and have adsorbability; the sulfur medicament is easy to react with heavy metal ions to generate insoluble sulfide precipitate. The added organic matters are combined with calcium and iron ions of other medicaments, so that the ground surface fine particle soil is promoted to form a large particle aggregate structure, harmful pollutants in the soil are fixed, and the processes of migration, diffusion and the like in the environment are prevented. Meanwhile, the capillary phenomenon of fine-grained soil is reduced, and the salinization formed by evaporation water carrying salt to the ground surface and gradual accumulation is greatly reduced.
In the invention, the organic matter is a composition of fulvic acid and at least one of fulvic acid and fulvic acid, wherein the fulvic acid has a lower molecular weight, is beneficial to activation, compatibilization and desorption of heavy metals, so that the heavy metals are not easy to be absorbed by crops, the crops are not easy to be polluted by the heavy metals, the fulvic acid and the fulvic acid have larger molecular weights, and have the functions of reducing, adsorbing and fixing the heavy metals, so that the effectiveness of the heavy metals can be reduced, such as the fixation of cadmium, mercury, lead and the like. The organic matter formed by the combination can play the best repairing role.
Preferably, in the organic matter, the mass ratio of at least one of the fulvic acid and the fulvic acid to the fulvic acid is 1-3: 1. under the preferable range, the finally obtained heavy metal contaminated soil composite remediation agent can obtain the best remediation effect.
Preferably, the composite repairing medicament comprises the following components in parts by weight:
25-38 parts of iron medicament, 5-12 parts of sulfur medicament and 40-59 parts of calcium medicament; 5-10 parts of organic matters.
Further preferably, the composite repairing medicament comprises the following components in parts by weight:
30-38 parts of iron medicament, 10-12 parts of sulfur medicament and 40-55 parts of calcium medicament; 5-10 parts of organic matters.
Preferably, the iron-based chemical is at least one of ferric oxide, ferrous sulfate, polymeric ferric sulfate and ferric sulfate.
Preferably, the sulfur-based chemical agent is at least one of calcium sulfide, sodium polysulfide, calcium polysulfide, and ferrous sulfide.
Preferably, the calcium-based chemical is at least one of dolomite, lime, portland cement, calcium hydroxide, and calcium carbonate.
Preferably, the preparation method of the composite repairing medicament comprises the following steps: the composite repairing medicament is prepared by respectively drying raw materials such as iron-based medicaments, sulfur-based medicaments and calcium-based medicaments, grinding the raw materials into a screen with 100-200 meshes, respectively activating the raw materials for 1-3 hours at 100-200 ℃, mixing the raw materials, adding organic substances, and uniformly mixing the raw materials.
The inventor finds that the treatment effect of the composite remediation agent for the heavy metal contaminated soil can be greatly improved by respectively activating the iron-based agent, the sulfur-based agent and the calcium-based agent and then mixing the activated agents with organic matters.
The invention relates to an application method of a heavy metal contaminated soil composite remediation agent, which comprises the following steps:
s1, crushing and screening the heavy metal contaminated soil, and controlling the particle size of the soil to be less than 3 cm;
s2, sequentially and uniformly adding the composite repairing medicament into the crushed and sieved soil in two batches, wherein the total addition amount is 2-15% of the soil mass, and 50-60% of the total amount of the composite repairing medicament is added for the first time;
s3, spraying a proper amount of water to moisten the soil, keeping the water content of the soil between 35 and 45 percent, mixing and stirring the composite repairing agent and the soil to enable the composite repairing agent and the soil to fully react;
s4, adding the residual 40-50% of the total amount of the composite repairing medicament again, and repeating the step S3;
s5, standing and maintaining the uniformly stirred soil for 3-5 days, and keeping the wettability of the soil, thereby improving the stabilization effect of the soil;
and S6, detecting the soil after the soil is maintained. The detection method adopts a standard leaching method (HJ/T299-2007 and HJ557-2009) to measure the heavy metal content in the soil leaching solution, finally, the treated soil is evaluated, the determined qualified soil is subjected to subsequent treatment, and the treated unqualified soil is subjected to medicament remediation and retreatment.
The invention has the beneficial effects that:
(1) the calcium medicament can change the pH value and the cation exchange capacity of soil, promote heavy metals to form oxide precipitates, effectively reduce the exchange state content of the heavy metals, and form a strength matrix to fix the heavy metals so that the heavy metals are not easy to leach out; the iron series medicament is a stronger reducing agent, can change the oxidation-reduction potential and the heavy metal valence state of the soil, reduce the heavy metal toxicity; part of calcium-based and iron-based compounds generated in the repair process are porous molecular structures and have adsorbability; the sulfur medicament is easy to react with heavy metal ions to generate insoluble sulfide precipitate. The organic matter is combined with calcium and iron ions of other agents, so that the ground surface fine particle soil is promoted to form a large particle aggregate structure, harmful pollutants in the soil are fixed, and the processes of migration, diffusion and the like in the environment are prevented. The agents are matched to restore the heavy metal contaminated soil, and a plurality of reaction mechanisms act simultaneously to generate synergism, so that the synchronous stabilization effect of a plurality of heavy metals is achieved under the conditions of environmental protection, economy and reasonableness.
(2) Aiming at different types of polluted soil, the dosage and the component proportion of each medicament can be adjusted according to the heavy metal content of the soil, and the application range of the composite remediation medicament is expanded.
(3) The heavy metal contaminated soil repaired by the composite agent can keep long-term stability and safety.
Drawings
FIG. 1 is a flow chart of the application of the present invention
FIG. 2 is an operation diagram of engineering application of the present invention, wherein FIG. 2(a) shows: crushing and screening soil to remove stones, uniformly spreading the soil after screening as shown in fig. 2(b), weighing the agent as shown in fig. 2(c), applying the agent as shown in fig. 2(d), mixing and stirring as shown in fig. 2(e), and stacking and maintaining as shown in fig. 2 (f).
Detailed Description
The present invention will be further described with reference to the following examples.
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. The conditions in the embodiments can be further adjusted according to specific conditions, and simple modifications of the method of the present invention based on the concept of the present invention are within the scope of the claimed invention.
Example 1
The soil composite repairing medicament comprises the following components in parts by weight: 30 parts of ferrous sulfate; 5 parts of calcium sulfide; 40 parts of lime; 19 parts of dolomite, 3 parts of black humic acid and 3 parts of yellow humic acid.
Respectively drying iron series medicament, sulfur series medicament and calcium series medicament, grinding into 150-mesh screen, respectively activating at 105 deg.C for 1.5h, mixing, adding organic matter, and mixing to obtain the final product.
Example 2
The soil composite repairing medicament comprises the following components in parts by weight: 25 parts of polymeric ferric sulfate; 4 parts of sodium polysulfide; 4 parts of sodium sulfide; 20 parts of calcium carbonate; 28 parts of Portland cement; 6 parts of black humic acid and 3 parts of yellow humic acid.
Respectively drying iron series medicament, sulfur series medicament and calcium series medicament, grinding into 150-mesh screen, respectively activating at 105 deg.C for 1.5h, mixing, adding organic matter, and mixing to obtain the final product.
Example 3
The soil composite repairing medicament comprises the following components in parts by weight: 30 parts of ferric oxide; 8 parts of ferrous sulfide; 2 parts of calcium sulfide; 25 parts of calcium hydroxide; 30 parts of lime; 2.5 parts of fulvic acid and 2.5 parts of fulvic acid.
Respectively drying iron series medicament, sulfur series medicament and calcium series medicament, grinding into 100-mesh screen, respectively activating at 150 ℃ for 2h, mixing, adding organic matter, and mixing to obtain the composite repairing medicament.
Example 4
The soil composite repairing medicament comprises the following components in parts by weight: 30 parts of polymeric ferric sulfate; 8 parts of ferric sulfate; 12 parts of calcium polysulfide; 40 parts of calcium carbonate; 4 parts of humic acid; 3.5 parts of fulvic acid and 2.5 parts of fulvic acid.
Respectively drying iron series medicament, sulfur series medicament and calcium series medicament, grinding into 100-mesh screen, respectively activating at 150 ℃ for 2h, mixing, adding organic matter, and mixing to obtain the composite repairing medicament.
Comparative example 1
The soil composite repairing medicament comprises the following components in parts by weight: 30 parts of ferrous sulfate; 5 parts of calcium sulfide; 40 parts of lime; 19 parts of dolomite and 3 parts of black humic acid.
Respectively drying iron series medicament, sulfur series medicament and calcium series medicament, grinding into 150-mesh screen, respectively activating at 105 deg.C for 1.5h, mixing, adding organic matter, and mixing to obtain the final product.
Comparative example 2
The soil composite repairing medicament comprises the following components in parts by weight: 30 parts of ferrous sulfate; 5 parts of calcium sulfide; 40 parts of lime; 19 parts of dolomite and 3 parts of fulvic acid.
Respectively drying iron series medicament, sulfur series medicament and calcium series medicament, grinding into 150-mesh screen, respectively activating at 105 deg.C for 1.5h, mixing, adding organic matter, and mixing to obtain the final product.
Comparative example 3
The soil composite repairing medicament comprises the following components in parts by weight: 30 parts of ferrous sulfate; 5 parts of calcium sulfide; 40 parts of lime; 19 parts of dolomite, 3 parts of black humic acid and 3 parts of yellow humic acid.
Uniformly mixing the iron medicament, the sulfur medicament and the calcium medicament, drying and grinding the mixture together, sieving the mixture with a 150-mesh sieve, respectively activating the mixture for 1.5h at 105 ℃, finally adding organic substances, and uniformly mixing the mixture to obtain the composite repairing medicament.
The specific implementation case is applied as follows:
by adopting the engineering application method of the composite remediation agent for the heavy metal contaminated soil, the total adding proportion of the composite remediation agent is 5% of the soil mass, the different contaminated heavy metal contaminated soil of a certain project in Hunan is remedied by adjusting the proportion of each component in the composite remediation agent, and meanwhile, a certain common agent A on the market is selected for comparison, and the total adding proportion of the agent A is 5% of the soil mass. Retesting is carried out after the sample is cured for 365 days, and long-term safety and stability of the repairing effect are discussed. The specific application method is as follows
S1, crushing and screening the heavy metal contaminated soil, and controlling the particle size of the soil to be less than 3 cm;
s2, weighing the composite repairing medicament according to the total adding proportion of the composite repairing medicament, and uniformly adding 60 percent of the composite repairing medicament into the crushed and sieved soil
S3, spraying a proper amount of water to moisten the soil, keeping the water content of the soil at 40%, mixing the medicament and the soil, and stirring to make the medicament and the soil fully react;
s4, uniformly adding 40% of the composite repairing medicament into the soil, and repeating the treatment of the step S3;
s5, standing and maintaining the uniformly stirred soil for 4 days, and keeping the wettability of the soil, thereby improving the stabilization effect of the soil;
the soil S6 is maintained and then detected, a standard leaching method (HJ/T299-2007 and HJ557-2009) is adopted in the detection method, heavy metal content in the soil leaching solution is measured, finally, the treated soil is evaluated, the qualified soil is measured and subjected to subsequent treatment, and the unqualified soil is subjected to medicament remediation and retreatment.
The detailed picture of the engineering application is shown in the attached figure 2, and the detection result is as follows (unit: mg/L):
the standard limits of cadmium, arsenic, lead and zinc in the above test were 0.005mg/L, 0.05mg/L and 1.0mg/L, respectively. By combining the data, compared with a certain common medicament A on the market, under the condition of the same dosage, the invention can repair the polluted soil with higher concentration by adjusting the component proportion of the composite medicament, so that the invention can adjust the formula according to the concentration of heavy metal in the soil, for example, for the soil with low concentration of heavy metal, the formula combination with low cost can be selected, such as the formula in example 1, and for the soil with high concentration of heavy metal, the formula in example 4 can be selected, and the formula in example 4 can realize excellent repairing effect on the soil with high concentration of heavy metal.
The composite repairing medicament has better repairing effect, wider application range and long-term stability and safety.
The specific comparative example was applied as follows:
by adopting the engineering application method of the composite remediation agent for heavy metal contaminated soil, the addition proportion of the composite remediation agent is 10%, the same batch of contaminated heavy metal contaminated soil in a certain project in Hunan is remediated through the embodiment 1 and the three groups of comparative examples, and the optimized composite remediation agent has a more remarkable remediation effect, wherein the remediation method is consistent with the application method in the implementation case.
The standard limits of cadmium, arsenic, lead and zinc in the above test were 0.005mg/L, 0.05mg/L and 1.0mg/L, respectively. By combining the data, under the condition of the same dosage, the composite repairing agent provided by the invention has the advantages that the fixing effect of cadmium and lead is improved by adding macromolecular black humic acid and brown humic acid, and the repairing effect is better by adding micromolecular yellow humic acid, adopting a reasonable agent activation mode and the like.
The invention has good repairing effect on the heavy metal contaminated soil, long-term stability, short repairing time, flexible medicament proportioning and small dosage, and saves the treatment cost; in addition, the raw materials of the invention are widely and easily available, the industrial production is realized, and the invention has good social and environmental benefits.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (3)
1. The composite remediation agent for the heavy metal contaminated soil is characterized by comprising the following components in parts by weight: the composite repairing medicament comprises the following components in parts by weight:
25-38 parts of iron medicament, 5-12 parts of sulfur medicament and 40-59 parts of calcium medicament; 5-10 parts of organic matters;
the organic matter is selected from fulvic acid, fulvic acid and at least one of fulvic acid and fulvic acid; in the organic matter, the mass ratio of at least one of fulvic acid and fulvic acid to fulvic acid is 1-3: 1;
the iron-based medicament is at least one of ferric oxide, ferrous sulfate, polymeric ferric sulfate and ferric sulfate,
the sulfur medicament is at least one of calcium sulfide, sodium polysulfide, calcium polysulfide and ferrous sulfide,
the calcium medicament is at least one of dolomite, lime, portland cement, calcium hydroxide and calcium carbonate,
the preparation method of the composite repairing medicament comprises the following steps: respectively drying and grinding the iron medicament, the sulfur medicament and the calcium medicament, sieving the ground medicaments by a 100-200-mesh sieve, respectively activating the ground medicaments for 1-3 h at 100-200 ℃, mixing the ground medicaments, adding organic substances, and uniformly mixing the mixed medicaments to obtain the composite repairing medicament.
2. The composite remediation agent for heavy metal contaminated soil according to claim 1, wherein: the composite repairing medicament comprises the following components in parts by weight:
30-38 parts of iron medicament, 10-12 parts of sulfur medicament and 40-55 parts of calcium medicament; 5-10 parts of organic matters.
3. The application method of the composite remediation agent for heavy metal contaminated soil according to any one of claims 1 to 2, wherein the application method comprises the following steps:
s1, crushing and screening the heavy metal contaminated soil, and controlling the particle size of the soil to be less than 3 cm;
s2, sequentially and uniformly adding the composite repairing medicament into the crushed and sieved soil in two batches, wherein the total addition amount is 2-15% of the soil mass, and 50-60% of the total amount of the composite repairing medicament is added for the first time;
s3, spraying a proper amount of water to moisten the soil, keeping the water content of the soil between 35 and 45 percent, mixing and stirring the composite repairing agent and the soil to enable the composite repairing agent and the soil to fully react;
s4, adding the residual 40-50% of the total amount of the composite repairing medicament again, and repeating the step S3;
s5, standing and maintaining the soil after being evenly stirred for 3-5 days,
and S6, detecting the soil after the soil is maintained.
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| CN112795383A (en) * | 2020-12-17 | 2021-05-14 | 赛恩斯环保股份有限公司 | Multiple heavy metal compound contaminated soil remediation agent and application method thereof |
| CN112777974B (en) * | 2020-12-31 | 2022-08-19 | 诚邦生态环境股份有限公司 | Special curing agent applied to soil with severe cadmium pollution and application method thereof |
| CN112940731A (en) * | 2021-01-19 | 2021-06-11 | 广西壮族自治区亚热带作物研究所（广西亚热带农产品加工研究所） | Heavy metal composite pollution site treatment and restoration agent |
| CN113528146B (en) * | 2021-08-19 | 2022-01-28 | 河南大学 | Preparation and application of surface-modified silicon dioxide-doped ferrous sulfide soil heavy metal passivator |
| CN114570758A (en) * | 2022-02-24 | 2022-06-03 | 河北华勘地质勘查有限公司 | Method for repairing hexavalent chromium contaminated soil and repairing agent |
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| JP2000328057A (en) * | 1999-05-24 | 2000-11-28 | Toyo Ink Mfg Co Ltd | Soil conditioner and method for preventing ground swell by using the same |
| JP5811393B2 (en) * | 2011-07-12 | 2015-11-11 | 公益財団法人鉄道総合技術研究所 | Method for estimating the amount of elution of heavy metal elements into water |
| CN102972114B (en) * | 2012-11-28 | 2015-07-22 | 中国水稻研究所 | Fertilizer applying method for controlling heavy metal cadmium accumulation of rice |
| CN104804747B (en) * | 2015-04-27 | 2018-08-10 | 衡阳保地环境科技有限公司 | A kind of calcium base weight metal soil-repairing agent and preparation 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 |
| CN106903150A (en) * | 2017-03-08 | 2017-06-30 | 中国地质科学院矿产资源研究所 | Heavy metal contaminated soil remediation material and application method thereof |
| CN108641726B (en) * | 2018-04-23 | 2021-03-26 | 永清环保股份有限公司 | Compound reagent for repairing heavy metal contaminated soil and application thereof |
| CN109370607A (en) * | 2018-12-10 | 2019-02-22 | 中国石油大学(华东) | The modified production soil conditioner of gasifier slag humic acid and its soil improvement reparation application |
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| CN109762569B (en) * | 2018-12-27 | 2021-03-19 | 广东开源环境科技有限公司 | Heavy metal cadmium and arsenic composite contaminated soil remediation agent and preparation method thereof |
| CN110144222A (en) * | 2019-04-15 | 2019-08-20 | 中国矿业大学(北京) | A kind of As contaminated soil passivation renovation agent and preparation method thereof |
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