CN110479754B - Passivation method for heavy metal contaminated farmland soil - Google Patents
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Abstract
The invention relates to a passivation method of heavy metal contaminated farmland soil, which comprises the following steps: 1) adding a passivator mainly playing a role in chemical reaction into the heavy metal contaminated soil, uniformly stirring, and standing for maintenance; 2) adding a passivating agent which mainly plays a role in adsorption into the mixture obtained in the step 1), uniformly stirring, and standing and maintaining; 3) adding water into the mixture obtained in the step 2), adjusting the water content to 20-40% by weight, and standing and maintaining. According to the invention, ferric oxide, calcium carbonate, calcium hydroxy phosphate, plant ash and bentonite are combined and used step by step, the advantages of chemical complexation, precipitation and physical adsorption of heavy metal pollutants of different passivation materials are fully exerted, the advantages of each component are combined together, an economic, efficient, green and environment-friendly heavy metal passivation medicament and a remediation method thereof are established, and effective remediation of heavy metal polluted farmlands is effectively realized.
Description
Technical Field
The invention belongs to the field of soil remediation in the technical field of environmental engineering, and particularly relates to a method for passivating heavy metal contaminated farmland soil.
Background
The heavy metal pollution of soil is one of the main environmental pollution problems in China. Along with the continuous and rapid development of mining, metal smelting, chemical industry, battery manufacturing and the like relating to the heavy metal industry, the emission of heavy metal pollutants is increased year by year, and in addition, the problems of excessive pollution discharge and the like of illegal enterprises are prominent, so that the heavy metal pollution in China presents a high-occurrence situation. The cultivated land area of China suffering from heavy metal pollution of different degrees is close to 0.1 hundred million hm2The yield of the grains is reduced by over 1000 ten thousand t each year due to heavy metal pollution, and the grains are polluted by the heavy metalEat up to 1200 million t.
The harm of soil heavy metal to crop production is mainly embodied in two aspects: firstly, the heavy metal content of agricultural products exceeds the standard; secondly, the toxic action on the crops causes the yield of the crops to be reduced and even the crops are not harvested. Even if the heavy metal arsenic is in low concentration, the sensitive crop seedlings such as rice, pepper, red cowpea and the like are extremely obviously poisoned, and the biomass is reduced by more than 10 percent. Heavy metals can finally enter the human body through the soil-plant system via the food chain, affecting the human health. And can harm the skin, respiratory, digestive, urinary, cardiovascular, neurological, hematopoietic, etc. systems of humans, and can induce cytological consequences of DNA structural damage such as cell chromosomal aberration, sister chromatid exchange, and micronuclei increase.
At present, the method for treating the heavy metal polluted farmland soil mainly used in China comprises a soil passivation method, agricultural regulation and control, phytoremediation, soil leaching, planting structure adjustment and the like. Among them, phytoremediation is the major technique used, but the treatment cycle of this technique is long.
The soil passivation means that a chemical conditioner or a passivator is added into soil, and the mobility of heavy metals is reduced through adsorption or coprecipitation, so that the content of effective states of the heavy metals in the soil is reduced, the absorption of crops to the heavy metals is reduced, and the toxicity of the heavy metals is reduced to the maximum extent. The method is simple, convenient, quick, good in effect, economical and practical, and is an effective method for restoring the polluted farmland soil.
The prior arts such as chinese invention patents CN201711464010, CN201610596960, CN201710178365, CN201810365538, CN201610079842, etc. disclose methods for soil passivation and passivating agents used in the methods, which mainly passivate soil by mixing different kinds of passivating agents with soil to react with heavy metals, but the principle of removing heavy metals by each kind of passivating agent is different, so that it is difficult to distinguish the actual action and interaction of each passivating agent, and further improve the effect of removing heavy metals. Furthermore, in the prior art, numerous effects such as adsorption and chemical effects are performed simultaneously, which may have a limiting effect between the different effects. Chinese invention patent CN201710902422 discloses a technical scheme of adding an adsorbent and then adding a chemical reaction reagent to remove heavy metals in soil, but adsorption of heavy metals may cause local excess in soil, and may have adverse effects on further improving soil passivation. Therefore, there is still a need for further research on how to improve the technical effect of soil passivation.
Disclosure of Invention
According to the invention, ferric oxide, calcium carbonate, calcium hydroxy phosphate, plant ash and bentonite are combined and used step by step, the advantages of chemical complexation, precipitation and physical adsorption of heavy metal pollutants of different passivation materials are fully exerted, the advantages of each component are combined together, an economic, efficient, green and environment-friendly heavy metal passivation medicament and a remediation method thereof are established, and effective remediation of heavy metal polluted farmlands is effectively realized.
In order to achieve the aim, the invention provides a passivation method of heavy metal contaminated farmland soil, which comprises the following steps:
1) adding a passivator mainly playing a role in chemical reaction into the heavy metal contaminated soil, uniformly stirring, and standing for maintenance;
2) adding a passivating agent which mainly plays a role in adsorption into the mixture obtained in the step 1), uniformly stirring, and standing and maintaining;
3) adding water into the mixture obtained in the step 2), adjusting the water content to 20-40% by weight, and standing and maintaining.
Preferably, the passivating agent mainly playing a role of chemical reaction is ferric oxide, calcium carbonate and calcium hydroxy phosphate, and the weight ratio of the passivating agent to the calcium hydroxy phosphate is 0.3-0.7: 0.15-0.35: 0.15-0.35.
Preferably, the passivator mainly playing a role of adsorption is plant ash and bentonite, and the weight ratio of the passivator to the plant ash to the bentonite is 0.25-0.75: 0.5-1.5.
Preferably, the weight ratio of the ferric oxide to the calcium carbonate to the calcium hydroxy phosphate is 0.5: 0.25: 0.25; the weight ratio of the plant ash to the bentonite is 0.5: 1.
preferably, the bentonite is calcium bentonite, and the main component of the bentonite is montmorillonite.
Preferably, the weight of the passivator mainly playing a role of chemical reaction is 0.6-1% of that of the heavy metal polluted soil; the weight of the passivator mainly playing a role in adsorption is 0.75-3% of that of the heavy metal contaminated soil.
Preferably, the curing time in the step 1) is 10-30 min; the curing time of the step 2) is 10-30 min; the curing time of the step 3) is 2-5 days.
Preferably, the heavy metal contaminated soil contains arsenic, copper, lead, nickel and zinc.
Preferably, the heavy metal contaminated soil is farmland soil which is polluted by heavy metals and is arranged at the periphery of a mining area.
Compared with the prior farmland soil remediation technology, the method has the following advantages:
(1) according to the application, the passivator mainly playing a role in chemical reaction is mixed with the heavy metal contaminated soil, so that more uniform distribution of the passivator and the heavy metal pollutants in the soil can be realized while the chemical reaction is realized, and the passivator and the heavy metal pollutants can be fully contacted in the soil body. Then adding a passivating agent which mainly plays a role in adsorption, and can adsorb heavy metal pollutants and simultaneously adsorb partial passivating agent which mainly plays a role in chemical reaction, so that a chemical reaction reagent is distributed around the adsorbent or is adsorbed in the adsorbent, thereby better realizing the unified chemical treatment of physically concentrated heavy metals, and further more effectively realizing the soil passivation effect. If the prior art carries out physical adsorption firstly, the concentration of heavy metal pollutants in the adsorbent is higher, the concentration of heavy metal pollutants in soil is lower, and when chemical reaction reagents are redistributed, although the chemical reaction reagents are uniformly distributed in the soil, when the chemical reaction reagents are used for removing the heavy metal pollutants with low concentration in the soil and high concentration in the adsorbent in uniform concentration, the situation that local chemical reaction reagents are excessive or insufficient exists, although soil passivation can be realized, the passivation effect is difficult to achieve the degree of the application.
(2) The application realizes the synergistic effect of the three substances when the ferric oxide, the calcium carbonate and the calcium hydroxy phosphate are adopted to remove the heavy metals. Ferric oxide can generate iron ions which react with heavy metal oxygen-containing acid radicals (such as arsenate) under the action of water, so that heavy metal pollutants can be passivated through chemical reaction, calcium carbonate is dissolved in water in a trace manner, calcium ions can also react with heavy metal oxygen-containing acid radicals (such as arsenate), so that heavy metal pollutants are passivated, carbonate and more heavy metal ions can generate carbonate, hydroxide generated by hydrolysis of the carbonate and more heavy metal ions can also generate hydroxide, and more heavy metal pollutants are removed. Calcium ions and hydroxyl ions generated by the part of calcium hydroxy phosphate dissolved in water can play a similar role in generating hydroxyl ions by hydrolyzing calcium ions and carbonate in calcium carbonate, but the generated phosphate radicals can also play a role in adjusting and buffering the pH value while reacting with part of heavy metal ions. For the removal of the heavy metal oxygen-containing acid radical, the iron ions are generally combined with the heavy metal oxygen-containing acid radical to cause the pH value of the soil to be reduced, and the calcium ions are combined with the heavy metal oxygen-containing acid radical more stably under the condition that the pH value is neutral and alkaline, so that the removal of the heavy metal oxygen-containing acid radical can be maintained under the efficient pH reaction condition under the pH buffering action of phosphate and carbonate polybasic acid radical. And for heavy metal ions, hydroxyl, carbonate and phosphate can also efficiently act with the heavy metal ions under the pH buffering action of phosphate and carbonate, so that mutual support of three components of ferric oxide, calcium carbonate and calcium hydroxy phosphate in action is realized, the reaction is always carried out under a proper condition, and the soil can be better passivated. Iron sesquioxide, calcium carbonate, and calcium hydroxy phosphate mainly play a role in chemical reaction, but have a certain specific surface area as a solid substance and also have an adsorption effect, but the adsorption effect is much smaller than that of an adsorbent. When the three reagents are applied, the three reagents are uniformly mixed in a soil bulk phase to form a composite passivator to play a synergistic role.
(3) The application adopts plant ash and bentonite as passivators which mainly play a role in adsorption. The plant ash is residue after incineration of agricultural herbage and woody plant, has alkalescence, larger specific surface area and pore volume, has stronger adsorption capacity and surface complexing capacity for heavy metal, and is beneficial to improving the pH of soil if the plant ash is weak or alkaline, and promotes the heavy metal to form hydroxide precipitate; the bentonite is a natural clay mineral, is rich in reserves in nature and low in price, the main component of the bentonite is montmorillonite, the particles are fine, the specific surface area and the porosity are large, an interlayer structure contains exchangeable inorganic cations, part of oxygen atom electrons are exposed on the surface of a crystal, heavy metal elements can be fixed through the actions of ion exchange, special adsorbent coprecipitation and the like, and in addition, the special structure of the clay mineral is beneficial to forming a soil aggregate structure, so that the fertilizer and water retention capacity of soil is improved. The plant ash and the bentonite mainly play a role in adsorption due to large specific surface area, and also have a role in pH adjustment and ion exchange, so that the plant ash and the bentonite can perform a synergistic effect with uniformly distributed ferric oxide, calcium carbonate and calcium hydroxy phosphate, and can further interact with the ferric oxide, the calcium carbonate and the calcium hydroxy phosphate by performing the functions of pH adjustment and ion exchange, so that the soil passivation effect is better.
Detailed Description
The present invention is further described with reference to specific examples to enable those skilled in the art to better understand the present invention and to practice the same, but the examples are not intended to limit the present invention.
In the following examples of the invention, the samples of heavy metal contaminated soil were from soil in farmland surrounding a mine area in the Hubei Jingmen. The sample is mainly polluted by arsenic, copper, lead, nickel, zinc and the like, and specific parameters are shown in table 1.
TABLE 1 soil sample parameters
Example 1
1) Adding 4g of ferric oxide, 2g of calcium carbonate and 2g of calcium hydroxy phosphate into 1kg of heavy metal contaminated soil, uniformly stirring, standing and maintaining for 20 min;
2) adding 5g of plant ash and 10g of calcium bentonite into the mixture obtained in the step 1), uniformly stirring, standing and maintaining for 20 min;
3) spraying tap water to the mixture obtained in the step 2), adjusting the water content to 30%, uniformly stirring, standing and maintaining for 3 days.
Example 2
1) Adding 3g of ferric oxide, 3.5g of calcium carbonate and 1.5g of calcium hydroxy phosphate into 1kg of heavy metal contaminated soil, uniformly stirring, standing and maintaining for 30 min;
2) adding 2g of plant ash and 13g of calcium bentonite into the mixture obtained in the step 1), uniformly stirring, and standing and maintaining for 10 min;
3) spraying tap water to the mixture obtained in the step 2), adjusting the water content to 30%, uniformly stirring, standing and maintaining for 3 days.
Example 3
1) Adding 4.5g of ferric oxide, 1g of calcium carbonate and 2.5g of calcium hydroxy phosphate into 1kg of heavy metal contaminated soil, stirring uniformly, standing and maintaining for 10 min;
2) adding 9g of plant ash and 6g of calcium bentonite into the mixture obtained in the step 1), uniformly stirring, standing and maintaining for 30 min;
3) spraying tap water to the mixture obtained in the step 2), adjusting the water content to 30%, uniformly stirring, standing and maintaining for 3 days.
Comparative example 1
1) Adding 4g of ferric oxide, 2g of calcium carbonate, 2g of calcium hydroxy phosphate, 5g of plant ash and 10g of calcium bentonite into 1kg of heavy metal contaminated soil, stirring uniformly, standing and maintaining for 40 min;
2) spraying tap water to the mixture obtained in the step 1), adjusting the water content to 30%, uniformly stirring, standing and maintaining for 3 days.
Comparative example 2
1) Adding 5g of plant ash and 10g of calcium bentonite into 1kg of heavy metal contaminated soil, uniformly stirring, standing and maintaining for 20 min;
2) adding 4g of ferric oxide, 2g of calcium carbonate and 2g of calcium hydroxy phosphate into the mixture obtained in the step 1), uniformly stirring, standing and maintaining for 20 min;
3) spraying tap water to the mixture obtained in the step 2), adjusting the water content to 30%, uniformly stirring, standing and maintaining for 3 days.
Comparative example 3
1) Adding 5g of ferric oxide and 3g of calcium carbonate into 1kg of heavy metal contaminated soil, uniformly stirring, standing and maintaining for 20 min;
2) adding 5g of plant ash and 10g of calcium bentonite into the mixture obtained in the step 1), uniformly stirring, standing and maintaining for 20 min;
3) spraying tap water to the mixture obtained in the step 2), adjusting the water content to 30%, uniformly stirring, standing and maintaining for 3 days.
Comparative example 4
1) Adding 5g of ferric oxide and 3g of calcium hydroxy phosphate into 1kg of heavy metal contaminated soil, uniformly stirring, standing and maintaining for 20 min;
2) adding 5g of plant ash and 10g of calcium bentonite into the mixture obtained in the step 1), uniformly stirring, standing and maintaining for 20 min;
3) spraying tap water to the mixture obtained in the step 2), adjusting the water content to 30%, uniformly stirring, standing and maintaining for 3 days.
Comparative example 5
1) Adding 4g of calcium carbonate and 4g of calcium hydroxy phosphate into 1kg of heavy metal contaminated soil, uniformly stirring, standing and maintaining for 20 min;
2) adding 5g of plant ash and 10g of calcium bentonite into the mixture obtained in the step 1), uniformly stirring, standing and maintaining for 20 min;
3) spraying tap water to the mixture obtained in the step 2), adjusting the water content to 30%, uniformly stirring, standing and maintaining for 3 days.
Comparative example 6
1) Adding 4g of ferric oxide, 2g of calcium carbonate and 2g of calcium hydroxy phosphate into 1kg of heavy metal contaminated soil, uniformly stirring, standing and maintaining for 20 min;
2) adding 15g of activated carbon into the mixture obtained in the step 1), uniformly stirring, standing and maintaining for 20 min;
3) spraying tap water to the mixture obtained in the step 2), adjusting the water content to 30%, uniformly stirring, standing and maintaining for 3 days.
The results of the study of passivated soil obtained by sampling and testing of examples 1-3 and comparative examples 1-6 are shown in Table 2.
TABLE 2 passivation test results
The results of the examples 1 to 3 show that the passivation method has a good passivation effect, can passivate the heavy metal in an effective state in the polluted farmland soil, and has a good passivation effect. It can be seen from the results of the comparative example 1 and the comparative examples 1 and 2 that the passivators mainly having a chemical reaction effect are uniformly distributed in the soil body phase polluted by the heavy metal, and then the passivators mainly having an adsorption effect are uniformly distributed in the mixture, so that the passivators and the heavy metal having the chemical reaction effect are uniformly mixed in the soil, and then the passivators and the heavy metal are concentrated on the surface or the periphery of the adsorbent, so that the chemical reaction can be carried out under uniform and effective conditions, and the more optimal passivation effect can be realized. It can be seen from comparative example 1 that if both the predominantly chemically reactive and the adsorbing passivators are added to the soil simultaneously, each reagent will be active simultaneously, the conditions under which the chemical reactions take place are uncertain, and the difference between the chemically reactive and the physically adsorbed reagents may result in part of the adsorbent adsorbing the excess contaminant and insufficient passivator contact, and the other part of the adsorbent adsorbing the excess passivator without contact with the appropriate amount of contaminant. It can be seen from comparative example 2 that if the passivating agent mainly playing a role of adsorption is added first, the heavy metal pollutants and the passivating agent mainly playing a role of chemical reaction are aggravated in uneven distribution, the chemical reaction environment in the soil bulk phase is not uniform, and although most of the heavy metals can be passivated, the passivation effect cannot reach the degree of example 1. As can be seen by comparing example 1 with comparative examples 3-5, the combined use of ferric oxide, calcium carbonate and calcium hydroxy phosphate functionally has a supporting effect, thereby creating a synergistic effect to passivate heavy metals by chemical reaction. The iron ions and the calcium ions can react with the heavy metal oxygen-containing acid radicals under the environment condition of neutral partial acid or neutral partial alkali, and can jointly play a reaction role under the buffer condition of phosphate radicals and carbonate radicals, so that the heavy metal oxygen-containing acid radicals can be effectively passivated under the stable chemical environment condition from weak acid to weak alkali. And carbonate ions, hydroxyl ions and phosphate ions also realize stable passivation on heavy metal ions under the buffering action of phosphate and carbonate. Therefore, only the three substances are adopted, so that a wide range of heavy metals can be removed, and the effect of adopting the three substances cannot be achieved by only adopting two of the substances, which also indicates that the three substances generate synergistic action. It can be seen from the comparison between example 1 and comparative example 6 that, when the passivating agent mainly playing a role of adsorption is replaced by activated carbon, better passivation effect can be obtained compared with the prior art, but if plant ash and bentonite which have functions of pH adjustment and ion exchange besides adsorption are adopted, the chemical adjustment and supplement with ferric oxide, calcium carbonate and calcium hydroxy phosphate can be better realized, and thus the passivation effect on heavy metal substances can be better realized.
According to the application, the passivator mainly playing a role in chemical reaction is added firstly, and the passivator mainly playing a role in adsorption is added, so that the organic combination of chemical action and physical action is realized, a uniform reaction environment is provided for removing heavy metals, and a better passivation effect is realized. The application further researches and develops the combination and the use step by step of the ferric oxide, the calcium carbonate, the calcium hydroxy phosphate, the plant ash and the bentonite, the combined use of the ferric oxide, the calcium carbonate and the calcium hydroxy phosphate has a synergistic effect, the synergistic effect can be further promoted by further adding the plant ash and the bentonite, and a good passivation effect is obtained.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (1)
1. A passivation method of heavy metal contaminated farmland soil comprises the following steps:
1) adding a passivator mainly playing a role in chemical reaction into the heavy metal contaminated soil, uniformly stirring, and standing for maintenance;
2) adding a passivating agent which mainly plays a role in adsorption into the mixture obtained in the step 1), uniformly stirring, and standing and maintaining;
3) adding water into the mixture obtained in the step 2), adjusting the water content to 20-40% by weight, standing and maintaining;
the passivator mainly playing a role of chemical reaction is ferric oxide, calcium carbonate and calcium hydroxy phosphate, and the weight ratio of the passivator to the calcium hydroxy phosphate is 0.5: 0.25: 0.25;
the weight of the passivator mainly playing a role of chemical reaction is 0.6-1% of that of the heavy metal contaminated soil;
the weight of the passivator mainly playing a role in adsorption is 0.75-3% of that of the heavy metal contaminated soil;
the passivator mainly playing a role in adsorption is plant ash and bentonite, and the weight ratio of the passivator to the plant ash to the bentonite is 0.5: 1;
the bentonite is calcium bentonite, and the main component of the bentonite is montmorillonite;
the heavy metal contaminated soil contains arsenic, copper, lead, nickel and zinc;
the heavy metal contaminated soil is farmland soil polluted by heavy metals at the periphery of a mining area;
wherein the curing time in the step 1) is 10-30 min; the curing time of the step 2) is 10-30 min; the curing time of the step 3) is 2-5 days.
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| LU102374A LU102374B1 (en) | 2019-08-21 | 2020-01-08 | Method for passivating heavy metal contaminated farmland soil |
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| CN111848304A (en) * | 2020-06-17 | 2020-10-30 | 中国科学院广州能源研究所 | Soil fixing agent and application thereof in soil polluted by heavy metals |
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