CN110947364A - Heavy metal contaminated soil remediation agent and application thereof - Google Patents
Heavy metal contaminated soil remediation agent and application thereof Download PDFInfo
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- CN110947364A CN110947364A CN201911275049.7A CN201911275049A CN110947364A CN 110947364 A CN110947364 A CN 110947364A CN 201911275049 A CN201911275049 A CN 201911275049A CN 110947364 A CN110947364 A CN 110947364A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
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Abstract
The invention discloses a heavy metal contaminated soil repairing agent and application thereof, wherein the repairing agent consists of attapulgite and charcoal, the mass ratio of the attapulgite to the charcoal is 1:1-3, wherein the charcoal is one of pig manure charcoal and rice husk charcoal; the repairing agent can repair the soil polluted by heavy metals, particularly the soil polluted by cadmium, copper and zinc, and the addition amount of the repairing agent is 1-3% of the mass of the soil. The soil remediation agent disclosed by the invention is good in remediation effect, cheap and easy to obtain, and can be widely applied to remediation of heavy metal contaminated soil.
Description
Technical Field
The invention relates to the field of soil heavy metal pollution treatment, in particular to a heavy metal polluted soil remediation agent and application thereof.
Background
Soil is one of the natural resources necessary for human survival, and is also burdened with providing food and other renewable resources to humans. However, with the development of industrial and agricultural production and the progress of modern technology, the problem of heavy metal pollution, especially soil heavy metal pollution, has become one of the main problems endangering global environmental quality and human survival and development. After heavy metals enter the soil, most of the heavy metals are gathered on the surface layer of the soil by relatively stable polymers and compounds or are adsorbed by the soil, and the functions and the structure of the soil are changed after the concentration of the heavy metals in the soil exceeds the self-cleaning capacity of the soil, so that the properties of the soil are difficult to recover to the state before pollution.
The biochar is a carbon-rich solid obtained by thermally cracking agricultural and forestry wastes under an oxygen-limited condition, is loose and porous in the interior, has a large specific surface area, has strong adsorption capacity, oxidation capacity and cation exchange capacity, and can be used for adsorbing heavy metals in soil. Moreover, the raw material source for preparing the biochar is wide, and industrial and agricultural wastes such as vinasse, straws, rice hull and pig manure can be used as the raw material of the biochar. The biochar can adsorb heavy metals in soil, keep soil moisture, increase soil organic matter content and maintain soil ecological balance.
The attapulgite is a hydrated magnesium aluminum silicate mineral with a layer chain structure, has a rod-shaped crystal structure of a natural nano material, and has the physicochemical characteristics of porous interior, large specific surface area, strong adsorption force, good cohesiveness, low density and the like. It can retain water in soil, regulate pH value, provide plant with certain trace elements, promote plant growth, raise fertilizer utilization and improve soil activity. Meanwhile, the attapulgite has good effect of adsorbing heavy metal ions, low cost and simple regeneration, and is a research hotspot in the field of removing the heavy metal ions by an adsorption method. The attapulgite clay has rich resources and low cost in China, can provide rich raw materials for treating national soil heavy metal pollution, expand the application field of the attapulgite clay, improve the utilization efficiency of the clay, and increase the utilization value of the clay.
At present, the method for repairing the soil polluted by heavy metal mainly comprises a physical method, a chemical method and a biological method, but the physical and chemical methods are high in repairing cost, the soil characteristics and a native soil microorganism area are easy to damage, and secondary pollution is easy to cause; the biological method is not beneficial to large-scale commercial application and large-area popularization, different organisms have different requirements on growth conditions, so that the use of the biological method is limited, and meanwhile, the biological method is easily influenced by external conditions in the soil pollution remediation process, and the remediation effect is difficult to predict.
Disclosure of Invention
In order to solve the problems, the invention provides a heavy metal contaminated soil remediation agent which consists of attapulgite and charcoal.
Further, the mass ratio of the attapulgite to the charcoal is 1: 1-3.
Furthermore, the mass ratio of the attapulgite to the biochar is 1: 2.
further, the biochar is pig manure carbon and/or rice husk carbon.
Furthermore, the mass ratio of the pig manure carbon to the rice hull ash is 1: 1.5.
Further, the preparation method of the pig manure carbon comprises the following steps:
s1, carbonizing the pig manure at 550 ℃ for 2 hours to obtain blocky pig manure carbon;
s2, putting the massive pig manure carbon in the S1 into a ball mill for ball milling;
s3, screening the ball-milled pig manure carbon through a 100-mesh sieve;
the particle size of the pig manure carbon is 80-100 meshes, the pH value is 7.54, and the ash content is 250 g/kg.
Further, the preparation method of the rice husk carbon comprises the following steps:
s4, carbonizing the rice hulls at the temperature of 500 ℃ for 2 hours to obtain rice hull carbon;
s5, putting the rice husk carbon in the S1 into a ball mill for ball milling;
s6, sieving the ball-milled rice husk carbon by a 100-mesh sieve;
the obtained rice husk carbon has the particle size of 80-100 meshes, the pH value of 7.92 and the ash content of 350 g/kg.
Furthermore, the addition amount of the soil remediation agent is 1-3% of the soil mass.
Furthermore, the addition amount of the soil remediation agent is 2% of the soil mass.
The heavy metal contaminated soil remediation agent disclosed by the invention is applied to remediation of heavy metal Cu, Cd and Zn contaminated soil.
The invention has the beneficial effects that:
the soil pollution repairing agent provided by the invention mixes attapulgite with pig manure carbon and/or rice husk carbon in a certain proportion to repair the soil polluted by heavy metal ions of Cu, Cd and Zn, so that the content of the heavy metal ions in the soil can be obviously reduced, and the content of organic matters in the soil can be increased.
In addition to the objects, features and advantages described above, other objects, features and advantages of the present invention are also provided. The present invention will be described in further detail below with reference to the drawings.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention.
FIG. 1 is a graph showing the change of organic matter content in soil when the amount of soil remediation agent added is 1%;
FIG. 2 is a graph showing the change of organic matter content in soil when the amount of soil remediation agent added is 2%;
FIG. 3 is a graph showing the change of organic matter content in soil when the amount of soil remediation agent added is 3%;
FIG. 4 is a graph showing the change of effective Cu content in soil when the amount of soil remediation agent added is 1%;
FIG. 5 is a graph showing the change of effective Cu content in soil when the amount of soil remediation agent added is 2%;
FIG. 6 is a graph showing the change of effective Cu content in soil when the amount of soil conditioner added is 3%;
FIG. 7 is a diagram showing the change of effective Cd content in soil when the addition amount of the soil remediation agent is 1%;
FIG. 8 is a diagram showing the change of effective Cd content in soil when the addition amount of the soil remediation agent is 2%;
FIG. 9 is a diagram showing the change of effective Cd content in soil when the addition amount of a soil remediation agent is 3%;
FIG. 10 is a graph showing the change of effective Zn content in soil when the amount of soil remediation agent added is 1%;
FIG. 11 is a graph showing the change of effective Zn content in soil when the amount of soil remediation agent added is 2%;
FIG. 12 is a graph showing the change of effective Zn content in soil when the amount of soil remediation agent added is 3%.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The attapulgite clay described in the following examples is commercially available in Gansu province, Zhangye City, Youzui county; the particle size of the attapulgite is 80-100 meshes, and the pH value is 6.88.
GB-15618-2008 soil environmental quality Standard is adopted to determine the content of Cu, Cd and Zn in the soil before and after treatment.
Referring to fig. 1 to 12, as shown in fig. 1 to 12, an embodiment of a heavy metal contaminated soil remediation agent and an application thereof according to the present invention is as follows:
example 1
The heavy metal contaminated soil repairing agent consists of attapulgite and rice husk carbon, wherein the mass ratio of the attapulgite to the rice husk carbon is 1:1.
Example 2
The heavy metal contaminated soil repairing agent consists of attapulgite and rice husk carbon, wherein the mass ratio of the attapulgite to the rice husk carbon is 1: 2.
Example 3
The heavy metal contaminated soil repairing agent consists of attapulgite and rice husk carbon, wherein the mass ratio of the attapulgite to the rice husk carbon is 1: 3.
Example 4
The heavy metal contaminated soil repairing agent consists of attapulgite and pig manure carbon, wherein the mass ratio of the attapulgite to the pig manure carbon is 1:1.
Example 5
The heavy metal contaminated soil repairing agent consists of attapulgite and pig manure carbon, wherein the mass ratio of the attapulgite to the pig manure carbon is 1: 2.
Example 6
The heavy metal contaminated soil repairing agent consists of attapulgite and pig manure carbon, wherein the mass ratio of the attapulgite to the pig manure carbon is 1: 3.
Example 7
The heavy metal contaminated soil repairing agent consists of attapulgite, pig manure carbon and rice hull ash, wherein the mass ratio of the attapulgite to the pig manure carbon is 1:0.4: 0.6.
Example 8
The heavy metal contaminated soil repairing agent consists of attapulgite, pig manure carbon and rice hull ash in a mass ratio of 1:0.8: 1.2.
Example 9
The heavy metal contaminated soil repairing agent consists of attapulgite, pig manure carbon and rice hull ash in a mass ratio of 1:1.2: 1.8.
The preparation method of the pig manure charcoal described in the embodiments 1 to 9 includes the following steps:
s1, carbonizing the pig manure at 550 ℃ for 2 hours to obtain blocky pig manure carbon;
s2, putting the massive pig manure carbon in the S1 into a ball mill for ball milling;
s3, screening the ball-milled pig manure carbon through a 100-mesh sieve.
The method for preparing rice husk carbon described in examples 1 to 9 comprises the following steps:
s4, carbonizing the rice hulls at the temperature of 500 ℃ for 2 hours to obtain rice hull carbon;
s5, putting the rice husk carbon in the S1 into a ball mill for ball milling;
s6, sieving the ball-milled rice husk carbon with a 100-mesh sieve.
Experimental example 1
Experimental methods
The heavy metal composite contaminated soil is collected from the contaminated soil in the sunny region of Hangzhou city, Zhejiang province.
1) Determination of parameters
Digging soil compositely polluted by heavy metals; naturally drying the soil, crushing and sieving by using an 8-mesh sieve; and (4) measuring the pH value, organic matters, total nitrogen, available phosphorus, available potassium, available copper, available cadmium and available zinc contents of the screened soil.
3) The result of the detection
Heavy metal combined contaminated soil: the pH value is 6.26, the organic matter content is 23.10g/kg, the total nitrogen content is 1.40g/kg, the available phosphorus content is 23.62mg/kg, the quick-acting potassium content is 223.40mg/kg, the available copper content is 75.66mg/kg, the available cadmium content is 10.20mg/kg and the available zinc content is 1255.83 mg/kg.
4) Experimental protocol
Accurately weighing a certain amount of the soil remediation agent of examples 1-9, respectively adding heavy metal contaminated soil and uniformly mixing with the soil, wherein the specific addition amount is shown in Table 1, standing for 10 days after uniform mixing, and measuring the contents of organic matters, effective copper, effective cadmium and effective zinc in the soil, and the results are shown in FIGS. 1-12.
Then putting the soil mixed with the soil remediation agent into a flowerpot, wherein each pot is 1500g, and planting 20 Suzhou sienna leaves, keeping 7 healthy and strong seedlings in each pot after seedling emergence, keeping the soil moisture at 60% of saturated moisture during planting, pulling out the Suzhou sienna leaves after 45 days, and measuring the organic matter content, the effective copper content, the effective cadmium content and the effective zinc content in the soil according to the graphs of 1-3, 4-6, 7-9 and 10-12.
TABLE 1 addition of soil remediation agent in heavy metal contaminated soil
As can be seen from fig. 1-3, the organic matter content of the blank control soil (CK) did not change significantly before and after planting of suzhou cydarius. Before planting, the soil remediation agent of the embodiments 1-9 and the comparative examples 1-9 is added into the soil, so that the organic matter content in the soil can be increased, the increase of the organic matter content is more obvious as the soil remediation agent is more applied, particularly, the organic matter content in the soil can be greatly increased by adopting the soil remediation agent of the embodiments 1-9, when the addition amount of the soil remediation agent is 3%, the organic matter content in the soil before planting Suzhou minor is about 54g/kg, which is increased by 2.34 times compared with a blank control group, the organic matter content in the soil after harvesting Suzhou minor is 75g/kg, which is increased by 3.26 times compared with the blank control group, so that the soil remediation agent can obviously increase the organic matter content in the heavy metal contaminated soil, and the organic matter content in the soil before planting or after harvesting Suzhou minor is greatly increased as the biochar content is increased, the reason is that the rice hull carbon and the pig manure carbon belong to carbon-rich organic substances, and also comprise various nutrient elements such as nitrogen, oxygen, sulfur and the like and inorganic carbonate components, and the application of the carbon can increase the organic carbon content of soil.
As can be seen from the graphs in 4-6, the content of the effective Cu in the soil can be obviously reduced by adding the soil repairing agent, compared with a blank control group, the content of the effective Cu in the soil is reduced by about 25%, when the addition amount of the soil repairing agent is 1%, the difference of different soil repairing agents in the aspect of reducing the content of the effective Cu in the soil is small, and the content of heavy metals in the soil before planting and after harvesting is not obviously changed; when the amount of the soil additive is 2% and 3%, the content of the available Cu in the soil can be obviously reduced, particularly when the addition amount is 3%, the content of the available Cu in the soil can be reduced from 81mg/kg to 49mg/kg by using the soil remediation agent in example 3, and the content of the available Cu in the soil after the Yunzushu is harvested is reduced to 43mg/kg, which shows that the content of the available Cu in the soil can be obviously reduced by mixing the attapulgite with the rice hull carbon; the reason is that the carbonate in the rice husk carbon can change the pH value of the soil and promote the further complexation of the effective Cu ions by the attapulgite.
7-9 are bar graphs of the repairing effect of the soil repairing agent of the invention on Cd pollution in soil, and it can be seen that the repairing effect of the soil repairing agent on Cd pollution in an effective state in soil is better than that of the soil repairing agents of examples 1-6 and comparative examples 1-9 by mixing attapulgite, pig manure carbon and rice husk carbon in a certain proportion, and when the addition amount of the soil repairing agent is 3%, the repairing result on Cd pollution in an effective state is better than that of the soil repairing agent of 1%, the soil repairing agent of example 9 with the addition amount of 3% can reduce the content of Cd in an effective state in soil from 17.5mg/kg to 6.2mg/kg, because the special mechanism of attapulgite can fix Cd ions in an effective state in soil, and the addition of rice husk carbon and pig manure carbon can further passivate the fixed Cd in an effective state, thereby influencing the migration of Cd ions in a effective state in soil, thereby greatly reducing the content of Cd in an effective state in the soil.
FIGS. 9 to 11 show the reduction of Zn content in contaminated soil by different soil remediation agents, and it can be seen from the graphs that the addition of the soil remediation agents of examples 1 to 9 and comparative examples 1 to 9 of the present invention for 10 days can reduce the Zn content in the soil in the available state by about 20%, while the addition of the soil remediation agents of examples 1 to 9 after harvesting the Sauropus japonicus can reduce the Zn content in the soil in the available state by a large amount, particularly the soil remediation agents of examples 4 to 6 can reduce the Zn content in the soil from 1420mg/kg to 650mg/kg, because a large amount of iron and manganese oxides contained in pig manure carbon can be combined with the Zn in the soil in the available state to fix the Zn in the pig manure carbon, and the ions of Mn, Al and the like in attapulgite can also promote the solidification of the pig manure carbon, meanwhile, partial Zn in an effective state can be adsorbed, so that the content of Zn ions in the effective state in the soil is reduced.
The soil pollution repairing agent provided by the invention mixes attapulgite with pig manure carbon and/or rice husk carbon in a certain proportion to repair the soil polluted by heavy metal ions of Cu, Cd and Zn, so that the content of the heavy metal ions in the soil can be obviously reduced, and the content of organic matters in the soil can be increased.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the invention, but rather the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the present invention.
Claims (10)
1. The heavy metal contaminated soil remediation agent is characterized by consisting of attapulgite and charcoal.
2. The heavy metal contaminated soil remediation agent of claim 1, wherein the mass ratio of attapulgite to charcoal is 1: 1-3.
3. The heavy metal contaminated soil remediation agent of claim 2, wherein the mass ratio of attapulgite to charcoal is 1: 2.
4. the heavy metal contaminated soil remediation agent of any one of claims 1 to 3, wherein said biochar is pig manure carbon and/or rice husk carbon.
5. The heavy metal contaminated soil remediation agent of claim 4, wherein the mass ratio of pig manure carbon to rice hull ash is 1: 1.5.
6. The heavy metal contaminated soil remediation agent of claim 4, wherein said preparation method of pig manure charcoal comprises the steps of:
s1, carbonizing the pig manure at 550 ℃ for 2 hours to obtain blocky pig manure carbon;
s2, putting the massive pig manure carbon in the S1 into a ball mill for ball milling;
s3, screening the ball-milled pig manure carbon through a 100-mesh sieve.
7. The heavy metal contaminated soil remediation agent of claim 4, wherein said rice husk char is prepared by a method comprising the steps of:
s4, carbonizing the rice hulls at the temperature of 500 ℃ for 2 hours to obtain rice hull carbon;
s5, putting the rice husk carbon in the S1 into a ball mill for ball milling;
s6, sieving the ball-milled rice husk carbon with a 100-mesh sieve.
8. The heavy metal contaminated soil remediation agent of any one of claims 1 to 3, wherein said soil remediation agent is added in an amount of 1 to 3% by mass of the soil.
9. The heavy metal contaminated soil remediation agent of claim 8, wherein said soil remediation agent is added in an amount of 2% by mass of the soil.
10. Use of the heavy metal contaminated soil remediation agent of any one of claims 1 to 3 in the remediation of heavy metal Cu, Cd and Zn contaminated soil.
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| CN111841497A (en) * | 2020-07-30 | 2020-10-30 | 盐城工学院 | Modified loofah sponge-based biomass charcoal and preparation method and application thereof |
| CN113265256A (en) * | 2021-04-16 | 2021-08-17 | 兰州大学 | Soil conditioner and preparation method and application thereof |
| CN114702360A (en) * | 2022-04-26 | 2022-07-05 | 东华大学 | Soil heavy metal restoration agent, and preparation method and application thereof |
| CN116251570A (en) * | 2023-03-31 | 2023-06-13 | 贵州民族大学 | Adsorption material for removing heavy metal zinc in water body and preparation method and application thereof |
| CN116536051A (en) * | 2023-05-18 | 2023-08-04 | 西藏自治区农牧科学院农业质量标准与检测研究所 | Arsenic-polluted soil passivating agent, preparation method and method for treating arsenic-polluted soil |
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Cited By (5)
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| CN111841497A (en) * | 2020-07-30 | 2020-10-30 | 盐城工学院 | Modified loofah sponge-based biomass charcoal and preparation method and application thereof |
| CN113265256A (en) * | 2021-04-16 | 2021-08-17 | 兰州大学 | Soil conditioner and preparation method and application thereof |
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| CN116251570A (en) * | 2023-03-31 | 2023-06-13 | 贵州民族大学 | Adsorption material for removing heavy metal zinc in water body and preparation method and application thereof |
| CN116536051A (en) * | 2023-05-18 | 2023-08-04 | 西藏自治区农牧科学院农业质量标准与检测研究所 | Arsenic-polluted soil passivating agent, preparation method and method for treating arsenic-polluted soil |
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