CN110746976A - Soil remediation agent for passivating soil heavy metals and preparation method thereof - Google Patents
Soil remediation agent for passivating soil heavy metals and preparation method thereof Download PDFInfo
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- CN110746976A CN110746976A CN201910985282.8A CN201910985282A CN110746976A CN 110746976 A CN110746976 A CN 110746976A CN 201910985282 A CN201910985282 A CN 201910985282A CN 110746976 A CN110746976 A CN 110746976A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/08—Aluminium compounds, e.g. aluminium hydroxide
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01B—SOIL WORKING IN AGRICULTURE OR FORESTRY; PARTS, DETAILS, OR ACCESSORIES OF AGRICULTURAL MACHINES OR IMPLEMENTS, IN GENERAL
- A01B79/00—Methods for working soil
- A01B79/02—Methods for working soil combined with other agricultural processing, e.g. fertilising, planting
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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
- B09C1/08—Reclamation of contaminated soil chemically
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2101/00—Agricultural use
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- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Environmental Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a soil remediation agent for passivating soil heavy metals and a preparation method thereof. According to the soil restoration agent, the biochar, the bentonite and the magnesium oxide are mixed together according to a specific dosage proportion to obtain the soil restoration agent with an efficient restoration effect on the soil heavy metal, the three components are combined together according to a specific proportion to have a synergistic passivation effect on the soil heavy metal, the effective state content of the heavy metal cadmium in the soil can be effectively reduced, and the effective state cadmium content can be reduced by 55-60% within 1 month. The soil remediation agent for remediating the heavy metal contaminated soil has the advantages of low remediation cost, simple operation, convenient maintenance and the like.
Description
Technical Field
The invention relates to a soil repairing agent for repairing soil, in particular to a soil repairing agent for passivating soil heavy metal and a preparation method thereof, belonging to the field of repairing of heavy metal contaminated soil.
Background
Among the soil pollution, heavy metal pollution is a global environmental problem in terms of its latency, concealment, longevity and irreversible conversion, and cadmium is one of the most toxic heavy metal elements. The cadmium pollution problem of farmland soil caused by the massive use of cadmium-containing fertilizers and pesticides in agricultural production and the introduction of industrial sewage for irrigation is severe. According to incomplete statistics, the cadmium-polluted farmland area in China exceeds 20 multiplied by 104hm2The quality fraction of cadmium produced by the method exceeds the standard every year and reaches 14.6 multiplied by 108And (kg). In recent years, people have worried about and panic food safety problems due to frequent exposure of cadmium rice, and how to prevent cadmium pollution is a major strategic demand which is urgently needed to be solved at present.
The harm of the heavy metal cadmium pollution of soil is huge, the soil has the characteristics of large toxicity, stability and difficulty in removal, and how to effectively repair the soil is a difficult point of current research. At present, the remediation measures for the cadmium-polluted soil are mainly divided into three categories: physical repair measures, chemical repair measures, biological repair measures. The physical remediation measures of the cadmium-polluted soil refer to the remediation of the polluted soil by a physical method, and the physical remediation has the advantages of high efficiency, quick response and capability of thoroughly remedying the polluted soil; however, physical remediation has the limitations of large engineering quantity, high cost, easy damage to soil structure, influence on soil fertility and the like. The chemical remediation measures are to apply chemical reagents and modifiers to the polluted soil, change the existing form of cadmium in the soil, the oxidation-reduction point position of the soil, the pH value and the like, and reduce the biological effectiveness of the cadmium through the actions of separation, adsorption, conversion, passivation and the like. Chemical remediation is simple and easy to operate, but because the chemical remediation only changes the existing form of cadmium in soil, the cadmium can be reactivated under specific conditions, and the aim of permanent remediation is difficult to achieve. Therefore, chemical remediation measures are only applicable to areas with low levels of cadmium contamination. Bioremediation is to utilize certain specific animals, plants and microorganisms as a restoration main body to adsorb, passivate, fix and transform cadmium in soil, so as to restore and treat the soil. Simple operation, wide applicability, low cost, no secondary pollution, accordance with ecological development rules and the like. However, biological repair is limited due to some factors of the organism, such as limited growth range of plant root systems, susceptibility of animal growth to environmental factors and the like.
The existing remediation agents for passivating soil heavy metal cadmium have the problems of long remediation period, long effect taking time, low passivation rate and the like in different degrees, and need to be improved.
Disclosure of Invention
One of the purposes of the invention is to provide a soil remediation agent for efficiently passivating soil heavy metals;
another purpose of the invention is to provide a method for preparing the soil remediation agent for efficiently passivating heavy metals in soil
The above object of the present invention is achieved by the following technical solutions:
a soil repairing agent for passivating soil heavy metal comprises biochar and bentonite;
the biochar is a product of resource utilization of waste, has strong adsorption effect on heavy metal ions such as cadmium and the like in an environmental medium due to developed pore structure, large specific surface area and unique surface chemical property, and further influences migration and homing of the heavy metal ions.
The biochar is a porous carbon material obtained by pyrolyzing and sieving materials such as crop straws or crop seed shells and the like at high temperature; the crop straws can be rice straws, sorghum straws, corn straws and other crop straws, and are preferably rice straws; the crop seed hulls can be rice hulls, peanut hulls, corn hulls and other seed hulls, and preferably the rice hulls; the porous biochar material can be prepared from the crop straws or crop seed shells by various conventional pyrolysis preparation methods by the skilled person.
For reference, the present invention provides a method for preparing biochar, comprising: pulverizing rice straw and/or rice hull, pyrolyzing at 500-600 deg.C, and sieving with 60-80 mesh sieve.
The main component of the bentonite comprises SiO2、AL2O3、CaO、Fe2O3Etc. of which SiO is2+AL2O3The content is more than or equal to 85 percent, the content of CaO is less than or equal to 1.2 percent, and Fe2O3The content is less than or equal to 1.3 percent.
In order to realize better passivation effect, the components in parts by weight can be as follows: 25-80 parts of biochar and 5-20 parts of bentonite; preferably, the weight parts of the components are as follows: 50-70 parts of biochar and 10-20 parts of bentonite; further preferably, the weight parts of the components are as follows: 53.3-66.7 parts of biochar and 10.0-16.7 parts of bentonite.
Further experiments show that the soil remediation agent obtained by adding a certain amount of magnesium oxide on the basis of the biochar and the bentonite has a synergistic effect of passivating heavy metals, and particularly can achieve the optimal passivation effect on the passivated soil heavy metal cadmium.
Therefore, the invention further provides a soil remediation agent for passivating soil heavy metals, which consists of biochar, bentonite and magnesium oxide;
the magnesium oxide of the invention is preferably magnesium oxide with MgO content more than or equal to 98.5%.
According to the invention, experiments show that the proportion of the components has a great influence on the passivation effect of the heavy metal cadmium; the invention is determined by a screening test, and the weight parts of the components can be as follows: 25-80 parts of biochar, 5-20 parts of bentonite and 0.5-4 parts of magnesium oxide; preferably, the weight parts of the components are as follows: 50-70 parts of biochar, 10-20 parts of bentonite and 0.5-2 parts of magnesium oxide; further preferably, the weight parts of the components are as follows: 53.3-66.7 parts of biochar, 10.0-16.7 parts of bentonite and 0.9-1.2 parts of magnesium oxide.
When the components are mixed according to the following two groups of dosage in parts by weight, compared with other dosage ratios, the optimal passivation effect (difference is significant) on the heavy metal cadmium in the passivated soil can be obtained: (1) 66.7 parts of biochar, 10.0 parts of bentonite and 0.7 part of magnesium oxide; or (2) 66.7 parts of biochar, 13.3 parts of bentonite and 0.9 part of magnesium oxide.
The soil polluted by heavy metals in the invention comprises soil polluted by heavy metals such as cadmium, lead, mercury, chromium and the like.
The invention also provides a method for preparing the soil remediation agent for efficiently passivating the heavy metals in the soil, which comprises the following steps: mixing biochar, bentonite and magnesium oxide uniformly, and sieving to obtain the final product.
Wherein, the sieving is preferably a 60-80 mesh sieve.
The invention further provides a method for passivating heavy metals in soil by applying the soil remediation agent, which comprises the following steps: according to the mass ratio, the prepared soil remediation agent is doped into cadmium-polluted soil according to the proportion of 6.8-8.5%, and meanwhile, the field water capacity of the soil is controlled to be about 70%; the content of the available cadmium in the soil can be obviously reduced after about one month.
According to the invention, the biochar, the bentonite and the magnesium oxide are mixed together according to a specific dosage proportion to obtain a soil remediation agent with an efficient remediation effect on soil heavy metals; the biochar is prepared by firing rice straws as a raw material at high temperature, the biochar material has very good adsorption performance on cadmium in soil, and bentonite and biochar have no pollution to the environment and cannot cause secondary pollution; the addition amount of MgO is small, and the soil is not polluted; the three substances are combined together according to a specific proportion, have a synergistic passivation effect on the heavy metal cadmium in the soil, well achieve a repair effect, efficiently reduce the effective state content of the cadmium in the soil, and can reduce the effective state cadmium content by 55-60% within 1 month; the soil remediation agent provided by the invention has the advantages of low remediation cost, simple operation, convenient maintenance and the like.
Detailed Description
The invention is further described below in conjunction with specific embodiments, the advantages and features of which will become apparent from the description. These examples are illustrative only and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be within the scope of the invention.
Preparative example 1 preparation of biochar
Mixing rice straw and rice hull together, crushing, pyrolyzing at the high temperature of 500-600 ℃, and sieving with a 60-80 mesh sieve to obtain the rice straw and rice hull composite material.
Example 1 preparation of soil remediation Agents
Grinding bentonite, sieving the ground bentonite by a 60-80 mesh pore size sieve, and then mixing the bentonite with biochar: 53.3 parts of bentonite and 10.0 parts of bentonite by mass are mixed to prepare the soil remediation agent.
Example 2 preparation of soil remediation Agents
Grinding bentonite, sieving the ground bentonite by a 60-80 mesh pore size sieve, and then mixing the bentonite with biochar: bentonite: 53.3 parts of MgO, 13.3 parts of MgO and 0.9 part of MgO are mixed to prepare the soil remediation agent.
Example 3 preparation of soil remediation Agents
Grinding bentonite, sieving the ground bentonite by a 60-80 mesh pore size sieve, and then mixing the bentonite with biochar: bentonite: 66.7 parts of MgO, 10.0 parts of MgO and 0.7 part of MgO are mixed according to the mass ratio to prepare the soil remediation agent.
Example 4 preparation of soil remediation Agents
After the rice straw carbon and the bentonite are ground and sieved by a 60-80 mesh pore size sieve, the weight ratio of the rice straw carbon to the bentonite is determined according to the following formula: bentonite: 66.7 parts of MgO, 13.3 parts of MgO and 0.9 part of MgO are mixed according to the mass ratio to prepare the soil remediation agent.
Example 5 preparation of soil remediation Agents
After the rice straw carbon and the bentonite are ground and sieved by a 60-80 mesh pore size sieve, the weight ratio of the rice straw carbon to the bentonite is determined according to the following formula: bentonite: 66.7 parts of MgO, 16.7 parts of MgO and 1.2 parts of MgO are mixed according to the mass ratio to prepare the soil remediation agent. Test example 1 soil remediation test Using soil remediation agent
1. Test method
6 test fields with the same area are selected, the heavy metal content of the soil in the 6 test fields is the same (the cadmium concentration is 1mg/kg), and other conditions including soil fertility, land establishment, management measures and the like are also completely the same.
The soil remediation agents prepared in examples 1-5 were added to the soil of 5 test plots at a ratio of 8.0%, water was added to each test plot to about 70% of the field capacity, the soil was maintained at about 30 ℃ for 30 days, and the effective cadmium content in the soil was determined by sampling at 7d (first sampling), 15d (second sampling), and 30d (third sampling), respectively, and was compared with a blank treatment group without any soil remediation agent. One test plot was kept without any soil remediation treatment as a blank treatment group.
2. Test results
The soil remediation agent prepared in the example 1 is added into soil of a test field by 8.0 percent, water is added to the soil of the test field to reach about 70 percent of the field water capacity, the soil is maintained for 30 days in an environment of about 30 ℃, samples are taken at 7d, 15d and 30d respectively to determine the effective cadmium content in the soil, and the effective cadmium content is respectively as follows: 0.64, 0.46, 0.47(mg/kg), the content of cadmium in the available state is reduced by 21.95%, 20.69% and 6.00% respectively, compared with the blank treatment (0.82, 0.58, 0.50(mg/kg)) without any soil remediation agent.
The soil remediation agent prepared in the example 2 is added into soil of a test field by 8.0 percent, water is added to the soil to reach about 70 percent of the field water capacity, the soil is maintained for 30 days in an environment of about 30 ℃, and samples are taken at 7d, 15d and 30d respectively to determine the effective cadmium content in the soil, which are respectively: 0.5643, 0.37 and 0.3342(mg/kg), compared with blank treatments (0.82, 0.58 and 0.50(mg/kg)) without any soil repairing agent, the cadmium content in the effective state is respectively reduced by 31.7 percent, 36.21 percent and 34.00 percent. A
The soil remediation agent prepared in the example 3 is added into soil of a test field by 8.0 percent, water is added to the soil to reach about 70 percent of the field water capacity, the soil is maintained for 30 days in an environment of about 30 ℃, and samples are taken at 7d, 15d and 30d respectively to determine the effective cadmium content in the soil, which are respectively: 0.43, 0.26 and 0.19(mg/kg), and compared with blank treatment (0.82, 0.58 and 0.50(mg/kg)) without any soil repairing agent, the content of cadmium in an effective state is respectively reduced by 47.56%, 55.17% and 62.00%.
The soil remediation composition prepared in example 4 is added into soil of a test field at a ratio of 8.0%, water is added to the soil to about 70% of the field capacity, the soil is maintained for 30 days in an environment of about 30 ℃, and samples are taken at 7d, 15d and 30d respectively to determine the content of available cadmium in the soil, wherein the content of the available cadmium in the soil is respectively as follows: 0.45, 0.37 and 0.30(mg/kg), respectively, the content of cadmium in the effective state was reduced by 43.90%, 36.21% and 40.00% as compared with the blank treatment (0.82, 0.58 and 0.50(mg/kg)) without the addition of the repair material.
The soil remediation composition prepared in example 5 is added into soil of a test field at a ratio of 8.0%, water is added to the soil to about 70% of the field capacity, the soil is maintained for 30 days in an environment of about 30 ℃, and samples are taken at 7d, 15d and 30d respectively to determine the content of available cadmium in the soil, wherein the content of the available cadmium in the soil is respectively as follows: 0.54, 0.39 and 0.32(mg/kg), the content of cadmium in the effective state was reduced by 34.15%, 32.76% and 37.00% respectively, as compared with the blank treatment (0.82, 0.58 and 0.50(mg/kg)) without adding the repair material.
TABLE 1 comparative analysis of percentage reduction of 3 sampling results of different examples compared with blank treatment
According to the third sampling result of the example 3, the reduction percentage of the content of the cadmium in the effective state in the soil is obviously higher than that of other treatment groups; the results of the three samplings of example 4 were significantly higher in percent than the blank treatments than the groups of examples 1, 2 and 5.
The percentage of reduction of the effective cadmium content in the soil 30 days after the soil remediation agent prepared in the example 3 is remarkably higher than that of the soil remediation agent prepared in the blank treatment, the best remediation effect can be achieved by adding remediation materials according to the proportion in the example 3, and the soil remediation agent belongs to recommended better treatment.
Claims (10)
1. A soil restoration agent for passivating soil heavy metals is characterized by consisting of biochar and bentonite.
2. The soil remediation agent of claim 1, wherein the components are, in parts by weight: 25-80 parts of biochar and 5-20 parts of bentonite; preferably, 50-70 parts of biochar and 10-20 parts of bentonite; more preferably, the weight parts of each component are as follows: 53.3-66.7 parts of biochar and 10.0-16.7 parts of bentonite.
3. A soil restoration agent for passivating soil heavy metals is characterized by consisting of biochar, bentonite and magnesium oxide.
4. The soil remediation agent of claim 3, wherein the components are, in parts by weight: 25-80 parts of biochar, 5-20 parts of bentonite and 0.5-4 parts of magnesium oxide; preferably, the weight parts of the components are as follows: 50-70 parts of biochar, 10-20 parts of bentonite and 0.5-2 parts of magnesium oxide; further preferably, the weight parts of the components are as follows: 53.3-66.7 parts of biochar, 10.0-16.7 parts of bentonite and 0.9-1.2 parts of magnesium oxide.
5. The soil remediation agent of claim 4, wherein the components are, in parts by weight: 66.7 parts of biochar, 10.0 parts of bentonite and 0.7 part of magnesium oxide; or: 66.7 parts of biochar, 13.3 parts of bentonite and 0.9 part of magnesium oxide.
6. The soil remediation agent of any one of claims 1 to 5 wherein the biochar is a porous carbonaceous material obtained by pyrolysis and sieving of any one of crop straw or crop seed hulls, or a mixture thereof; preferably, the crop straws comprise rice straws, sorghum straws or corn straws; the crop seed hulls include rice hulls, peanut hulls, or corn hulls.
7. The soil remediation agent of any one of claims 1 to 5 wherein the biochar is produced by a process comprising: pulverizing rice straw and/or rice hull, pyrolyzing at 500-600 deg.C, and sieving with 60-80 mesh sieve.
8. A method of preparing the soil remediation agent of any one of claims 1 to 5 wherein the components are mixed together and sieved.
9. The soil remediation agent of any one of claims 1 to 5 for use in passivating heavy metals in soil.
10. The use according to claim 9, characterized in that the soil amendment composition is incorporated into heavy metal contaminated soil in a proportion of 6.8 wt% to 8.5 wt% by mass while controlling the field water holding capacity of the soil to be about 70%; preferably, the heavy metal is cadmium.
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