CN111218287A - Formula, method and application of combined remediation agent for heavy metals of tin and lead in soil - Google Patents
Formula, method and application of combined remediation agent for heavy metals of tin and lead in soil Download PDFInfo
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Abstract
The invention discloses a formula, a method and application of a combined repairing agent for heavy metal tin and lead in soil. The raw materials adopt zeolite, blast furnace slag, biochar fired by agricultural wastes and cement; the mass ratio is as follows: 2-4 parts of cement, 2-4 parts of blast furnace slag, 0.5-2.5 parts of zeolite, 0-1 part of biochar and 2-6.7 parts of biochar; the repairing agent accounts for 1-5% of the weight of the polluted soil, and the water content in a mixed system of the polluted soil and the repairing agent is 10-30%; the combined repairing agent is prepared by directly mixing zeolite, blast furnace slag, biochar and cement, the heavy metal contaminated soil and the repairing agent are uniformly mixed by using a stirrer, and then the solidified sample is obtained through molding, demolding and maintaining in sequence. The efficient and environment-friendly repairing agent and method for the heavy metal composite polluted soil are suitable for the heavy metal polluted soil with high-concentration composite pollution, particularly have good curing and repairing effects on Sn and Pb, and have certain strength and frost resistance.
Description
Technical Field
The invention belongs to a soil remediation scheme in the field of environmental heavy metal adsorption, and particularly relates to a remediation agent for soil heavy metal Sn and Pb combined pollution, and a preparation method and application thereof.
Background
A large number of industrial contaminated sites are a huge burden in developed and developing countries of the world. And the rapid promotion of industrialization and urbanization causes a large number of polluted sites, the negative effects of heavy metal pollution are gradually shown in the process of re-development and utilization of the polluted sites, the ecological environment and the health of human beings are threatened, so that the polluted sites must be treated by adopting corresponding measures to meet the requirements of re-development and utilization.
According to the proved data, the tin ore resources In China are rich, the tin reserves of the old mines are In the forefront of the world, the old tin ores also contain Cu and Pb, and are associated with various metals such as Zn, Fe, Mn, W, In and the like.
But the exploitation and utilization of tin ore resources cause great pollution and harm to the surrounding ecological environment. In the process of mining the tin ore, the discharge and stockpiling of mine wastes pose a great threat to the environment, and a large amount of associated resources in the tin ore are wasted and have great potential harm to the environment. A large amount of heavy metals (such as Cu, Pb, Zn and the like) in tailings migrate and transform into rivers and soil in various forms and manners. Dust, waste water, waste rocks and the like generated in underground mining operations are main heavy metal pollution sources.
In summary, although the methods and means for treating heavy metals in China are different day by day, the research on heavy metals of Yunnan tin ore is mostly to determine the heavy metals in mining areas and surrounding waste areas and the content of the heavy metals in plants and vegetables aiming at the treatment of heavy metal tin by searching a database, so that few documents can be found, and the treatment of heavy metal tin is not related to the various heavy metal remediation methods listed above, but only one of the heavy metal remediation methods is to adopt a phytoremediation method. The flower plant who has selected 73 kinds of confessions promptly high strength selects ligusticum (gao) originally, balloonflower and wild grass to pollute the stronger tolerance to Sn through soil potted plant experiment and water planting simulation experiment altogether, and is stronger to Sn enrichment ability, has reached the critical content standard of super accumulator plant, has satisfied the essential character of Sn super accumulator plant, tentatively thinks that these 3 plants are potential super accumulator plant.
In summary, the heavy metal solidifying materials and methods adopted at present mainly have the following problems: (1) strong alkalinity, one of the main solidification principles is that hydroxide precipitates are generated with heavy metals, the products are amphoteric substances, and the possibility of re-leaching of the heavy metals is high in the peracid and over-alkali environments; (2) the environment is not friendly, the energy consumption is large in the production process of cement, lime and the like, and atmospheric pollutants such as SO2, NO2, CO2 and the like can be released. (3) The existing formula not only needs to add chemical reagents, but also has more components of a repairing agent, and some materials have complex manufacturing processes and higher repairing cost. (4) The concentration of the treated heavy metal is generally low, and the repair requirement of the high-concentration heavy metal at the periphery of the tailings cannot be met.
The existing soil heavy metal restoration agent generally has the following problems: the repair materials required to be added are various in types and high in addition proportion, and some materials are required to be modified, so that the technical difficulty is increased, and the repair cost is high. The prior art lacks a repairing agent with low preparation cost and excellent repairing effect.
Disclosure of Invention
In order to solve the problems in the background art, the invention provides a formula, a method and application of a combined repairing agent for heavy metal tin and lead in soil, which is an efficient and environment-friendly method for heavy metal combined polluted soil, is suitable for high-concentration combined polluted heavy metal polluted soil, has good curing and repairing effects on Pb and Sn, and has certain strength and frost resistance.
According to the invention, the biochar, the zeolite and the blast furnace slag are used for replacing part of cement, so that the efficient and environment-friendly repairing agent is prepared, and the soil with multiple heavy metal combined pollutions can be effectively treated.
As shown in fig. 1, the technical scheme adopted by the invention is as follows:
a formula of a combined repairing agent for heavy metals of tin and lead in soil is as follows:
the main raw materials are zeolite, blast furnace slag, biochar fired by agricultural wastes and cement, and no excitant is added; the raw materials used were in the following proportions: 2-4 parts of cement, 2-4 parts of blast furnace slag, 0.5-2.5 parts of zeolite, 0-1 part of biochar and 2-6.7 parts of biochar.
The zeolite is natural zeolite or 4A zeolite.
The agricultural wastes are rice hulls, rice straws and walnut shells.
The biochar is rice straw biochar.
Blast furnace slag, a product derived from industrial by-products.
The repairing agent accounts for 1-5% of the weight of the polluted soil, and the water content in a mixed system of the polluted soil and the repairing agent is 10-30%.
The invention relates to a repairing agent for Sn and Pb composite polluted soil.
The application in treating the heavy metal Sn and Pb combined pollution of soil.
Secondly, a preparation method of a soil heavy metal tin and lead combined repairing agent formula comprises the following steps:
the combined repairing agent is prepared by directly mixing zeolite, blast furnace slag, biochar and cement.
Thirdly, a repairing and using method of the soil heavy metal tin and lead combined repairing agent formula:
the method comprises the following steps:
the method comprises the steps of uniformly mixing the heavy metal contaminated soil and a repairing agent by using a stirrer, and then sequentially carrying out molding, demolding and maintaining to obtain a solidified sample, wherein the culture age of the solidified sample is 7-90 days.
The heavy metals added to the simulated soil of the specific implementation were configured with analytically pure Pb (NO3)2 and tin particles, respectively. In the experiment, the addition amount of Pb and Sn is 2500 mg/kg-5000 mg/kg.
The preparation and the test of the cured sample are carried out according to the following steps:
firstly, pouring deionized water into screened soil (using a 20-mesh sieve) until the water content reaches 20% (namely the optimal water content of untreated soil is formed), and fully mixing the soil and water by using a table type electric stirrer to form a uniform soil-water mixture;
then, adding a predetermined weight of the remediation agent to the soil-water mixture, and sufficiently stirring for about 6 minutes to achieve homogeneity to obtain a preliminary mixture;
then, pouring the preliminary mixture into a cylindrical mold with the diameter of 50mm and the height of 100mm, and compacting by a molding machine in three layers;
finally, the sample was carefully removed from the cylindrical mold using a stripper and cured under standard curing conditions for 7, 14, 28 and 90 days.
The heavy metal contaminated soil contains two heavy metals of Pb and Sn.
The invention can improve the compression strength of the solidified body by using the zeolite, can make up the adverse effect of cement on the stability of the solidified product due to strong alkaline environment and air drying process, and can possibly improve the firmness and durability of the common cement in extreme environment.
The invention selects blast furnace slag, zeolite and other materials to replace cement, comprises a novel mineral restoration agent with 5 percent of the total addition of all auxiliary materials of industrial byproducts and agricultural wastes, is used for efficiently restoring high-concentration heavy metal composite polluted soil of Pb and Sn, and is used for efficiently restoring high-concentration heavy metal composite polluted soil of Pb and Sn. Therefore, the problem of cement materials is solved, and the strength of the solidified soil is improved.
The invention selects natural mineral material zeolite, industrial byproduct blast furnace slag and the like as main materials, burns agricultural wastes of rice and straws into biochar, and then synthesizes a low-cost and high-efficiency composite repairing agent formula which is suitable for treating high-concentration heavy metal tin and lead in tin ore tailings with the assistance of a small amount of ordinary portland cement. The maximum treatment concentration of both metals is expected to be 5000 mg/kg.
After the formula is tested by related indexes (such as unconfined compressive strength, leaching toxicity and freeze-thaw cycle) which are universal at home and abroad, the invention is expected to be applied to actual site repair. The formula can realize foundation solidification while repairing heavy metals, and is suitable for secondary development of polluted sites, so that the formula achieves more excellent economic, environmental and social effects compared with similar researches.
In addition, the invention adopts natural mineral zeolite, industrial by-product blast furnace slag and biochar fired by agricultural wastes, namely rice and straw, to replace most of cement, thereby achieving the purpose of resource recycling.
In the specific implementation and use, the heavy metal contaminated soil and the repairing agent are stirred and mixed, so that a series of physical and chemical reactions occur between the repairing agent and the soil body to form a solidified body with low permeability coefficient, and thus, the heavy metal is adsorbed and wrapped in the product of the soil and the repairing agent, so that the purposes of stabilizing heavy metal ions, reducing the leaching characteristic of the heavy metal and improving the physical and mechanical characteristics of the soil body are achieved. Compared with other restoration technologies (such as chemical leaching and biological restoration), the treatment method provided by the invention has the advantages of low restoration cost, convenience in construction, high strength and strong stability of the treated foundation soil, and is particularly suitable for restoration of heavy metal polluted sites.
1) The prior literature also has examples of heavy metal remediation with zeolites, but the concentrations of heavy metals treated are not as high as in the present invention, and most can only treat a single heavy metal.
2) The prior literature lacks a proper formula capable of treating heavy metal tin, and the invention can treat high-concentration tin and lead simultaneously.
3) The unconfined compressive strength of the soil treated by the formula can reach the limit of 350kPa specified by the American environmental protection program after 28 days, the leaching toxicity is lower than the solid waste leaching toxicity standard in China, and the mass loss is less than 5% after 12 times of freeze-thaw cycles, which shows that the formula has high environmental protection value and is beneficial to popularization to engineering application.
The invention has the beneficial effects that:
the invention therefore has the following significance: 1. filling the blank of repairing high-concentration tin in soil in China; 2. the solidification stabilization method is adopted for treating the high-concentration tin pollution for the first time 3. on the basis of treating tin, associated element lead of tin ore can be treated simultaneously, and the common condition of tin and lead existing simultaneously is treated; 4. the low-cost and high-efficiency composite heavy metal restoration agent is obtained through research, and can provide practical industrial application for the restoration of the heavy metal of the Yunnan tin ore.
The formula of the invention is mainly suitable for in-situ remediation of high-concentration and various heavy metal polluted sites, greatly reduces the construction cost and can realize secondary development and utilization of the sites as soon as possible compared with ex-situ remediation widely used at present.
The formula can realize the reinforcement of the soft foundation while repairing heavy metals, and the finished technical indexes strictly meet the environmental protection requirement, thereby being more beneficial to the multifunctional development of the field.
The formula of the invention is expected to greatly improve the effect of only depending on the common Portland cement in the aspects of improving the heavy metal restoration amount, improving the gel strength, shortening the gel time, prolonging the anti-aging time, increasing the thawing cycle, improving the acid and alkali resistance, enhancing the chemical stability and the like.
Because the technology used by the invention is an in-situ repairing technology, the dosage of the repairing agent only accounts for 5 percent of the total dosage of the construction earthwork, and the cost of the repairing agent is only about 1000 yuan/m3The present invention has significant cost advantages. The existing other similar repairing agents have the defects that the total using amount of the repairing agent is large due to the fact that the kinds of materials selected by the repairing agent are various, and some repairing agents also need to use chemical exciting agents, and the total using amount of the repairing agent is up to 20-30% of the total using amount of construction earthwork, so that the cost is increased sharply.
Drawings
FIG. 1 is a technical scheme of the process of the present invention.
Detailed Description
The invention is described in further detail below with reference to the figures and the embodiments.
The method is implemented according to the following steps:
(1) preparing a repairing agent;
(2) mixing the heavy metal contaminated soil and a repairing agent according to a certain proportion;
(3) molding according to the industry standard, demolding, and maintaining for a certain time (7 days, 14 days, 28 days and 60 days to obtain a cured sample;
(4) the test and verification of various performances of the formula are carried out according to indexes such as Unconfined Compressive Strength (UCS), freeze-thaw cycle, leaching toxicity and the like, and the product is simultaneously used for roadbeds or some building materials, and is beneficial to secondary development and utilization after high-concentration industrial polluted sites are repaired.
And carrying out unconfined compressive strength test, leaching concentration test and freeze-thaw test on the cured sample.
The experimental results show that: the unconfined compressive strength of the soil repaired by the method can reach the limit of 350kPa specified by the American environmental protection agency after 28 days, the leaching concentration of heavy metals is effectively reduced, the mass loss is less than 5 percent after 12 times of freeze-thaw cycles, and the unconfined compressive strength of the solidified soil is improved after 12 times of freeze-thaw cycles.
4.1 unconfined compressive strength test
The unconfined compressive strength was determined according to the unconfined compressive strength test method for inorganic binder stabilized materials (T0805-1994). During testing, the testing machine is compressed downwards at the speed of 2mm/min until the test sample is broken, the peak strength at the moment is recorded as the unconfined compressive strength, and the unconfined compressive strengths of various formulas in 7 days, 14 days, 28 days and 90 days of curing are respectively measured.
4.2. Freezing and thawing cycle experiment
And (3) performing a freeze-thaw cycle experiment after the sample is maintained for 28 days according to a freeze-thaw test method for the inorganic binder stable material (T0805-2009), setting the low temperature to be 18 ℃ below zero, the freezing time to be 16 hours, the melting temperature to be 20 ℃, the melting time to be 8 hours, starting freeze thawing, taking out the sample after the melting is finished, weighing the sample, and determining the freeze-thaw strength of the sample, wherein the freeze-thaw resistance of the sample is measured by strength loss and mass loss.
4.3. Leaching toxicity test
A toxicity leaching experiment of a solidified sample is carried out according to a solid waste leaching toxicity leaching method-acetic acid buffer solution method (HJ/T300-2007), the sample which is maintained for 28 days is firstly sieved by a standard set of sieves with the length of 3mm, then 50g of the sample is poured into an extraction bottle, 500mL of an extraction agent prepared by acetic acid is added, the sample is oscillated on a horizontal oscillator for 16h at room temperature and then is kept still for 8h and then is filtered, the oscillation frequency is 110 +/-10 times/min, the amplitude is 40mm, an atomic absorption spectrometer is used for measuring the concentrations of heavy metals Cu, Pb, Zn and Sn in a leachate, and the test standard refers to a hazardous waste identification standard-leaching toxicity identification (GB 5085.3-2007).
The embodiment of the invention tests unconfined compressive strength, leaching toxicity, freezing and thawing resistance and the concentration of heavy metal capable of being treated.
The examples of the invention are as follows:
example 1
The soil to be tested is taken from uncontaminated bare red clay on the ground surface in Wuchuan county, collected soil samples are air-dried, ground and sieved by a 20-mesh sieve for later use. Selecting Pb (NO)3)2And preparing polluted soil by taking the tin powder as a polluted raw material, preparing the polluted raw material into a solution, adding Pb into the soil, mixing Pb with the soil according to the addition amount of 5000mg/kg, mixing Sn with the soil according to the addition amount of 2500mg/kg, and air-drying the mixture for later use after fully and uniformly stirring.
Zeolite and straw biochar (RS) are selected as main raw materials to prepare the repairing agent. The main components of the repairing agent are shown in the following table 1:
TABLE 1 major Components of Rehabitant
| Composition (I) | Cement | Blast furnace slag | Natural zeolite | Biochar |
| 1 | 1.3 parts by mass | 1.7 parts by mass | 1 part by mass | 1 part by mass |
| 2 | 1.3 parts by mass | 1.7 parts by mass | 1 part by mass | 3 parts by mass |
The preparation of the cured samples was carried out as follows: first, deionized water is poured into the screened contaminated soil until the water content reaches 20% (i.e., the optimum water content of the soil). The soil and water were thoroughly mixed with an electric stirrer to form a homogeneous mixture. Secondly, the restoration agent is added to the soil-water mixture to form a mixture so that cement, blast furnace slag, and natural zeolite are added to account for 1.3%, 1.7%, and 1% of the total mixture's solid content, and biochar is added to account for 1%, and 3% of the total mixture's solid content, and the mixture is sufficiently stirred for about 6 minutes to achieve homogeneity. The mixture was then poured into a cylindrical mold of phi 50mm x H100 mm and compacted in three layers using a molding machine. Finally, the sample was carefully removed from the mold using a stripper and cured under standard conditions for 7d, 14d, 28 d. And carrying out unconfined compressive strength test and leaching concentration test on the sample, and carrying out freeze-thaw cycle test on the sample of 28 d.
The cured samples of 7D, 14D and 28D were subjected to an unconfined compressive strength test at a constant strain rate of 1%/min as specified in ASTM D4219. A certain amount of fresh soil was carefully sampled from the cracked sample, and then a leaching concentration test was performed. The unconfined compressive strength test results are shown in tables 2 and 3 below:
TABLE 21% unconfined compressive strength of biochar at various ages
| Age of age | 14d | 28d | 60d | 90d |
| UCS(MPa) | 0.98 | 1.86 | 2.37 | 2.29 |
TABLE 33% unconfined compressive strength of biochar at various ages
| Age of age | 7d | 14d | 28d |
| UCS(MPa) | 2.54 | 3.84 | 4.74 |
The test results show that the unconfined compressive strength of the cured sample is increased along with the increase of the age, the unconfined compressive strength is increased along with the increase of the proportion of the biochar, and the strength of each age meets the 0.35MPa specified by the United states environmental protection agency on a refuse landfill site. The unconfined compressive strength of the added 3 percent of the biochar is respectively increased by 2.86MPa (292 percent) and 3.08MPa (186 percent) in 14d and 28d compared with the unconfined compressive strength of the added 1 percent. The reason is that the addition of the biochar promotes the hydration of cement, so that the strength of the soil body is enhanced, and in addition, the water absorption rate of the macroporous biochar is higher, so that the local water-cement ratio is reduced, a higher densification effect is generated, and the strength of the soil body is also improved.
The leaching concentration of heavy metals was evaluated using TCLP-EPA method 1311. TCLP extract (5.7ml CH)3COOH and 64.3ml of 1mol/L NaOH) was 4.93. + -. 0.05. The leaching concentration results are shown in tables 4 and 5 below:
table 41% heavy metal leaching concentration by biochar treatment
| Maintenance time | 28d | 60d | 90d |
| Pb leaching concentration (mg/L) | 180.667 | 182.002 | 183.037 |
| Sn Leaching concentration (mg/L) | 1.604 | 12.194 | 14.257 |
Table 53% heavy metal leaching concentration by charcoal treatment
| Maintenance time | 14d | 28d |
| Pb leaching concentration (mg/L) | 139.461 | 155.608 |
| Sn Leaching concentration (mg/L) | 6.627 | 0.906 |
The results of the tests (table 4) show that the solidification rate of Pb by 1% biochar treatment was 96.39%, 96.36%, 96.34% at age 28 days, 60 days and 90 days, respectively, and the data show that the leaching concentration of Pb after 28 days had substantially stabilized. The solidification rate of Sn is 99.94 percent, 99.51 percent and 99.43 percent respectively at 28 days, 60 days and 90 days of age, the leaching concentration of Sn is slightly fluctuated between 60 days and 90 days, but the fixed total amount is still high, which shows that the durability of the formula is still good. The 3% biochar treatment at 14d had a Pb cure rate of 97.21% and a tin cure rate of 97.35%.
Therefore, the repairing agent can effectively fix the combined pollution of Sn and Pb in soil at the same time.
Comparative example 1
The repairing agent is prepared from blast furnace slag, zeolite and cement, and is used for efficiently repairing high-concentration heavy metal composite polluted soil of Pb and Sn. The main components of the repairing agent are as follows:
TABLE 6 major Components of Rehabitant
| Cement | Blast furnace slag | Natural zeolite |
| 2.3 parts by mass | 1.7 parts by mass | 1 part by mass |
The components and contents of the repairing agent are as follows:
TABLE 7 ingredients contained in the repairing agent and their contents
The soil to be tested is taken from uncontaminated bare red clay on the ground surface in Wuchuan county, collected soil samples are air-dried, ground and sieved by a 20-mesh sieve for later use. Selecting Pb (NO)3)2And preparing polluted soil by taking the tin powder as a polluted raw material, preparing the polluted raw material into a solution, adding the solution into the soil, mixing Pb and Sn with the soil according to the addition amount of 5000 mg/mg and 2500mg/kg respectively, fully stirring uniformly, and air-drying for later use.
The repairing agent is added into simulated polluted soil, so that cement, blast furnace slag and natural zeolite which are added account for 2.3 percent, 1.7 percent and 1 percent of the solid content of the total mixture are uniformly stirred to prepare a cylindrical sample with phi 50mm multiplied by H100 mm. And (3) curing the test sample under standard conditions after demoulding, measuring the unconfined compressive strength of the test sample when the test sample is cured for 7d, 14d, 28d, 90d and 180d, carefully sampling a certain amount of fresh soil from the cracked sample, then performing a TCLP test, and performing a freeze-thaw cycle test when the test sample is cured for 28 d.
The test results of unconfined compressive strength tests with a fixed strain rate of 1%/min for samples cultured for 7D, 14D, 28D, 90D and 180D as specified in ASTM D4219 are as follows:
TABLE 8 unconfined compressive strength at each age
The results show that the strength of the cured samples all increased with age, and the strength of each age satisfied 0.35MPa specified by the us epa for landfill sites. The unconfined compressive strength at 28d and 90d is reduced by 0.24MPa (12.90%) and 0.71MPa (31.00%) compared with that of the treatment of adding 1% of biochar; the unconfined compressive strength at 7d, 14d and 28d is reduced by 1.99MPa (78.35%), 2.59MPa (67.45%) and 3.12MPa (65.82%) compared with the treatment of adding 3% biochar. In general, the unconfined compressive strength of the cured sample of the formula is greatly reduced compared with that of the formula of the case one (added with the biochar), the curing effect is not ideal as that of the case 1, and the related standard is also met. Long-term tests of 90d and 180d are carried out at the same time, and the results show that the unconfined compressive strength of the sample slightly floats but basically tends to be stable after 28 days.
The leaching concentration of heavy metals was evaluated using TCLP-EPA method 1311. TCLP extract (5.7ml CH)3COOH and 64.3ml of 1mol/L NaOH) was 4.93. + -. 0.05. The leach concentration results are shown in table 9 below:
TABLE 9 heavy Metal Leaching concentration
The results of tests with no biochar added, with blast furnace slag, zeolite and cement only added, show (table 9): although the leaching concentration of heavy metal Pb is slightly increased along with the increase of the age, the fixation rate of lead in the soil to be repaired is still 94.96% even when the leaching concentration of lead reaches the maximum value in 90 days.
The combination of two indexes of unconfined compressive strength and leaching concentration finds that: the repairing agent does not contain biochar, the leaching concentration is not as stable as that of the biochar in the long-term maintenance process, the strength is not as high as that of the biochar, and the overall treatment effect does not reach the optimal effect.
Comparative example 2
The soil to be tested is taken from uncontaminated bare red clay on the ground surface in Wuchuan county, collected soil samples are air-dried, ground and sieved by a 20-mesh sieve for later use. Selecting Pb (NO)3)2And preparing polluted soil by taking the tin powder as a polluted raw material, preparing the polluted raw material into a solution, adding Pb into the soil, mixing Pb with the soil according to the addition amount of 5000mg/kg, mixing Sn with the soil according to the addition amount of 2500mg/kg, and air-drying the mixture for later use after fully and uniformly stirring.
The 4A zeolite is selected to replace natural zeolite to develop a repairing agent, and the repairing effect of the 4A zeolite on the heavy metal polluted soil is researched. The main components of the repairing agent are as follows:
TABLE 10 major ingredients of restoratives
The repairing agent is added into simulated polluted soil, so that cement, blast furnace slag and 4A zeolite account for 2.3 percent, 1.7 percent and 1 percent of the solid content of the total mixture after being added, and the mixture is uniformly stirred to prepare a cylindrical sample with phi 50mm multiplied by H100 mm. The samples were demolded for curing, and unconfined compressive strength tests were performed for sample curing at 14d, 28d, 60d, and 90d, respectively, and TCLP tests were performed for sample curing at 28 d. Table 11 below is the results of items relevant to the examination of 4A zeolite.
TABLE 114A Zeolite related indices
The cured samples of 14D, 28D, 60D and 90D were subjected to an unconfined compressive strength test at a set strain rate of 1%/min as specified in ASTM D4219. A certain amount of fresh soil was carefully sampled from the cracked sample, and then a leaching concentration test was performed. The unconfined compressive strength test results are given in table 12 below:
TABLE 12 unconfined compressive strength at each age
| Age of age | 14d | 28d | 60d | 90d |
| UCS(MPa) | 0.85 | 1.43 | 1.85 | 2.18 |
The test results show that the strength of the cured samples increases along with the increase of ages, and the strength of each age is greater than 0.5MPa, which meets the 0.35MPa specified by the United states environmental protection agency on refuse landfill sites. The strength of the soil body added with the 4A zeolite is lower than that of the soil body added with the straw biochar in all ages, and the strength of the soil body added with the 4A zeolite is respectively reduced by 0.13MPa (13.27%), 0.43MPa (23.12%), 0.52MPa (21.94%) and 0.11MPa (4.80%) compared with the strength of the soil body added with the 1% biochar in the ages of 14 days, 28 days, 60 days and 90 days. The 14d and 28d are respectively reduced by 2.99MPa (77.86%) and 3.31MPa (69.83%) compared with the group added with 3% of treatment. The unconfined compressive strength of the cured sample of the formulation is generally not as desirable as that of example 1.
The leaching concentration of heavy metals was evaluated using TCLP-EPA method 1311. TCLP extract (5.7ml CH)3COOH and 64.3ml of 1mol/L NaOH) was 4.93. + -. 0.05. The leach concentration results are given in table 13 below:
TABLE 13 heavy metal leach out concentration
The test results show that the effect of Pb and Sn after the addition of the 4A zeolite is better than that of the natural zeolite (the effect is better when the leaching concentration is smaller) but the effect is still not as good as that after the addition of the biochar in each age period.
The conclusion can be drawn by combining the test results: the repairing agent does not contain biochar, the leaching concentration is not as stable as that of the biochar in the long-term maintenance process, the strength is not as high as that of the biochar, and the overall treatment effect does not reach the optimal effect.
Comparative example 3
Soil was collected from southern lake wetland parks in inner Mongolia autonomous region and Haote City. The sampling depth is 0-20cm, the collected soil sample is air-dried, ground and sieved by a 20-mesh sieve for later use. The particle size of the soil was measured by a laser particle sizer, the liquid plastic limit value measured by the soil sample was combined, and according to the classification plastic diagram, the test soil used was low liquid limit Clay (CL), and the particle size analysis results are shown in table 14 below. The basic physicochemical properties of the soil are shown in Table 15 below.
TABLE 14 analysis results of particle size of soil
| Particle size/mm | <0.005 | 0.005–0.075mm | 0.075–2mm |
| Mass fraction/% | 1.77 | 22.07 | 76.16 |
TABLE 15 basic physical Properties of the soil
| Optimum moisture content (%) | Liquid limit (%) | Plastic limit (%) | Plastic limit index (%) |
| 20 | 27.5 | 18.2 | 9.3 |
Preparing simulated polluted soil by selecting Pb (NO)3)2And preparing a solution by taking the tin powder as a pollution raw material, adding the solution into soil, mixing Pb with the soil according to the addition amount of 5000mg/kg, mixing Sn with the soil according to the addition amount of 2500mg/kg, and air-drying the mixture after fully and uniformly stirring the mixture for later use.
The main components of the repairing agent are shown in the following table 16:
TABLE 16 repair agent principal Components
The agents were mixed and stirred uniformly to prepare a restoration agent according to the formulation shown in table 16, the prepared restoration agent was added to the simulated contaminated soil so that cement, blast furnace slag, and biochar were added to account for 2.3%, 1.7%, and 1% of the total mixture in terms of solid content, and the mixture was mixed and stirred uniformly to prepare a cylindrical sample of phi 50mm × H100 mm. And (3) demolding the sample, curing, and performing unconfined compressive strength tests and heavy metal leaching toxicity tests when the sample is cured for 7d, 14d, 28d and 60d respectively.
The cured samples of 7D, 14D, 28D and 60D were subjected to an unconfined compressive strength test at a set strain rate of 1%/min as specified in ASTM D4219. A certain amount of fresh soil was carefully sampled from the 28d cracked sample and then subjected to the TCLP test. The unconfined compressive strength test results are given in table 17 below:
TABLE 17 unconfined compressive strength (MPa) at each age
The test results show (Table 17) that the strength of the cured specimens all increased with age. In general, the unconfined compressive strength of the cured sample of the formula is lower than that of the case 1, and is respectively reduced by 0.39MPa (20.97%) and 0.85MPa (35.86%) at 28d and 60d compared with the treatment of adding 1% of biochar. The reduction in the concentration of the additive was 2.03MPa (79.92%), 2.61MPa (67.97%), 3.27MPa (68.99%) at 7d, 14d and 28d, respectively, compared with the addition of the 3% treatment group
The leaching concentration of heavy metals was evaluated using TCLP-EPA method 1311. TCLP extract (5.7ml CH)3COOH and 64.3ml of 1mol/L NaOH) was 4.93. + -. 0.05. The leach concentration results are given in table 18 below:
table 18 heavy metal 28d leach concentration (mg.l)-1)
The test result shows thatAfter the polluted soil is treated by adding zeolite and only blast furnace slag, biochar and cement, Pb and Sn can be repaired, but the solidification rate of lead can only reach 95.72%, and the solidification rate of tin can only reach 98.46%. Leaching concentration of Pb is more than 1% biochar effect (180.667 mg.L)-1) The increase is 18.54 percent, and the leaching concentration of Sn is 22.94 times higher than the effect (1.604) of 1 percent of biochar; and the leaching concentration of Sn is more than that of the case where only zeolite, blast furnace slag and cement are added and no biochar is added (27.450 mg.L.)-1) The increase difference is 39.89%. The combination of unconfined compressive strength is generally lower than that of case 1 and the treatment of adding blast furnace slag, zeolite and cement, so that the ideal effect is not achieved.
Comparative example 4
Soil was collected from southern lake wetland parks in inner Mongolia autonomous region and Haote City. The sampling depth is 0-20cm, the collected soil sample is air-dried, ground and sieved by a 20-mesh sieve for later use. The particle size of the soil was measured by a laser particle sizer, the liquid plastic limit value measured by the soil sample was combined, and according to the classification plastic diagram, the test soil used was low liquid limit Clay (CL), and the particle size analysis results are shown in table 19 below. The basic physicochemical properties of the soil are shown in table 20 below.
TABLE 19 analysis results of particle size of soil
| Particle size/mm | <0.005 | 0.005–0.075mm | 0.075–2mm |
| Mass fraction/% | 1.77 | 22.07 | 76.16 |
TABLE 20 basic physical Properties of the soil
| Optimum moisture content (%) | Liquid limit (%) | Plastic limit (%) | Plastic limit index (%) |
| 20 | 27.5 | 18.2 | 9.3 |
Preparing simulated polluted soil by selecting Pb (NO)3)2And preparing a solution by taking the tin powder as a pollution raw material, adding the solution into soil, mixing Pb with the soil according to the addition amount of 5000mg/kg, mixing Sn with the soil according to the addition amount of 2500mg/kg, and air-drying the mixture after fully and uniformly stirring the mixture for later use.
The main components of the repairing agent are shown in the following table 21:
TABLE 21 Repair agent principal Components
The repairing agent is prepared by mixing the above materials according to the formulation shown in Table 21, wherein the activating agents are CaO, MgO, and SiO2、Na2SO4The addition amount of the repairing agent accounts for 8 percent, 0.4 percent and 0.6 percent of the main repairing agent, and the prepared repairing agent is added into the simulated polluted soil to ensure thatThe cement and the biochar which are added account for 12 percent and 3 percent of the solid content of the total mixture. The mixture was stirred uniformly to prepare a cylindrical sample having a diameter of 50 mm. times.H 100 mm. And (3) demolding the sample, curing, and performing unconfined compressive strength tests and TCLP tests when the sample is cured for 7d, 14d, 28d and 60d respectively.
The cured samples of 7D, 14D, 28D and 60D were subjected to an unconfined compressive strength test at a set strain rate of 1%/min as specified in ASTM D4219. A certain amount of fresh soil was carefully sampled from the 28d fractured samples and then subjected to the leaching concentration test. The unconfined compressive strength test results are given in table 22 below:
TABLE 22 unconfined compressive strength (MPa) at each age
The test results show that the strength of the cured samples increases along with the increase of the age, and the cured samples meet the 0.35MPa specified by the United states environmental protection agency on the landfill site.
The leaching concentration of heavy metals was evaluated using TCLP-EPA method 1311. TCLP extract (5.7ml CH)3COOH and 64.3ml of 1mol/L NaOH) was 4.93. + -. 0.05. The leach concentration results are given in table 23 below:
table 23 leaching concentration (mg.l) of heavy metal 28d-1)
The test result shows that after the repairing agent is added, Pb and Sn can be cured, wherein the curing rate of lead reaches 95.66%, and the curing rate of tin reaches 85.95%. And the unconfined compressive strength of the soil body after solidification is increased, because the addition amount of cement and biochar is larger and reaches more than 15%, and a large amount of chemical reagents are added as an excitant, the unconfined compressive strength is higher. But from leachingFrom the viewpoint of concentration effect, the leaching concentration of Pb at 28 days was higher than that of the blast furnace slag and 1% biochar-treated group (180.667 mg.L.)-1) 20.18% higher, Sn leaching concentration ratio was added to blast furnace slag, 1% biochar treatment group (1.604 mg.L)-1) Higher by 20.9 times. For Sn, the leaching concentration of 28d was 27.98% higher than that after the treatment with zeolite, blast furnace slag and cement.
Therefore, the curing effect of the conventional method of adding a part of the activator, cement and biochar is higher than the curing effect of adding zeolite and biochar in strength, but the heavy metal leaching concentration effect is not as excellent as the effect of adding zeolite, biochar and the like of the present invention.
Comparative example 5
The soil to be tested is taken from uncontaminated bare red clay on the ground surface in Wuchuan county, collected soil samples are air-dried, ground and sieved by a 20-mesh sieve for later use. And (3) determining the particle size of the soil by using a laser particle sizer, combining the liquid plastic limit value determined by the soil sample, and adopting the test soil which is low liquid limit silt red clay according to a classification plastic diagram. The basic physical properties of the soil and the results of the particle size analysis are shown in tables 19 and 25 below:
TABLE 24 basic physical Properties of the soil
| Air-dried moisture content (%) | Optimum moisture content (%) | Liquid limit (%) | Plastic limit (%) | Plastic limit index (%) | Natural dry density (g/cm)-3) | Maximum dry Density (g/cm)-3) |
| 3.9 | 15.47 | 41.0 | 19.4 | 21.6 | 2.710 | 2.13 |
TABLE 25 analysis results of particle size of soil
| Particle size/mm | <0.005 | 0.005-0.01 | 0.01-0.05 | 0.05-0.075 | 0.075-0.25 |
| Mass fraction/% | 5.31 | 18.23 | 57.22 | 10.62 | 8.62 |
Preparing simulated polluted soil by selecting Pb (NO)3)2And preparing a solution by taking the tin powder as a pollution raw material, adding the solution into soil, mixing Pb with the soil according to the addition amount of 5000mg/kg, mixing Sn with the soil according to the addition amount of 2500mg/kg, and air-drying the mixture after fully and uniformly stirring the mixture for later use.
The repairing agent is prepared by taking cement and blast furnace slag as components, and the main components are as follows
TABLE 26 repair Agents principal Components
The agents were mixed and stirred uniformly to prepare a repairing agent according to the formulation shown in table 26, the prepared repairing agent was added to the simulated contaminated soil so that cement and blast furnace slag were added to account for 2.3% and 1.7% of the total mixture in terms of solid content, and the mixture was stirred uniformly to prepare a cylindrical sample having a diameter of 50mm × H100 mm. And (4) demolding the sample, maintaining, respectively performing unconfined compressive strength tests and heavy metal leaching toxicity tests when the sample is maintained for 7d and 14 d.
The cured 7D and 14D specimens were subjected to an unconfined compressive strength test at a set strain rate of 1%/min as specified in ASTM D4219. A certain amount of fresh soil was carefully sampled from the cracked sample, and then a leaching concentration test was performed. The unconfined compressive strength test results are given in table 27 below:
TABLE 27 unconfined compressive strength (MPa) at each age
The test results show that the strength of the cured samples increases along with the increase of the age, and the cured samples meet the 0.35MPa specified by the United states environmental protection agency on refuse landfill sites.
The leaching concentration of heavy metals was evaluated using TCLP-EPA method 1311. TCLP extract (5.7ml CH)3COOH and 64.3ml of 1mol/L NaOH) was 4.93. + -. 0.05. The leach concentration results are given in table 28 below:
table 28 heavy metal 28d leach concentration (mg.l)-1)
The test results show that the curing rate of Pb does not reach 95% after 28 days of curing after only adding the cement and the blast furnace slag. Although the leaching concentration of Sn is not so large, the Sn leaching concentration is higher than the effect of the treatment of adding zeolite and 1% of biochar at the same time (1.604 mg.L)-1) 26.89 times higher than that of zeolite, blast furnace slag and cement without biochar (27.450 mg.L)-1) Increased by 62.99%, increased by 16.51% compared with the effect of adding biochar, blast furnace slag and cement without zeolite (38.401mg.L-1), and also compared with the effect of adding cement, biochar and part of excitant only (35.131 mg.L)-1) The increase is 27.35%. In general, the effect of treatment by adding only cement and blast furnace slag is better than that by adding zeolite and biochar in strength, but the effect of heavy metal leaching concentration is much higher than that by adding zeolite and biochar, and the effect is not ideal.
For the phenomenon that the strength of comparative example 4 and comparative example 5 is increased, the technical problem of the combined repair of heavy metals of tin and lead is solved, and the comparative example 4 and comparative example 5 can not be effectively completed, but the invention can be realized.
Comparative example 6
Preparing simulated contaminated soil, selecting Pb (NO3)2 and tin powder as contaminated raw materials, preparing a solution, adding the solution into the soil, mixing Pb with soil according to the addition amount of 50 mg/kg, mixing Sn with the soil according to the addition amount of 100 mg/kg, and air-drying the mixture for later use after fully and uniformly stirring.
The main components of the repairing agent are shown in the following table 29:
TABLE 29 repair Agents principal Components
The repairing agent is prepared by mixing and stirring the medicaments uniformly according to the formula shown in the table, the prepared repairing agent is added into simulated polluted soil, so that the added blast furnace slag and zeolite account for 15 percent and 5 percent of the solid content of the total mixture, and the mixture is uniformly mixed and stirred to prepare a cylindrical sample with phi 50mm multiplied by H100 mm. The samples were demolded and cured, and unconfined compressive strength tests were performed for samples cured at 7d, 14d, and 28d, respectively, and a TCLP test was performed.
The cured samples of 7D, 14D and 28D were subjected to an unconfined compressive strength test at a constant strain rate of 1%/min as specified in ASTM D4219. A certain amount of fresh soil was carefully sampled from the 28d fractured samples and then subjected to the leaching concentration test. The unconfined compressive strength test results are given in table 30 below:
TABLE 30 unconfined compressive strength (MPa) at each age
The test results show that the strength of the cured samples increases with the increase of ages, and the strength of each age meets the 0.35MPa specified by the United states environmental protection agency on refuse landfill sites. The unconfined compressive strength of the cured samples of the formula at 14d and 28d is respectively reduced by 0.11MPa (11.22%) and 0.42MPa (22.58%) after being treated by adding 1% of biochar.
The leaching concentration of heavy metals was evaluated using TCLP-EPA method 1311. The TCLP extract (5.7ml CH3 COOH and 64.3ml 1mol/L NaOH) had an initial pH of 4.93. + -. 0.05. The leach concentration results are shown in table 31 below:
table 31 leaching concentration (mg.l) of heavy metal 28d-1)
The test result shows that the Pb and Sn can be solidified and polluted after only adding blast furnace slag and zeolite, wherein the solidification rate of lead reaches 98.97%, and the solidification rate of tin reaches 99.99%. However, the initial concentration of the treated Pb is low, and the addition amount is up to 20%, whereas the formula disclosed by the invention is that the repairing agent prepared from cement or cement and biochar is added on the basis of blast furnace slag and zeolite, the total addition amount of all materials is only 5%, so that the Pb concentration can be treated up to 5000mg/kg, and the tin concentration can also be treated up to 2500 mg/kg.
Therefore, after cement and charcoal are removed, blast furnace slag cannot be effectively excited to achieve an ideal repairing effect. In combination with unconfined compressive strength, although blast furnace slag and zeolite have certain restoration capability on Pb and Sn composite contaminated soil, the effect of adding cement or cement and biochar on the basis of the two materials is not good.
The following conclusions are therefore drawn from the above case:
1. the repairing agent prepared from the biochar, the zeolite, the blast furnace slag and the cement serves as raw materials, and shows excellent effects on unconfined compressive strength and heavy metal leaching concentration when high-concentration Pb (5000 mg/kg) Sn (2500 mg/kg) compound contaminated soil is repaired at the same time.
2. The addition of zeolite or 4A zeolite, blast furnace slag and cement or biochar, blast furnace slag and cement can have a certain curing effect on heavy metals, but the effect on unconfined compressive strength and heavy metal leaching concentration is not as good as that of biochar.
3. The cement, the biochar and part of the excitant are added, the unconfined compressive strength is higher due to the large addition amount of the excitant and the action of the excitant, but the leaching concentration of heavy metal, particularly Sn, is more than 30 times higher than that of the biochar after 1 percent is added, and is also more than 27.98 percent higher than that of the biochar after zeolite, blast furnace slag and cement are added.
4. The addition of cement and blast furnace slag alone is not as effective in leaching heavy metals as the addition of zeolite or biochar.
5. Only blast furnace slag and zeolite are selected and added up to 20%, and low-concentration Pb (50 mg/kg) and Sn (100 mg/kg) can be repaired at the same time.
Finally, the implementation proves that the repairing agent material simultaneously added with the zeolite, the blast furnace slag, the biochar and the cement can effectively repair the heavy metal Sn polluted soil and the heavy metal Sn and Pb composite polluted soil, the repairing agent can be implemented only when the four components are simultaneously added, and the repairing agent can also be implemented under the condition of higher heavy metal concentration.
Claims (7)
1. The formula of the combined repairing agent for heavy metals of tin and lead in soil is characterized in that: the main raw materials are zeolite, blast furnace slag, biochar fired by agricultural wastes and cement; the raw materials used were in the following proportions: 2-4 parts of cement, 2-4 parts of blast furnace slag, 0.5-2.5 parts of zeolite, 0-1 part of biochar and 2-6.7 parts of biochar.
2. The application of the combined repairing agent formula of the heavy metals of tin and lead in the soil according to claim 1 is characterized in that: the repairing agent accounts for 1-5% of the weight of the polluted soil, and the water content in a mixed system of the polluted soil and the repairing agent is 10-30%.
3. The application of the combined repairing agent formula of the heavy metals of tin and lead in the soil according to claim 1 is characterized in that: the application in treating the heavy metal Sn and Pb combined pollution of soil.
4. A preparation method of a combined repairing agent formula of heavy metals of tin and lead in soil is characterized by comprising the following steps:
the combined repairing agent is prepared by directly mixing zeolite, blast furnace slag, biochar and cement.
5. A repairing and using method of a soil heavy metal tin and lead combined repairing agent formula is characterized in that: the method comprises the following steps: the method comprises the steps of uniformly mixing the heavy metal contaminated soil and a repairing agent by using a stirrer, and then sequentially carrying out molding, demolding and maintaining to obtain a solidified sample, wherein the culture age of the solidified sample is 7-90 days.
6. The method for repairing and using the combined repairing agent formula for the heavy metals of tin and lead in the soil according to claim 5, is characterized in that: the preparation and testing of the cured samples were carried out as follows:
firstly, pouring deionized water into screened soil until the water content reaches 20 percent (namely the optimal water content of untreated soil is formed), and fully mixing the soil and water by using a table type electric stirrer to form a uniform soil-water mixture;
then, adding a predetermined weight of the remediation agent to the soil-water mixture, and sufficiently stirring for about 6 minutes to obtain a preliminary mixture;
then, pouring the preliminary mixture into a cylindrical mold with the diameter of 50mm and the height of 100mm, and compacting by a molding machine in three layers;
finally, the sample was carefully removed from the cylindrical mold using a stripper and cured under standard curing conditions for 7, 14, 28 and 90 days.
7. The method for repairing and using the combined repairing agent formula for the heavy metals of tin and lead in the soil according to claim 5, is characterized in that: the heavy metal contaminated soil contains two heavy metals of Pb and Sn.
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