CN111330966A - In-situ slurry stabilization restoration method for heavy metal polluted site - Google Patents
In-situ slurry stabilization restoration method for heavy metal polluted site Download PDFInfo
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- CN111330966A CN111330966A CN202010160662.0A CN202010160662A CN111330966A CN 111330966 A CN111330966 A CN 111330966A CN 202010160662 A CN202010160662 A CN 202010160662A CN 111330966 A CN111330966 A CN 111330966A
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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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/354—After-treatment
- C01B32/36—Reactivation or regeneration
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/354—After-treatment
- C01B32/372—Coating; Grafting; Microencapsulation
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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
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
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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
- C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation
Abstract
The invention discloses an in-situ slurry stabilization restoration method for a heavy metal polluted site, which comprises the following steps: isolation, determination of the water content of heavy metal contaminated soil, slurrying of heavy metal contaminated soil, addition of stabilizing agents, standing, separation, wastewater treatment, soil aging, acceptance evaluation, cyclic treatment and covering maintenance. The invention reduces dust pollution in the treatment process, is beneficial to uniform mixing between the stabilizing agent and the heavy metal polluted soil, ensures the full reaction between the stabilizing agent and the heavy metal, and improves the solidification and stabilization effect of the heavy metal.
Description
Technical Field
The invention relates to the technical field of soil remediation, in particular to an in-situ slurry stabilization remediation method for a heavy metal contaminated site.
Background
With the rapid development of industry, agriculture and scientific technology, the population expands and the natural environment deteriorates increasingly. Heavy metals in soil are continuously enriched and exceed the self-cleaning capacity of the soil, so that the composition, structure and function of the soil are changed, and the soil pollution is caused. According to investigation, the annual loss of grain in China due to heavy metal pollution of soil reaches 1200 million tons, and the economic loss of over 200 million yuan is directly caused. Heavy metal pollution generally refers to pollution in the environment caused by metals or their compounds with specific gravity greater than 5 or 4 (mainly including Cu, Zn, Cd, Pb, Hg, Cr, As, Ni, Co). The toxicity of different heavy metals to organisms is very different, and the toxicity of lead and cadmium is very high. Heavy metals in soil cannot be biodegraded, are not easy to lose, are enriched in soil, and circulate in nature along with food chains. Along with the extension of the food chain, the enrichment condition is gradually amplified, various diseases are caused finally, and the health of the human body is directly harmed. Therefore, the hazard and remediation control of heavy metal contaminated soil has been a global problem.
Disclosure of Invention
The invention provides an in-situ slurry stabilization restoration method for a heavy metal polluted site, and aims to solve the problems that in the prior art, the restoration step of the heavy metal polluted site is complicated, and the soil restoration is not complete.
The invention aims to solve the technical problem of providing an in-situ slurry stabilization restoration method for a heavy metal polluted site, which comprises the following steps:
step 1, isolation: isolating the heavy metal contaminated soil from the soil which is not contaminated around the heavy metal contaminated soil;
step 2, determining the water content of the heavy metal contaminated soil: determining the water content of the heavy metal contaminated soil according to a drying method;
step 3, slurrying the heavy metal contaminated soil: loosening the soil polluted by the heavy metal, injecting water according to the moisture content after loosening the soil, and stirring to change the soil polluted by the heavy metal into in-situ slurry of a heavy metal polluted site;
step 4, adding a stabilizing agent: adding a stabilizing agent into the in-situ slurry of the heavy metal polluted site in a stirring state;
step 5, standing: after the stabilizing agent is added, continuously stirring the in-situ slurry in the heavy metal polluted site for 1-2 hours at the stirring speed of adding the stabilizing agent, and standing for 10-12 hours after stirring is finished;
step 6, separation: after standing, pumping out an upper solution of the in-situ slurry of the heavy metal polluted site and placing the upper solution in a sewage pool;
step 7, wastewater treatment and soil aging: carrying out wastewater treatment on the upper solution discharged into the sewage tank and carrying out soil aging treatment on the lower layer of the in-situ slurry of the heavy metal polluted site;
and 8: acceptance evaluation: carrying out soil aging treatment on the lower layer of the in-situ slurry of the heavy metal polluted site, and then carrying out acceptance evaluation;
and 9, cyclic treatment: if the acceptance evaluation does not reach the standard, the lower layer of the in-situ slurry of the heavy metal polluted site is processed again in the steps 1-8 so that the lower layer of the in-situ slurry of the heavy metal polluted site reaches the standard of the acceptance evaluation;
step 10, covering and maintaining: and if the acceptance evaluation reaches the standard, performing covering maintenance on the lower layer of the in-situ slurry of the heavy metal polluted site.
Preferably, in step 3 of the in-situ slurry stabilization and remediation method for the heavy metal contaminated site, the depth of loose soil in the heavy metal contaminated soil is 4-6 m.
Preferably, in step 3 of the method for stabilizing and repairing in-situ slurry in a heavy metal contaminated site, the water content of the in-situ slurry in the heavy metal contaminated site is 140-160%.
Preferably, in the method for in-situ slurry stabilization remediation of a heavy metal contaminated site, the weight-area ratio of the addition amount of the stabilizing agent to the heavy metal contaminated soil is (0.5-1.5): 1 (kg/m)2)。
Preferably, in step 3 of the in-situ slurry stabilization remediation method for a heavy metal contaminated site, the water is one of tap water, river water or treated industrial water.
Preferably, in the method for in-situ mud stabilization and remediation of the heavy metal contaminated site, the stabilizing agent comprises the following components in parts by weight: 20-40 parts of activated carbon or modified activated carbon, 30-60 parts of quicklime and 5-10 parts of complexing agent.
Preferably, in the method for in-situ mud stabilization and remediation of the heavy metal contaminated site, the stabilizing agent comprises the following components in parts by weight: 20-40 parts of activated carbon or modified activated carbon, 30-60 parts of quicklime, 5-10 parts of complexing agent, 7-15 parts of phosphate and 4-6 parts of magnesium chloride.
More preferably, the stabilizing agent comprises the following components in parts by weight: 20-40 parts of modified activated carbon, 30-60 parts of quicklime, 5-10 parts of complexing agent, 7-15 parts of phosphate and 4-6 parts of magnesium chloride.
Preferably, in the method for in-situ sludge stabilization and remediation of the heavy metal contaminated site, the preparation method of the modified activated carbon comprises the following steps:
s1, sieving the activated carbon in a 5-20 mesh sieve to obtain 5-20 mesh activated carbon;
s2, taking 5-10 parts by weight of the 5-20 mesh activated carbon, soaking in 300 parts by weight of sodium hydroxide aqueous solution 200-1.5 h, washing with water for 3-5 times, then drying at the temperature of 120-130 ℃ for 2-4h, cooling to room temperature, soaking in saturated copper sulfate solution for 1-3h to obtain activated carbon;
s3, adding 300 parts by weight of water, 8-16 parts by weight of sodium carboxymethylcellulose, 15-20 parts by weight of 1,2,3, 4-butanetetracarboxylic acid and 5-10 parts by weight of sodium dihydrogen phosphate into the activated carbon, manually stirring for 1-2min to obtain a mixed solution, then carrying out ultrasonic treatment on the mixed solution for 10-30min, stirring for 5-7h under the condition of 100 revolutions per minute to uniformly mix the mixed solution, standing the uniformly mixed solution for 10-12h, filtering, pre-drying the precipitate obtained after filtering at the temperature of 70-90 ℃, wherein the pre-drying time is 11-13h, quickly heating the precipitate to 200 ℃ after the pre-drying is finished, keeping for 5-8min, then alternately washing for 3-5 times by using water and ethanol at the temperature of 60-70 ℃, drying to obtain the modified activated carbon.
Preferably, in the method for in-situ sludge stabilization and remediation of the heavy metal contaminated site, the complexing agent is one or more of gluconic acid and tartaric acid.
Preferably, in the method for in-situ slurry stabilization remediation of the heavy metal contaminated site, the complexing agent is prepared from gluconic acid and tartaric acid in a weight ratio of (1-2): (4-5) in proportion.
Has the advantages that:
the invention makes the soil polluted by heavy metal to be slurried, then adds the stabilizing agent in a stirring state, makes the stabilizing agent fully contact with the soil polluted by heavy metal, the heavy metal contaminated soil is fully contacted with the stabilizing agent, then is kept stand for layering, the upper layer solution is pumped out for independent sewage treatment, the lower layer is aged and evaluated, the method reduces dust pollution in the treatment process, is beneficial to uniform mixing between the stabilizing agent and the heavy metal polluted soil, ensures full reaction between the stabilizing agent and the heavy metal, improves the solidification and stabilization effect of the heavy metal, and simultaneously ensures the problem of insufficient repair of the heavy metal polluted site.
Detailed Description
The invention provides an in-situ slurry stabilization restoration method for a heavy metal polluted site, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the embodiment, an excavator is adopted to stir the soil in the heavy metal pollution site into slurry in the stirring process, and a stirring head in the excavator is a stirring head with the model of HX-X3 and is purchased from super power equipment, Inc. of Bazhou.
In the embodiment, the upper solution discharged into the sewage tank is subjected to sampling analysis according to a treatment site, and then a treatment process is determined, wherein the treatment process can be any one of a chemical precipitation method, a redox method, an MBR (membrane bioreactor), an ion exchange method and an electrochemical method.
In the embodiment, the main method for carrying out soil aging treatment on the lower layer of the in-situ slurry of the heavy metal polluted site comprises the steps of aging the soil for 30-60 days at room temperature, turning the soil once every three days, and simultaneously keeping the water content of the soil at about 20%.
In the embodiment, the covering maintenance is carried out by maintaining the solidified soil for three days, keeping the water content of the soil at about 20%, and simultaneously covering with rain cloth.
In the embodiment, the acceptance evaluation standard adopts GB/T14848-93 'underground water environment quality standard' to carry out acceptance.
Examples activated carbon was purchased from Zhengzhou bamboo forest activated carbon development Co., Ltd.
In the examples, 200 mesh quicklime was used as quicklime and was purchased from Huatong calcium industries, Ltd.
The phosphate used in the examples was monopotassium phosphate, technical grade, available from Jining chemical Co., Ltd.
The examples are magnesium chloride, industrial grade, and are purchasable at the Weifang Jiuzhuo chemical Co., Ltd.
In the examples, sodium carboxymethylcellulose, technical grade, was purchased from Jinquan chemical Co., Ltd.
Examples butane tetracarboxylic acid, technical grade, available from Shanxi Asia chemical industries, Inc.
In the examples, sodium dihydrogen phosphate, technical grade, was purchased from Suzhou Longlong chemical technology Co.
Examples gluconic acid, industrial grade, was purchased from saao chemical, inc.
In the examples, tartaric acid, technical grade, was purchased from Shenyang Ellipx chemical Co.
Examples of heavy Metal contaminated soils
Operation of the drying method in the examplesThe method comprises the following steps: selecting 20g of soil polluted by heavy metals, and quickly filling the soil with the weight of W1In the aluminum box, the weight of the aluminum box and the soil sample is weighed to be W2Then placing the soil sample in a 105 ℃ constant temperature oven for 6h, taking out the aluminum box with the soil sample, cooling for 30min, weighing, repeatedly drying in the constant temperature oven, cooling and weighing until the difference between two times of continuous weighing is not more than 0.05g, determining that the constant weight is achieved, and recording the weight as W3And calculating the water content W% of the soil by the following formula: w% (% W) is 100%2-W3)/(W3-W1)。
In addition, the embodiment of the invention uniformly divides a heavy metal polluted site with a larger area into the same areas for restoration, and the areas of the heavy metal polluted sites restored in each embodiment are the same.
Example 1
An in-situ slurry stabilization restoration method for a heavy metal polluted site comprises the following steps:
step 1, isolation: isolating the heavy metal contaminated soil from soil which is not contaminated around the heavy metal contaminated soil, wherein the isolation adopts a cement wall to isolate the heavy metal contaminated soil from the soil which is not contaminated by the heavy metal;
step 2, determining the water content of the heavy metal contaminated soil: determining the water content of the heavy metal contaminated soil to be 18% according to a drying method;
step 3, slurrying the heavy metal contaminated soil: loosening the soil polluted by the heavy metal, wherein the loosening depth is 5m, and after loosening, injecting tap water according to the water content and stirring at the stirring speed of 50-100r/min to change the soil polluted by the heavy metal into in-situ slurry of a heavy metal polluted site, wherein the water content of the slurry is 150%;
step 4, adding a stabilizing agent: adding a stabilizing agent into the in-situ slurry of the heavy metal polluted site in a stirring state, wherein the weight area ratio of the addition amount of the stabilizing agent to the heavy metal polluted soil is 1: 1 (kg/m)2)；
Step 5, standing: after the stabilizing agent is added, continuously stirring the in-situ slurry in the heavy metal polluted site for 1.5 hours at the stirring speed of adding the stabilizing agent, and standing for 10 hours after stirring is finished;
step 6, separation: after standing, pumping out an upper solution of the in-situ slurry of the heavy metal polluted site and placing the upper solution in a sewage pool;
step 7, wastewater treatment and soil aging: carrying out wastewater treatment on the upper solution discharged into the sewage tank and carrying out soil aging treatment on the lower layer of the in-situ slurry of the heavy metal polluted site;
and 8: acceptance evaluation: carrying out soil aging treatment on the lower layer of the in-situ slurry of the heavy metal polluted site, and then carrying out acceptance evaluation to reach the acceptance standard;
step 9, covering and maintaining: and if the acceptance evaluation reaches the standard, performing covering maintenance on the lower layer of the in-situ slurry of the heavy metal polluted site.
The stabilizing agent comprises the following components in parts by weight: 30 parts of modified activated carbon, 40 parts of quicklime, 8 parts of complexing agent, 10 parts of phosphate and 5 parts of magnesium chloride.
The preparation method of the modified activated carbon comprises the following steps:
s1, sieving the activated carbon in a 15-mesh screen to obtain 15-mesh activated carbon;
s2, soaking 8 parts by weight of the 15-mesh activated carbon in 250 parts by weight of an aqueous solution of sodium hydroxide for 0.5-1.5h, wherein the concentration of the sodium hydroxide is 180g/L, washing with water for 4 times, drying at 120 ℃ for 3h, cooling to room temperature, and soaking in a saturated copper sulfate solution for 2h to obtain activated carbon;
s3, adding 250 parts by weight of water, 10 parts by weight of sodium carboxymethylcellulose, 15 parts by weight of 1,2,3, 4-butanetetracarboxylic acid and 5 parts by weight of sodium dihydrogen phosphate into the activated carbon, manually stirring for 1.5min to obtain a mixed solution, then carrying out ultrasonic treatment on the mixed solution for 20min at 30 ℃ by using an ultrasonic cleaning machine, stirring for 6h at 100r/min to uniformly mix the mixed solution, standing the uniformly mixed solution for 10h, filtering, pre-drying the filtered precipitate at 80 ℃, wherein the pre-drying time is 12h, quickly heating the precipitate to 150 ℃ after the pre-drying is finished, continuing for 5min, then alternately washing for 4 times by using water and ethanol at 60 ℃, and drying to obtain the modified activated carbon.
The complexing agent is prepared from gluconic acid and tartaric acid in a weight ratio of 2: 5, and mixing the components in a ratio of 5.
Example 2
An in-situ slurry stabilization restoration method for a heavy metal polluted site comprises the following steps:
step 1, isolation: isolating the heavy metal contaminated soil from soil which is not contaminated around the heavy metal contaminated soil, wherein the isolation adopts a cement wall to isolate the heavy metal contaminated soil from the soil which is not contaminated by the heavy metal;
step 2, determining the water content of the heavy metal contaminated soil: determining the water content of the heavy metal contaminated soil to be 18% according to a drying method;
step 3, slurrying the heavy metal contaminated soil: loosening the soil polluted by the heavy metal, wherein the loosening depth is 5m, and after loosening, injecting tap water according to the water content and stirring at the stirring speed of 50-100r/min to change the soil polluted by the heavy metal into in-situ slurry of a heavy metal polluted site, wherein the water content of the slurry is 150%;
step 4, adding a stabilizing agent: adding a stabilizing agent into the in-situ slurry of the heavy metal polluted site in a stirring state, wherein the weight area ratio of the addition amount of the stabilizing agent to the heavy metal polluted soil is 1: 1 (kg/m)2)；
Step 5, standing: after the stabilizing agent is added, continuously stirring the in-situ slurry in the heavy metal polluted site for 1.5 hours at the stirring speed of adding the stabilizing agent, and standing for 10 hours after stirring is finished;
step 6, separation: after standing, pumping out an upper solution of the in-situ slurry of the heavy metal polluted site and placing the upper solution in a sewage pool;
step 7, wastewater treatment and soil aging: carrying out wastewater treatment on the upper solution discharged into the sewage tank and carrying out soil aging treatment on the lower layer of the in-situ slurry of the heavy metal polluted site;
and 8: acceptance evaluation: carrying out soil aging treatment on the lower layer of the in-situ slurry of the heavy metal polluted site, and then carrying out acceptance evaluation;
and 9, cyclic treatment: the acceptance evaluation does not reach the standard, the lower layer of the in-situ slurry of the heavy metal polluted site is processed in the steps 1-8 again to enable the lower layer of the in-situ slurry of the heavy metal polluted site to reach the standard of the acceptance evaluation, and the acceptance is up to the standard after the circulation is carried out twice;
step 10, covering and maintaining: and if the acceptance evaluation reaches the standard, performing covering maintenance on the lower layer of the in-situ slurry of the heavy metal polluted site.
The stabilizing agent comprises the following components in parts by weight: 30 parts of modified activated carbon, 40 parts of quicklime, 8 parts of gluconic acid, 10 parts of phosphate and 5 parts of magnesium chloride.
The preparation method of the modified activated carbon comprises the following steps:
s1, sieving the activated carbon in a 15-mesh screen to obtain 15-mesh activated carbon;
s2, soaking 8 parts by weight of the 15-mesh activated carbon in 250 parts by weight of an aqueous solution of sodium hydroxide for 0.5-1.5h, wherein the concentration of the sodium hydroxide is 180g/L, washing with water for 4 times, drying at 120 ℃ for 3h, cooling to room temperature, and soaking in a saturated copper sulfate solution for 2h to obtain activated carbon;
s3, adding 250 parts by weight of water, 10 parts by weight of sodium carboxymethylcellulose, 15 parts by weight of 1,2,3, 4-butanetetracarboxylic acid and 5 parts by weight of sodium dihydrogen phosphate into the activated carbon, manually stirring for 1.5min to obtain a mixed solution, then carrying out ultrasonic treatment on the mixed solution for 20min at 30 ℃ by using an ultrasonic cleaning machine, stirring for 6h at 100r/min to uniformly mix the mixed solution, standing the uniformly mixed solution for 10h, filtering, pre-drying the filtered precipitate at 80 ℃, wherein the pre-drying time is 12h, quickly heating the precipitate to 150 ℃ after the pre-drying is finished, continuing for 5min, then alternately washing for 4 times by using water and ethanol at 60 ℃, and drying to obtain the modified activated carbon.
Example 3
An in-situ slurry stabilization restoration method for a heavy metal polluted site comprises the following steps:
step 1, isolation: isolating the heavy metal contaminated soil from soil which is not contaminated around the heavy metal contaminated soil, wherein the isolation adopts a cement wall to isolate the heavy metal contaminated soil from the soil which is not contaminated by the heavy metal;
step 2, determining the water content of the heavy metal contaminated soil: determining the water content of the heavy metal contaminated soil to be 18% according to a drying method;
step 3, slurrying the heavy metal contaminated soil: loosening the soil polluted by the heavy metal, wherein the loosening depth is 5m, and after loosening, injecting tap water according to the water content and stirring at the stirring speed of 50-100r/min to change the soil polluted by the heavy metal into in-situ slurry of a heavy metal polluted site, wherein the water content of the slurry is 150%;
step 4, adding a stabilizing agent: adding a stabilizing agent into the in-situ slurry of the heavy metal polluted site in a stirring state, wherein the weight area ratio of the addition amount of the stabilizing agent to the heavy metal polluted soil is 1: 1 (kg/m)2)；
Step 5, standing: after the stabilizing agent is added, continuously stirring the in-situ slurry in the heavy metal polluted site for 1.5 hours at the stirring speed of adding the stabilizing agent, and standing for 10 hours after stirring is finished;
step 6, separation: after standing, pumping out an upper solution of the in-situ slurry of the heavy metal polluted site and placing the upper solution in a sewage pool;
step 7, wastewater treatment and soil aging: carrying out wastewater treatment on the upper solution discharged into the sewage tank and carrying out soil aging treatment on the lower layer of the in-situ slurry of the heavy metal polluted site;
and 8: acceptance evaluation: carrying out soil aging treatment on the lower layer of the in-situ slurry of the heavy metal polluted site, and then carrying out acceptance evaluation;
and 9, cyclic treatment: the acceptance evaluation does not reach the standard, the lower layer of the in-situ slurry of the heavy metal polluted site is processed in the steps 1-8 again to enable the lower layer of the in-situ slurry of the heavy metal polluted site to reach the standard of the acceptance evaluation, and the acceptance is up to the standard after the circulation is carried out twice;
step 10, covering and maintaining: and if the acceptance evaluation reaches the standard, performing covering maintenance on the lower layer of the in-situ slurry of the heavy metal polluted site.
The stabilizing agent comprises the following components in parts by weight: 30 parts of modified activated carbon, 40 parts of quicklime, 8 parts of tartaric acid, 10 parts of phosphate and 5 parts of magnesium chloride.
The preparation method of the modified activated carbon comprises the following steps:
s1, sieving the activated carbon in a 15-mesh screen to obtain 15-mesh activated carbon;
s2, soaking 8 parts by weight of the 15-mesh activated carbon in 250 parts by weight of an aqueous solution of sodium hydroxide for 0.5-1.5h, wherein the concentration of the sodium hydroxide is 180g/L, washing with water for 4 times, drying at 120 ℃ for 3h, cooling to room temperature, and soaking in a saturated copper sulfate solution for 2h to obtain activated carbon;
s3, adding 250 parts by weight of water, 10 parts by weight of sodium carboxymethylcellulose, 15 parts by weight of 1,2,3, 4-butanetetracarboxylic acid and 5 parts by weight of sodium dihydrogen phosphate into the activated carbon, manually stirring for 1.5min to obtain a mixed solution, then carrying out ultrasonic treatment on the mixed solution for 20min at 30 ℃ by using an ultrasonic cleaning machine, stirring for 6h at 100r/min to uniformly mix the mixed solution, standing the uniformly mixed solution for 10h, filtering, pre-drying the filtered precipitate at 80 ℃, wherein the pre-drying time is 12h, quickly heating the precipitate to 150 ℃ after the pre-drying is finished, continuing for 5min, then alternately washing for 4 times by using water and ethanol at 60 ℃, and drying to obtain the modified activated carbon.
Example 4
Essentially the same as example 1, except that:
the complexing agent is prepared from gluconic acid and tartaric acid in a weight ratio of 1: 5, and mixing the components in a ratio of 5.
Example 5
Essentially the same as example 1, except that:
the complexing agent is prepared from gluconic acid and tartaric acid in a weight ratio of 1:2, and mixing the components in a ratio of 2.
Example 6
Essentially the same as example 1, except that:
the complexing agent is prepared from gluconic acid and tartaric acid in a weight ratio of 1: 4, and mixing the components in a ratio of 4.
Example 7
An in-situ slurry stabilization restoration method for a heavy metal polluted site comprises the following steps:
step 1, isolation: isolating the heavy metal contaminated soil from soil which is not contaminated around the heavy metal contaminated soil, wherein the isolation adopts a cement wall to isolate the heavy metal contaminated soil from the soil which is not contaminated by the heavy metal;
step 2, determining the water content of the heavy metal contaminated soil: determining the water content of the heavy metal contaminated soil to be 18% according to a drying method;
step 3, slurrying the heavy metal contaminated soil: loosening the soil polluted by the heavy metal, wherein the loosening depth is 5m, and after loosening, injecting tap water according to the water content and stirring at the stirring speed of 50-100r/min to change the soil polluted by the heavy metal into in-situ slurry of a heavy metal polluted site, wherein the water content of the slurry is 150%;
step 4, adding a stabilizing agent: adding a stabilizing agent into the in-situ slurry of the heavy metal polluted site in a stirring state, wherein the weight area ratio of the addition amount of the stabilizing agent to the heavy metal polluted soil is 1: 1 (kg/m)2)；
Step 5, standing: after the stabilizing agent is added, continuously stirring the in-situ slurry in the heavy metal polluted site for 1.5 hours at the stirring speed of adding the stabilizing agent, and standing for 10 hours after stirring is finished;
step 6, separation: after standing, pumping out an upper solution of the in-situ slurry of the heavy metal polluted site and placing the upper solution in a sewage pool;
step 7, wastewater treatment and soil aging: carrying out wastewater treatment on the upper solution discharged into the sewage tank and carrying out soil aging treatment on the lower layer of the in-situ slurry of the heavy metal polluted site;
and 8: acceptance evaluation: carrying out soil aging treatment on the lower layer of the in-situ slurry of the heavy metal polluted site, and then carrying out acceptance evaluation;
and 9, cyclic treatment: the acceptance evaluation does not reach the standard, the lower layer of the in-situ slurry of the heavy metal polluted site is processed in the steps 1-8 again to enable the lower layer of the in-situ slurry of the heavy metal polluted site to reach the standard of the acceptance evaluation, and the acceptance is up to the standard after the circulation is carried out for three times;
step 10, covering and maintaining: and if the acceptance evaluation reaches the standard, performing covering maintenance on the lower layer of the in-situ slurry of the heavy metal polluted site.
The stabilizing agent comprises the following components in parts by weight: 30 parts of activated carbon, 40 parts of quicklime and 8 parts of complexing agent.
The complexing agent is prepared from gluconic acid and tartaric acid in a weight ratio of 2: 5, and mixing the components in a ratio of 5.
Example 8
An in-situ slurry stabilization restoration method for a heavy metal polluted site comprises the following steps:
step 1, isolation: isolating the heavy metal contaminated soil from soil which is not contaminated around the heavy metal contaminated soil, wherein the isolation adopts a cement wall to isolate the heavy metal contaminated soil from the soil which is not contaminated by the heavy metal;
step 2, determining the water content of the heavy metal contaminated soil: determining the water content of the heavy metal contaminated soil to be 18% according to a drying method;
step 3, slurrying the heavy metal contaminated soil: loosening the soil polluted by the heavy metal, wherein the loosening depth is 5m, and after loosening, injecting tap water according to the water content and stirring at the stirring speed of 50-100r/min to change the soil polluted by the heavy metal into in-situ slurry of a heavy metal polluted site, wherein the water content of the slurry is 150%;
step 4, adding a stabilizing agent: adding a stabilizing agent into the in-situ slurry of the heavy metal polluted site in a stirring state, wherein the weight area ratio of the addition amount of the stabilizing agent to the heavy metal polluted soil is 1: 1 (kg/m)2)；
Step 5, standing: after the stabilizing agent is added, continuously stirring the in-situ slurry in the heavy metal polluted site for 1.5 hours at the stirring speed of adding the stabilizing agent, and standing for 10 hours after stirring is finished;
step 6, separation: after standing, pumping out an upper solution of the in-situ slurry of the heavy metal polluted site and placing the upper solution in a sewage pool;
step 7, wastewater treatment and soil aging: carrying out wastewater treatment on the upper solution discharged into the sewage tank and carrying out soil aging treatment on the lower layer of the in-situ slurry of the heavy metal polluted site;
and 8: acceptance evaluation: carrying out soil aging treatment on the lower layer of the in-situ slurry of the heavy metal polluted site, and then carrying out acceptance evaluation;
and 9, cyclic treatment: the acceptance evaluation does not reach the standard, the lower layer of the in-situ slurry of the heavy metal polluted site is processed in the steps 1-8 again to enable the lower layer of the in-situ slurry of the heavy metal polluted site to reach the standard of the acceptance evaluation, and the acceptance is up to the standard after the circulation is carried out for three times;
step 10, covering and maintaining: and if the acceptance evaluation reaches the standard, performing covering maintenance on the lower layer of the in-situ slurry of the heavy metal polluted site.
The stabilizing agent comprises the following components in parts by weight: 30 parts of activated carbon, 40 parts of quicklime, 8 parts of complexing agent, 10 parts of phosphate and 5 parts of magnesium chloride.
The complexing agent is prepared from gluconic acid and tartaric acid in a weight ratio of 2: 5, and mixing the components in a ratio of 5.
Example 9
An in-situ slurry stabilization restoration method for a heavy metal polluted site comprises the following steps:
step 1, isolation: isolating the heavy metal contaminated soil from soil which is not contaminated around the heavy metal contaminated soil, wherein the isolation adopts a cement wall to isolate the heavy metal contaminated soil from the soil which is not contaminated by the heavy metal;
step 2, determining the water content of the heavy metal contaminated soil: determining the water content of the heavy metal contaminated soil to be 18% according to a drying method;
step 3, slurrying the heavy metal contaminated soil: loosening the soil polluted by the heavy metal, wherein the loosening depth is 5m, and after loosening, injecting tap water according to the water content and stirring at the stirring speed of 50-100r/min to change the soil polluted by the heavy metal into in-situ slurry of a heavy metal polluted site, wherein the water content of the slurry is 150%;
step 4, adding a stabilizing agent: adding a stabilizing agent into the in-situ slurry of the heavy metal polluted site in a stirring state, wherein the weight area ratio of the addition amount of the stabilizing agent to the heavy metal polluted soil is 1: 1 (kg/m)2)；
Step 5, standing: after the stabilizing agent is added, continuously stirring the in-situ slurry in the heavy metal polluted site for 1.5 hours at the stirring speed of adding the stabilizing agent, and standing for 10 hours after stirring is finished;
step 6, separation: after standing, pumping out an upper solution of the in-situ slurry of the heavy metal polluted site and placing the upper solution in a sewage pool;
step 7, wastewater treatment and soil aging: carrying out wastewater treatment on the upper solution discharged into the sewage tank and carrying out soil aging treatment on the lower layer of the in-situ slurry of the heavy metal polluted site;
and 8: acceptance evaluation: carrying out soil aging treatment on the lower layer of the in-situ slurry of the heavy metal polluted site, and then carrying out acceptance evaluation;
and 9, cyclic treatment: the acceptance evaluation does not reach the standard, the lower layer of the in-situ slurry of the heavy metal polluted site is processed in the steps 1-8 again to enable the lower layer of the in-situ slurry of the heavy metal polluted site to reach the standard of the acceptance evaluation, and the acceptance is up to the standard after the circulation is carried out for three times;
step 10, covering and maintaining: and if the acceptance evaluation reaches the standard, performing covering maintenance on the lower layer of the in-situ slurry of the heavy metal polluted site.
The stabilizing agent comprises the following components in parts by weight: 30 parts of modified activated carbon, 40 parts of quicklime and 8 parts of complexing agent.
The preparation method of the modified activated carbon comprises the following steps:
s1, sieving the activated carbon in a 15-mesh screen to obtain 15-mesh activated carbon;
s2, soaking 8 parts by weight of the 15-mesh activated carbon in 250 parts by weight of an aqueous solution of sodium hydroxide for 0.5-1.5h, wherein the concentration of the sodium hydroxide is 180g/L, washing with water for 4 times, drying at 120 ℃ for 3h, cooling to room temperature, and soaking in a saturated copper sulfate solution for 2h to obtain activated carbon;
s3, adding 250 parts by weight of water, 10 parts by weight of sodium carboxymethylcellulose, 15 parts by weight of 1,2,3, 4-butanetetracarboxylic acid and 5 parts by weight of sodium dihydrogen phosphate into the activated carbon, manually stirring for 1.5min to obtain a mixed solution, then carrying out ultrasonic treatment on the mixed solution for 20min at 30 ℃ by using an ultrasonic cleaning machine, stirring for 6h at 100r/min to uniformly mix the mixed solution, standing the uniformly mixed solution for 10h, filtering, pre-drying the filtered precipitate at 80 ℃, wherein the pre-drying time is 12h, quickly heating the precipitate to 150 ℃ after the pre-drying is finished, continuing for 5min, then alternately washing for 4 times by using water and ethanol at 60 ℃, and drying to obtain the modified activated carbon.
The complexing agent is prepared from gluconic acid and tartaric acid in a weight ratio of 2: 5, and mixing the components in a ratio of 5.
Test example:
the testing steps of the contents of the effective cadmium, lead, chromium, arsenic and mercury in the heavy metal contaminated site before restoration and the soil cured in the examples 1 to 9 are as follows:
step one, preparation of a sample: collecting samples (generally not less than 500g) of the heavy metal polluted site before restoration, uniformly mixing, and dividing to about 100g by a quartering method. Air drying (natural air drying or freeze drying) the soil sample after being divided, removing foreign matters such as stones and animal and plant residues in the soil sample, grinding and pressing the soil sample by using a wood stick (or an agate stick), passing through a 2mm nylon sieve (removing gravel with the size of more than 2 mm), and uniformly mixing. The screened soil sample was ground with agate until all passed through a 0.149mm nylon sieve to obtain a test sample.
Step two, measuring the pH value of the soil: test sample 10g (to an accuracy of 0.001g) was weighed into a 50mL beaker and CO removal added225mL of water (soil-to-liquid ratio: 1:2.5), stirring for 1min to fully disperse the soil particles, standing for 30min, and measuring.
Step three, testing: weighing a test sample into a plastic bottle of 180mL, adding 25mL of 0.15mol/L hydrochloric acid, oscillating for 90min on a reciprocating oscillation machine, filtering by using medium-speed quantitative filter paper to obtain clear liquid, absorbing 1mL of filtrate, diluting by 10 times, measuring cadmium, lead and chromium in effective states by using an inductively coupled plasma mass spectrometer (manufactured by Thermo-elementary company of America, the model is x-SERIES), and measuring arsenic and mercury in effective states by using an atomic fluorescence spectrometer (purchased from HongZhou laboratory instruments science and technology Limited in Guangzhou City, the model is LUMINA-3400).
Similarly, the soil samples cured in examples 1-9 were subjected to the above procedures to test the contents of available cadmium, lead, chromium, arsenic and mercury in the soil cured in examples 1-9.
The test results are shown in table 1:
TABLE 1 contents of available cadmium, lead, chromium, arsenic and mercury in the soil
As can be seen from table 1, the contents of cadmium, lead, chromium, arsenic and mercury in the soil after curing in examples 1 to 9 are all lower than the standards of cadmium, lead, chromium, arsenic and mercury in the soil specified in the standard GB15618-1995 "soil environmental quality standard", wherein the contents of cadmium, lead, chromium, arsenic and mercury in the soil after curing in example 1 are all lower than the contents of cadmium, lead, chromium, arsenic and mercury in the soil after curing in examples 2 to 8, and as can be seen from examples 1 to 9, the in-situ slurry stabilization remediation of the heavy metal contaminated site was performed only once in example 1, and no cyclic treatment was performed.
Claims (10)
1. An in-situ slurry stabilization restoration method for a heavy metal polluted site is characterized by comprising the following steps:
step 1, isolation: isolating the heavy metal contaminated soil from the soil which is not contaminated around the heavy metal contaminated soil;
step 2, determining the water content of the heavy metal contaminated soil: determining the water content of the heavy metal contaminated soil according to a drying method;
step 3, slurrying the heavy metal contaminated soil: loosening the soil polluted by the heavy metal, injecting water according to the moisture content after loosening the soil, and stirring to change the soil polluted by the heavy metal into in-situ slurry of a heavy metal polluted site;
step 4, adding a stabilizing agent: adding a stabilizing agent into the in-situ slurry of the heavy metal polluted site in a stirring state;
step 5, standing: after the stabilizing agent is added, continuously stirring the in-situ slurry in the heavy metal polluted site for 1-2 hours at the stirring speed of adding the stabilizing agent, and standing for 10-12 hours after stirring is finished;
step 6, separation: after standing, pumping out an upper solution of the in-situ slurry of the heavy metal polluted site and placing the upper solution in a sewage pool;
step 7, wastewater treatment and soil aging: carrying out wastewater treatment on the upper solution discharged into the sewage tank and carrying out soil aging treatment on the lower layer of the in-situ slurry of the heavy metal polluted site;
and 8: acceptance evaluation: carrying out soil aging treatment on the lower layer of the in-situ slurry of the heavy metal polluted site, and then carrying out acceptance evaluation;
and 9, cyclic treatment: if the acceptance evaluation does not reach the standard, the lower layer of the in-situ slurry of the heavy metal polluted site is processed again in the steps 1-8 so that the lower layer of the in-situ slurry of the heavy metal polluted site reaches the standard of the acceptance evaluation;
step 10, covering and maintaining: and if the acceptance evaluation reaches the standard, performing covering maintenance on the lower layer of the in-situ slurry of the heavy metal polluted site.
2. The in-situ mud stabilization remediation method for the heavy metal contaminated site as claimed in claim 1, wherein the depth of the loose soil in the heavy metal contaminated soil in the step 3 is 4-6 m.
3. The method for in-situ sludge stabilization and remediation of a heavy metal contaminated site as claimed in claim 1, wherein the water content of the in-situ sludge of the heavy metal contaminated site in the step 3 is 140-160%.
4. The in-situ mud stabilization and remediation method for the heavy metal contaminated site as claimed in claim 1, wherein the weight-area ratio of the addition amount of the stabilizing agent to the heavy metal contaminated soil is (0.5-1.5): 1 (kg/m)2)。
5. The method for in-situ sludge stabilization and remediation of a heavy metal contaminated site as claimed in claim 1, wherein the water in step 3 is one of tap water, river water or treated industrial water.
6. The in-situ mud stabilization and remediation method for the heavy metal contaminated site according to claim 1, wherein the stabilizing agent comprises the following components in parts by weight: 20-40 parts of activated carbon or modified activated carbon, 30-60 parts of quicklime and 5-10 parts of complexing agent.
7. The in-situ mud stabilization and remediation method for the heavy metal contaminated site as claimed in claim 6, wherein the stabilizing agent comprises the following components in parts by weight: 20-40 parts of activated carbon or modified activated carbon, 30-60 parts of quicklime, 5-10 parts of complexing agent, 7-15 parts of phosphate and 4-6 parts of magnesium chloride.
8. The in-situ mud stabilization remediation method for the heavy metal contaminated site as claimed in claim 7, wherein the stabilizing agent comprises the following components in parts by weight: 20-40 parts of modified activated carbon, 30-60 parts of quicklime, 5-10 parts of complexing agent, 7-15 parts of phosphate and 4-6 parts of magnesium chloride.
9. The in-situ mud stabilization remediation method for the heavy metal contaminated site according to claim 8, wherein the preparation method of the modified activated carbon comprises the following steps:
s1, sieving the activated carbon in a 5-20 mesh sieve to obtain 5-20 mesh activated carbon;
s2, taking 5-10 parts by weight of the 5-20 mesh activated carbon, soaking in 300 parts by weight of sodium hydroxide aqueous solution 200-1.5 h, washing with water for 3-5 times, then drying at the temperature of 120-130 ℃ for 2-4h, cooling to room temperature, soaking in saturated copper sulfate solution for 1-3h to obtain activated carbon;
s3, adding 300 parts by weight of water, 8-16 parts by weight of sodium carboxymethylcellulose, 15-20 parts by weight of 1,2,3, 4-butanetetracarboxylic acid and 5-10 parts by weight of sodium dihydrogen phosphate into the activated carbon, manually stirring for 1-2min to obtain a mixed solution, then carrying out ultrasonic treatment on the mixed solution for 10-30min, stirring for 5-7h under the condition of 100 revolutions per minute to uniformly mix the mixed solution, standing the uniformly mixed solution for 10-12h, filtering, pre-drying the precipitate obtained after filtering at the temperature of 70-90 ℃, wherein the pre-drying time is 11-13h, quickly heating the precipitate to 200 ℃ after the pre-drying is finished, keeping for 5-8min, then alternately washing for 3-5 times by using water and ethanol at the temperature of 60-70 ℃, drying to obtain the modified activated carbon.
10. The method for in-situ mud stabilization and remediation of a heavy metal contaminated site according to claim 6, 7 or 8, wherein the complexing agent is one or more of gluconic acid and tartaric acid.
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