CN114540034A - Hexavalent chromium contaminated soil remediation agent and preparation and application thereof - Google Patents
Hexavalent chromium contaminated soil remediation agent and preparation and application thereof Download PDFInfo
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Abstract
The application discloses a hexavalent chromium contaminated soil remediation agent, a preparation method and an application thereof: the preparation method comprises the following steps: (1) crushing crab shells, and performing primary pyrolysis treatment under the protection of inert gas: (2) adding yellow wine fermentation wastewater into the carbonized crab shells subjected to the primary pyrolysis treatment until the yellow wine fermentation wastewater permeates the carbonized crab shells, and continuously mixing for 5-200 min; (3) naturally airing the carbonized crab shells soaked with the yellow wine fermentation wastewater or dehydrating the carbonized crab shells by using waste heat until the water content is lower than 30%; (4) carrying out secondary pyrolysis treatment on the dehydrated carbonized crab shells under the protection of inert gas: (5) and (4) grinding the carbonized crab shells subjected to secondary pyrolysis treatment again to 1-200 meshes to obtain the carbonized crab shell. The agent prepared by the method obviously improves the stabilizing efficiency of hexavalent chromium in the polluted soil, and realizes the resource utilization of yellow wine fermentation wastewater.
Description
Technical Field
The invention relates to the technical field of soil remediation, and particularly relates to a hexavalent chromium contaminated soil remediation agent, and preparation and application thereof.
Background
Chromium is widely applied to industries such as electroplating, metal processing, tanning, dye, steel, chemical industry and the like, and industrial enterprises related to chromium use often have the problem of soil chromium pollution. Chromium in the chromium-polluted soil generally exists in a trivalent form and a hexavalent form, wherein the hexavalent chromium has high environmental mobility and obvious toxic action on organisms and human bodies, and can inhibit the growth and development of crops and threaten the health of human bodies.
A common hexavalent chromium polluted soil remediation method is a stabilizing chemical reduction method which is a common method for treating soil hexavalent chromium pollution, namely, a reducing agent is added into chromium polluted soil to convert Cr (VI) with high toxicity into Cr (III) with low toxicity, and common iron reduction agents and sulfur reduction agents are available. The chemical reducing agents need to be further combined with other stabilizing or curing agents to achieve the purposes of reducing and limiting environmental migration of chromium elements, the overall reaction strength is high, and secondary pollution can be brought to soil when the chemical reducing agents are added in large quantities.
Disclosure of Invention
The application provides a hexavalent chromium contaminated soil remediation agent, and preparation and application thereof, which have no secondary pollution, remarkably improve the stabilization efficiency of hexavalent chromium in contaminated soil, and simultaneously realize resource utilization of yellow wine fermentation wastewater.
A preparation method of a hexavalent chromium contaminated soil remediation agent comprises the following steps:
(1) crushing crab shells to a particle size of less than 1cm, and performing primary pyrolysis treatment under the protection of inert gas:
(2) adding yellow wine fermentation wastewater into the carbonized crab shells subjected to primary pyrolysis treatment until the yellow wine fermentation wastewater permeates the carbonized crab shells, and continuously mixing for 5-200 min until CODcr in the mixed material keeps continuous and stable;
(3) naturally airing the carbonized crab shells soaked with the yellow wine fermentation wastewater or dehydrating the carbonized crab shells by using waste heat until the water content is lower than 30%;
(4) carrying out secondary pyrolysis treatment on the dehydrated carbonized crab shells under the protection of inert gas:
(5) and (4) grinding the carbonized crab shells subjected to secondary pyrolysis treatment again to 1-200 meshes to obtain the carbonized crab shell.
Several alternatives are provided below, but not as an additional limitation to the above general solution, but merely as a further addition or preference, each alternative being combinable individually for the above general solution or among several alternatives without technical or logical contradictions.
Optionally, in the step (2), the water content of the carbonized crab shell is calculated to be 35-45% by adding the yellow wine fermentation wastewater.
Optionally, in the step (2), the continuous mixing time is 90min to 200 min. And performing CODcr detection on the wastewater of the mixed materials in the stirring process, and stopping stirring when the CODcr concentration is not reduced obviously any more.
Optionally, the yellow wine fermentation wastewater is rice swill, rice pouring water, jar (jar) washing water or washing water generated in the yellow wine brewing process.
Optionally, the yellow wine fermentation wastewater with CODcr concentration of over 50000mg/L is selected as the yellow wine fermentation wastewater.
Optionally, the yellow wine fermentation wastewater with CODcr concentration of 50000 mg/L-200000 mg/L is selected as the yellow wine fermentation wastewater.
Optionally, in the primary pyrolysis treatment: heating from room temperature at a heating rate of 4-10 ℃/min until the pyrolysis temperature reaches 400-600 ℃, and maintaining at 400-600 ℃ for 5-120 min;
in the secondary pyrolysis treatment: heating from room temperature at a heating rate of 4-10 deg.C/min until the pyrolysis temperature reaches 400-600 deg.C, and maintaining at 400-600 deg.C for 5-120 min.
Further, in the primary pyrolysis treatment: heating from room temperature at a heating rate of 8 ℃/min until the pyrolysis temperature reaches 400 ℃, and maintaining at 400 ℃ for 20-40 min;
in the secondary pyrolysis treatment: heating from room temperature at a heating rate of 4-10 deg.C/min until the pyrolysis temperature reaches 600 deg.C, and maintaining at 600 deg.C for 20-40 min.
Optionally, after the primary pyrolysis treatment and the secondary pyrolysis treatment are finished, both the primary pyrolysis treatment and the secondary pyrolysis treatment are naturally cooled, and inert gas is introduced for protection before the temperature is lower than 300 ℃.
The application also provides a hexavalent chromium contaminated soil remediation agent prepared by the preparation method.
The application also provides a restoration method of hexavalent chromium contaminated soil, which comprises the following steps:
adding the hexavalent chromium contaminated soil remediation agent into the contaminated soil to be treated at least once according to the proportion, adding a proportional amount of clear water into the contaminated soil to be treated while adding the agent each time, mixing, and maintaining for 3-8 days; the adding amount of the hexavalent chromium polluted soil remediation agent accounts for 3-5% of the total weight of the polluted soil to be treated each time; the adding amount of the clear water in each time accounts for 30-50% of the total weight of the polluted soil to be treated.
And (4) maintaining for about 5 days, and sampling the polluted soil and detecting the heavy metal leaching (according to a solid waste leaching toxicity leaching method horizontal oscillation method (GB 5086.2-1997)). If the heavy metal pollutants in the leaching solution do not reach the remediation target, supplementing and adding a medicament into the maintained polluted soil, adding a proper amount of clear water according to 30-50% of the total amount of the soil again, and uniformly mixing and stirring the medicament and the soil.
Compared with the prior art, the application has at least one of the following beneficial effects:
(1) inhibiting migration of hexavalent chromium in a soil environment;
(2) promoting the transformation from high-toxicity hexavalent chromium to low-toxicity trivalent chromium;
(3) and recycling the yellow wine fermentation wastewater.
Drawings
FIG. 1 is a process flow diagram of a method of preparation of the present application;
fig. 2 is an SEM image of the pharmaceutical agent of application example 1 after adsorbing chromium.
Detailed Description
The technical solutions in the embodiments of the present application will be described clearly and completely with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only some embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
The biochar (prepared from biomass such as straw, cornstalk and the like after pyrolysis, activation and modification) has the potential of repairing hexavalent chromium polluted soil, and has the characteristics of small secondary pollution risk, mild reaction and the like. Therefore, further improving the reduction and stabilization repairing effect of the biochar on the hexavalent chromium is an important development direction of related repairing technologies. Waste crab shells are common waste of seafood processing factories in coastal areas, and are easy to cause negative effects on the environment when not properly disposed. The yellow wine fermentation wastewater is from fermentation tank washing wastewater and fermentation residual wastewater in the fermentation process of glutinous rice or rice, and is high COD wastewater rich in amino acid, starch, soluble saccharide and organic acid.
The application provides a medicament which is prepared by taking waste crab shells and yellow wine fermentation wastewater as main raw materials and simultaneously has hexavalent chromium reduction capacity and stabilization capacity through a mode of primary pyrolysis, adsorption and secondary pyrolysis aiming at hexavalent chromium polluted soil. The agent exerts the reductive group generated after crab shell pyrolysis to promote Cr (VI) to Cr (III), and further exerts the adsorption capacity and reductive action of activated carbon particles generated by pyrolysis of organic acid, soluble starch, amino acid and other substances in yellow wine fermentation wastewater on Cr (VI), and the two aspects are synergistic to jointly promote the stabilization of hexavalent chromium in polluted soil.
The process flow is shown in figure 1, and comprises the following specific steps:
(1) the waste crab shells are air-dried and then ground until the particle size is less than 1 cm.
(2) And introducing nitrogen into the pyrolysis furnace in advance to finish the treatment of the discharged air. And (3) putting the ground waste crab shells into a pyrolysis furnace, heating and pyrolyzing at a heating rate of 4 DEG/min-10 DEG/min until the temperature in the pyrolysis furnace reaches 400-600 ℃, keeping for 5-120 min (preferably 20-40 min) after reaching the optimal temperature, and turning off a power supply of the pyrolysis furnace for natural cooling.
The cooling process is accompanied by nitrogen gas introduction to prevent oxidation or burning of the crab shells in the furnace while protecting the reducing groups (-C ═ C-, -OH, amino groups, etc.) formed during the pyrolysis process. After the temperature in the furnace is lower than 300 ℃, the nitrogen gas is stopped.
(3) And (3) placing the pyrolyzed carbonized crab shell in a container, and then slowly pouring yellow wine fermentation wastewater until the fermentation wastewater permeates the carbonized crab shell, wherein the water content is controlled to be about 40%, so that the fermentation wastewater is prevented from freely seeping. Then slowly stirring (preventing the carbonized crab shells from rising and scattering) for 5-200 min. And performing CODcr detection on the wastewater in the mixed material in the stirring process, and stopping stirring when the CODcr concentration is not reduced obviously any more.
The yellow wine fermentation wastewater is rice swill, rice pouring water, jar washing water or rinsing water generated in the yellow wine brewing process.
The principle of the step is as follows: the carbonized crab shell has adsorbability, and can adsorb soluble starch, organic acid, amino acid, sugar and other substances in the fermentation wastewater to form agglomerates on the surface of the carbonized crab shell. The purpose of preventing the fermentation wastewater from freely seeping out is that part of components capable of precipitating and reducing hexavalent chromium in the crab shells can be dissolved in water, so that the substances are prevented from running off along with the water.
(4) And (3) placing the carbonized crab shells soaked with the yellow wine fermentation wastewater in a sunlight room or dehydrating the carbonized crab shells by using waste heat until the water content is lower than 30%, and completing preparation before secondary pyrolysis enters a furnace.
(5) And (3) putting the carbonized crab shell in the last step into a pyrolysis furnace, introducing nitrogen to finish air exhaust treatment, and starting pyrolysis at the heating rate of 4-10 DEG/min until the temperature in the pyrolysis furnace reaches 400-600 ℃. Keeping the temperature for 5min to 120min (preferably 20min to 40min) after reaching the temperature, closing a power supply of the pyrolysis furnace for natural cooling, and introducing nitrogen to protect the reducing groups until the temperature in the furnace is lower than 300 ℃.
The principle is as follows: starch, amino acid and organic acid substances in the fermentation wastewater are adsorbed on the carbonized crab shells, and then the organic substances are pyrolyzed under the protection of inert gas in the secondary pyrolysis process to be carbonized, and a large amount of fine carbon particles and reducing groups are formed on the surfaces of the carbonized crab shells. The carbon particles have higher adsorption capacity, and the groups generated by pyrolysis can have reduction effect on hexavalent chromium. (6) Collecting the cooled secondary pyrolysis crab shells, and grinding the secondary pyrolysis crab shells to a particle size of 1-200 meshes, wherein the particle size is preferably 50-100 meshes; and (5) finishing the preparation of the medicament.
The following description is given by way of specific examples:
example 1
(1) The waste crab shells are air-dried and then ground until the particle size is less than 1 cm.
(2) And introducing nitrogen into the pyrolysis furnace in advance to finish the treatment of the discharged air. And (3) putting the ground waste crab shells into a pyrolysis furnace, heating and pyrolyzing at a heating rate of 8 DEG/min until the temperature in the pyrolysis furnace reaches 400 ℃, keeping for 30min after reaching the optimal temperature, and turning off a power supply of the pyrolysis furnace for natural cooling. After the temperature in the furnace is lower than 300 ℃, the nitrogen gas is stopped.
(3) And (3) placing the pyrolyzed carbonized crab shells in a container, and then slowly pouring yellow wine fermentation wastewater (wastewater of a regulating reservoir of a wastewater treatment system of a certain Shaoxing yellow wine factory) until the fermentation wastewater permeates the carbonized crab shells, wherein the water content is controlled to be about 40%, so that the fermentation wastewater is prevented from freely seeping. Then slowly stirring (preventing the carbonized crab shell from rising and scattering) for 60 min.
(4) And (3) placing the carbonized crab shells soaked with the yellow wine fermentation wastewater in a sunlight room or dehydrating the carbonized crab shells by using waste heat until the water content is lower than 30%, and completing preparation before secondary pyrolysis enters a furnace.
(5) And (3) putting the carbonized crab shells in the last step into a pyrolysis furnace, introducing nitrogen to finish air exhaust treatment, and starting pyrolysis at a heating rate of 8 DEG/min until the temperature in the pyrolysis furnace reaches 600 ℃. Keeping for 30min after reaching the temperature, closing a power supply of the pyrolysis furnace for natural cooling, and introducing nitrogen to protect the reducing groups until the temperature in the furnace is lower than 300 ℃.
(6) Collecting the cooled secondarily pyrolyzed crab shells, and grinding the secondarily pyrolyzed crab shells to a particle size of 50-100 meshes; and (5) finishing the preparation of the medicament.
Comparative example 1
(1) The waste crab shells are air-dried and then ground until the particle size is less than 1 cm.
(2) And introducing nitrogen into the pyrolysis furnace in advance to finish the treatment of the discharged air. And (3) putting the ground waste crab shells into a pyrolysis furnace, heating and pyrolyzing at a heating rate of 5 DEG/min until the temperature in the pyrolysis furnace reaches 260 ℃, keeping for 20min after reaching the optimal temperature, and turning off a power supply of the pyrolysis furnace for natural cooling.
(3) And (3) putting the carbonized crab shells obtained in the step (2) into a pyrolysis furnace, introducing nitrogen to finish air exhaust treatment, and starting pyrolysis at a heating rate of 5 ℃/min until the temperature in the pyrolysis furnace reaches 400 ℃. And keeping for 20min after the temperature is reached, and turning off a power supply of the pyrolysis furnace for natural cooling.
Application example 1
Taking chromium-contaminated soil, adding the hexavalent chromium-contaminated soil remediation agent prepared in the example 1 into the chromium-contaminated soil, simultaneously adding a certain amount of clear water into the soil, and mixing for protection: the adding amount of the agent is 4% of the total amount of the polluted soil by mass; the first curing time was 6 days.
The agent prepared in comparative example 1 was also used as a control.
Evaluating the reduction and stabilization effects of hexavalent chromium by adopting a horizontal oscillation method (HJ557-2010) of a solid waste leaching toxicity leaching method; the concentration of hexavalent chromium in the polluted soil is 400 mg/kg; the addition amount of the control medicament and the preparation medicament of the embodiment is 4 percent of the total weight of the polluted soil, and the addition amount of the clear water is 40 percent of the total weight of the polluted soil.
The bench test results are shown in table 1:
TABLE 1
Small experiments show that the medicament can greatly reduce the leaching concentration of hexavalent chromium and total chromium, and the effect is also obviously better than that of a single carbonized crab shell. Meanwhile, the concentration and the proportion of hexavalent chromium in the leaching solution can be reduced, and the reduction effect of hexavalent chromium is proved to be obviously superior to that of single carbonized crab shells.
SEM images of the agents prepared in example 1 and the agent prepared in comparative example 1 after adsorbing chromium are shown in fig. 2, wherein (a) and (c) in fig. 2 are microscopic surface images (adsorbing a certain amount of chromium agglomerate) of the agent prepared in comparative example 1 after adsorbing chromium at different magnification ratios, and (b) and (d) are microscopic surface images (adsorbing a certain amount of chromium agglomerate) of the agent prepared in example 1 after adsorbing chromium at different magnification ratios.
As can be seen from comparison of the graphs (a) and (b) and (c) and (d), the examples have a larger number of chromium agglomerate grains with a smaller volume on the microscopic surface than the comparative examples, thus demonstrating a stronger adsorption effect of the examples on heavy metal chromium.
The above-mentioned embodiments only express several embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of a hexavalent chromium contaminated soil remediation agent is characterized by comprising the following steps:
(1) crushing crab shells, and then carrying out primary pyrolysis treatment under the protection of inert gas:
(2) adding yellow wine fermentation wastewater into the carbonized crab shells subjected to primary pyrolysis treatment until the yellow wine fermentation wastewater permeates the carbonized crab shells, and continuously mixing until CODcr in the mixed material keeps continuous and stable;
(3) naturally airing the carbonized crab shells soaked with the yellow wine fermentation wastewater or dehydrating the carbonized crab shells by using waste heat until the water content is lower than 30%;
(4) carrying out secondary pyrolysis treatment on the dehydrated carbonized crab shells under the protection of inert gas:
(5) and (4) grinding the carbonized crab shells subjected to secondary pyrolysis treatment again to 1-200 meshes to obtain the carbonized crab shell.
2. The preparation method according to claim 1, wherein in the step (2), the yellow wine fermentation wastewater is added in an amount such that the water content of the carbonized crab shells reaches 35-45%.
3. The method according to claim 1, wherein the mixing is continued for 90 to 200min in the step (2).
4. The preparation method of claim 1, wherein the yellow wine fermentation wastewater is rice swill, rice pouring water, jar (jar) washing water or washing water generated in a yellow wine brewing process.
5. The preparation method of claim 1, wherein the yellow wine fermentation wastewater is yellow wine fermentation wastewater with CODcr concentration of more than 50000 mg/L.
6. The preparation method of claim 5, wherein the yellow wine fermentation wastewater is the yellow wine fermentation wastewater with CODcr concentration of 50000 mg/L-200000 mg/L.
7. The production method according to claim 1, wherein in the primary pyrolysis treatment: heating from room temperature at a heating rate of 4-10 ℃/min until the pyrolysis temperature reaches 400-600 ℃, and maintaining at 400-600 ℃ for 5-120 min;
in the secondary pyrolysis treatment: heating from room temperature at a heating rate of 4-10 deg.C/min until the pyrolysis temperature reaches 400-600 deg.C, and maintaining at 400-600 deg.C for 5-120 min.
8. The preparation method according to claim 1, wherein the primary pyrolysis treatment and the secondary pyrolysis treatment are naturally cooled after the primary pyrolysis treatment and the secondary pyrolysis treatment are carried out, and inert gas is introduced for protection before the temperature is lower than 300 ℃.
9. The hexavalent chromium polluted soil remediation agent prepared by the preparation method of any one of claims 1 to 8.
10. A restoration method of hexavalent chromium contaminated soil is characterized by comprising the following steps:
the hexavalent chromium contaminated soil remediation agent of claim 9 is added to the contaminated soil to be treated at least once according to the ratio, and a ratio of clean water is added to the contaminated soil to be treated while the agent is added each time, and the mixture is maintained for 3 to 8 days; the adding amount of the hexavalent chromium polluted soil remediation agent accounts for 3-5% of the total weight of the polluted soil to be treated each time; the adding amount of the clear water in each time accounts for 30-50% of the total weight of the polluted soil to be treated.
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