CN112317529A - Chemical stabilization/high-temperature immobilization restoration method for organic arsenic contaminated soil in breeding industry - Google Patents
Chemical stabilization/high-temperature immobilization restoration method for organic arsenic contaminated soil in breeding industry Download PDFInfo
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Abstract
The invention discloses a chemical stabilization/high temperature immobilization restoration method for organic arsenic contaminated soil in breeding industry, which is characterized in that the organic arsenic contaminated soil is added into a stabilization agent after being pretreated and is uniformly stirred. And then, heating the contaminated soil doped with the stabilizing agent in an electric heating rotary kiln, cooling, and then adding water for maintenance to adjust the pH value of the soil, thereby realizing the remediation of the organic arsenic contaminated soil. The invention generates the cracking of organic arsenic and Fe in the heating process of the rotary kiln2+The composite material is coprecipitated with arsenic and subjected to high-temperature immobilization reaction of arsenic, chemical stabilization and high-temperature immobilization technology combination is realized, organic arsenic-polluted soil is quickly and effectively repaired, the pH value of the repaired soil can reach the standard by increasing and decreasing the amount of CaO, and the subsequent utilization of the soil is facilitated.
Description
Technical Field
The invention belongs to the technical field of soil remediation, and particularly relates to a chemical stabilization/high-temperature immobilization remediation method for organic arsenic contaminated soil in the breeding industry.
Background
With the development of social economy and the increasing pursuit of people for high-quality life, the livestock breeding industry is gradually changed from a decentralized type to an intensive type so as to meet the increasing demand of the public on meat products. The organic arsenic feed additive has the functions similar to insecticides and antibiotics, can block the growth and reproduction of parasites and intestinal pathogenic bacteria, improves the advantages of skin pigmentation of livestock and poultry products and the like, and is widely applied to livestock and poultry breeding. However, most of the organic arsenic compounds enter animal bodies and are discharged out of the bodies of the animals through excrement and urine in an original form and are not absorbed by the animals. And the organic arsenic enters the soil and is converted into a compound with higher mobility and stronger toxicity through the interaction of the environment, organisms and the like, and finally the problem of environmental pollution is caused.
At present, people have few researches on repairing organic arsenic polluted soil and a repairing method is single. For example, in the Chinese patent document "combined microwave oxidation composite remediation system and method (CN201310586047.6) for organic arsenic pollution in soil", a technology combining microwave thermal desorption and strong oxidation is adopted to treat arsenic-containing organic matters. The organic arsenic in the breeding industries such as rocarsone, arsanilic acid and the like can not achieve the thermal desorption effect by thermal decomposition, and the strong oxidation method can only oxidize the arsenic into stable compounds and needs microbial degradation in the later period, so the time consumption is long. In consideration of the environmental risk and public safety of organic arsenic in the breeding industry, a more efficient method for treating polluted soil is developed, and the method has good social benefit and environmental benefit.
Disclosure of Invention
In order to solve the technical problems, the invention provides a chemical stabilization/high temperature immobilization restoration method for organic arsenic polluted soil in breeding industry, which can quickly and efficiently restore the organic arsenic polluted soil.
The invention solves the technical problems by the following technical scheme:
the invention provides a chemical stabilization/high temperature immobilization restoration method for organic arsenic contaminated soil in breeding industry, which comprises the following steps of pretreating the organic arsenic contaminated soil, mixing and stirring the pretreated organic arsenic contaminated soil and a stabilizing agent uniformly, then cracking and stabilizing the mixture at high temperature through an electric heating rotary kiln device, cooling the soil after high temperature treatment, and then adding water to maintain the cooled soil properly to obtain the qualified soil after treatment, wherein the method specifically comprises the following steps:
(1) and adding the stabilizing agent and the pretreated polluted soil into an electric heating rotary kiln device through a sample feeding metering system to perform chemical stabilization/high-temperature immobilization combined treatment.
"chemical stabilization" specifically refers to the reduction of the environmental risk of arsenic by reducing its toxicity or mobility by chemical means.
The high-temperature immobilization specifically means that arsenic-containing soil is converted into a mineral phase form mainly containing iron and arsenic at a relatively high temperature and then is wrapped by formed glass molten state under a higher temperature condition, so that stable ferrosilicon arsenate is formed, and the leaching toxicity of arsenic is obviously reduced.
(2) And (2) adding water into the soil treated in the step (1) to enable the water content to reach 25-35%, covering a moisturizing material, and maintaining for 5-7 days to obtain the qualified treated soil.
The qualified soil is the soil polluted by organic arsenic, the leaching concentration of the arsenic after treatment is lower than 0.05mg/L, and the pH value meets 5.5-9.
The steps (1) and (2) are indispensable to the acquisition of qualified soil, the step (1) is to carry out chemical stabilization and high-temperature fixation on the soil polluted by organic arsenic, then the maintenance of the step (2) has the effect of promoting the chemical stabilization, and meanwhile, the pH value of the soil is adjusted to 5.5-9; and (3) the soil treated by the steps (1) and (2) is qualified soil meeting the standard.
The method also comprises a pretreatment step before the step (1): and (3) air-drying, removing impurities, crushing and screening the organic arsenic polluted soil by using a screen to obtain the pretreated polluted soil.
Wherein the organic arsenic comprises one or two of 3-nitro-4-hydroxy benzene arsenic acid (also known as roxarsone) and p-aminophenyl arsenic acid (also known as arsonic acid).
Wherein, the aperture size of the screen is 5 mm.
In the step (1), the stabilizing agent comprises the following components and the addition amount (mass percentage) of each component in the organic arsenic-polluted soil: FeSO4·7H25-10% of O; 0.5 to 2 percent of CaO; 10-20% of water.
In the step (1), the preparation method of the stabilizing agent is to take FeSO with a certain proportion4·7H2O, CaO and water, mixing and stirring, and dispersing.
In the step (1), since the pH has a great influence on the final arsenic leaching concentration, the addition amount of CaO in the reagent needs to be controlled in practical engineering application to ensure that the final leaching solution is within a proper range. Specifically, water is added into a medicament pool, CaO is added into the medicament pool, the mixture is continuously stirred uniformly, and then FeSO is added into the mixture4·7H2O, stirringAnd (4) uniformly mixing, finally adding the mixture into the polluted soil, and uniformly stirring to ensure that the pH value of the repaired soil is 5.5-9.
In the step (1), the temperature of the electric heating rotary kiln is set to be 300-350 ℃, and the retention time of the polluted soil in the kiln is 30-60 min; preferably, the temperature of the electrically heated rotary kiln is set at 350 ℃ and the residence time of the contaminated soil in the kiln is 60 min.
In the step (1), the electric heating rotary kiln is of a jacket type structure and comprises an inner cylinder and an outer cylinder, high-temperature-resistant heat-insulating cotton covers the inner surface of the outer cylinder, electric heating belts are orderly arranged on the surface of the heat-insulating cotton, and the inner cylinder rotates inside in a rotary kiln mode, so that the polluted soil is uniformly heated.
Wherein the rotating speed of the electric heating rotary kiln is 5-10 r/min; preferably, it is 10 r/min.
Wherein the rotating speed of the electric heating rotary kiln is related to the soil treatment amount per unit time and the effective heating length of the electric heating rotary kiln.
In the step (1), more than 99% of organic arsenic is converted into inorganic arsenic after combined treatment of chemical stabilization and high-temperature immobilization, and the leaching concentration of heavy metal arsenic in the repaired soil is lower than the IV-class water standard in the ground water quality standard (GB/T14848-93).
And (2) the tail gas generated in the step (1) firstly enters a condenser, and a bag-type dust remover is further used for filtering dust in the tail gas after condensation, so that atmospheric pollution is avoided.
In the step (2), the pH value of the soil is adjusted by increasing or decreasing the amount of CaO, so that the pH value of the repaired soil is 5.5-9 and meets the pH standard of GB14848 on IV-class underground water.
And (3) adding water into the treated soil in the step (2), covering with a moisture-preserving material, and maintaining for 5-7 days to adjust the pH value of the soil, thereby realizing the remediation of the soil polluted by the organic arsenic.
The moisturizing material refers to a material such as a plastic film that reduces water evaporation.
In a specific embodiment, the method specifically comprises the steps of:
(1) a pretreatment step: air-drying, impurity-removing and crushing the organic arsenic-polluted soil, and then sieving the organic arsenic-polluted soil by a 5mm sieve to obtain pretreated polluted soil;
(2) adding a stabilizing agent into the pretreated polluted soil, and stirring for ten minutes;
(3) the soil mixed with the stabilizing agent in the step (2) is processed by an electric heating rotary kiln device through a sample feeding metering system to achieve the effects of cracking and high-temperature stabilization;
(4) after cooling, adding a proper amount of water into the soil after high-temperature treatment to enable the water content to be about 35%, and covering a moisturizing material for curing for 5-7 days to repair organic arsenic pollution and adjust the pH value of the soil;
(5) and (4) the tail gas generated in the step (3) firstly enters a condenser, and a bag-type dust collector is further used for filtering dust in the tail gas after condensation.
The invention also provides a stabilizing agent which comprises the following components in percentage by mass: FeSO4·7H2O5-10%; 0.5 to 2 percent of CaO; 10-20% of water.
The invention also provides application of the stabilizing agent in chemical stabilization/high-temperature immobilization remediation of organic arsenic-polluted soil in the breeding industry.
Experiments show that the As-C bond on the benzene ring structure is broken, the arsenate radical structure is stripped from the benzene ring, the arsenic element is converted from the organic arsine form into the inorganic arsenic form, and conditions and possibility are provided for chemical stabilization and high-temperature immobilization of organic arsenic at the temperature of about 300 ℃ in the rocarsine and arsanilic acid, so that cracking of the organic arsenic and Fe sequentially occur in the electric heating rotary kiln2+Co-precipitation with arsenic and high-temperature immobilization of arsenic, and thus the combined chemical stabilization/high-temperature immobilization technology has an excellent treatment effect.
The invention has the beneficial effects that: according to the invention, common calcium oxide and ferrous sulfate are used as raw materials to form a cheap and easily-obtained chemical stabilizer, and a high-temperature immobilization technology is combined, so that the pentavalent arsenic is solidified/stabilized while organic arsenic is cracked into the pentavalent arsenic in a heating process. The method not only can quickly and effectively restore the soil polluted by the organic arsenic, but also can increase and decrease the amount of CaO according to the pH value of the polluted soil, so that the pH value of the restored soil reaches the standard, and the subsequent utilization of the soil is facilitated. In addition, the chemical stabilizer used in the invention has the advantages of wide raw material source, low cost, simple preparation method, easy operation of the whole process, short period and good treatment effect on the soil polluted by organic arsenic.
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FIG. 1 is a flow chart of the chemical stabilization/high temperature immobilization remediation method of organic arsenic contaminated soil in the breeding industry.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples and drawings, and the procedures, conditions, reagents, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for those specifically mentioned below, and the present invention is not particularly limited thereto.
The invention provides a chemical stabilization/high temperature immobilization restoration method for organic arsenic contaminated soil in breeding industry, which comprises the following steps:
(1) and (3) air-drying the soil polluted by the roxarsone and the arsonic acid, removing impurities, crushing, and pre-treating by a 5mm screen.
(2) Adding water, adding CaO, stirring, and adding FeSO4·7H2O, evenly stirring, finally mixing the O with the polluted soil, and evenly stirring for ten minutes, wherein the FeSO4·7H2The addition amount of O is 5-10% of the mass of the organic arsenic polluted soil; the addition amount of CaO is 0.5-2% of the mass of the soil polluted by the organic arsenic; the addition amount of water is 10-20% of the mass of the organic arsenic polluted soil.
(3) And (3) passing the soil doped with the stabilizing agent in the step (2) through an electric heating rotary kiln device by a sample injection metering system, wherein the temperature of the electric heating rotary kiln is set at 300-350 ℃, and the retention time of the polluted soil in the furnace is 30-60 min. The rotating speed of the rotary kiln is set to be 5-10 r/min.
(4) After the soil after high-temperature treatment is cooled, adding a proper amount of water to enable the water content to be about 35%, covering a moisturizing material, maintaining for 5-7 days, and adjusting the pH value of the soil by increasing or decreasing the amount of CaO to enable the pH value of the repaired soil to be 5.5-9. So that the qualified soil after the organic arsenic pollution is repaired and the pH value is adjusted can be obtained.
(5) And (4) the tail gas generated in the step (3) firstly enters a condenser, and a bag-type dust collector is further used for filtering dust in the tail gas after condensation, so that atmospheric pollution is avoided.
Example 1
In a remediation experiment of organic arsenic contaminated soil in a certain aquaculture industry, the combined chemical stabilization/high temperature immobilization technology shown in fig. 1 is adopted to treat the soil contaminated by organic arsenic (roxarsone and arsonic acid). Drying contaminated soil, removing impurities, crushing, sieving, adding water, adding CaO, stirring, and adding FeSO4·7H2O, evenly stirring, finally mixing the O, the CaO and the FeSO into the polluted soil, and evenly stirring for ten minutes, wherein the water, the CaO and the FeSO are mixed4·7H2The addition amount of O is 20%, 2% and 10% of the mass of the soil polluted by the organic arsenic. And then, the contaminated soil doped with the stabilizing agent enters an electric heating rotary kiln through a sample injection metering device, the temperature of the rotary kiln is set to be 350 ℃, the rotating speed is 10r/min, and the retention time of the contaminated soil in the rotary kiln is ensured to be 60 min. After heating, cooling at normal temperature by a discharging device, adding a proper amount of water to enable the water content to be about 35%, covering a moisturizing material, and maintaining for 5 days. Performing leaching toxicity analysis on the soil before and after remediation by referring to a solid waste leaching toxicity leaching method sulfuric acid-nitric acid method (HJ/T299-2007); measuring the total arsenic concentration in the leachate by referring to atomic fluorescence photometry for measuring arsenic in water (SL 327.1-2005); the concentration of the roxarsone and the arsanilic acid in the soil before and after the restoration is 0.5 mol.L-1H3PO4The extraction was shaken for 16h and then determined by liquid chromatography. The removal of organic arsenic and the fixation of arsenic were measured and shown in Table 1.
Table 1 removal of organic arsenic from soil and fixation of arsenic by the treatment method described in example 1
According to the IV-class water standard of ground water quality standard (GB/T14848-93), the arsenic leaching standard (mg/L) is 0.05, and the pH value of the leachate is 5.5-9. As can be seen from Table 1, the organic arsenic-contaminated soil treated in example 1 all meets the standard.
Example 2
In the organic arsenic contaminated soil remediation experiment of a certain breeding industry, the chemical stabilization technology is adopted to treat the soil contaminated by organic arsenic (roxarsone and arsonic acid). Drying contaminated soil, removing impurities, crushing, sieving, adding water, adding CaO, stirring, and adding FeSO4·7H2O, evenly stirring, finally mixing the O, the CaO and the FeSO into the polluted soil, and evenly stirring for ten minutes, wherein the water, the CaO and the FeSO are mixed4·7H2The addition amount of O is 20%, 2% and 10% of the mass of the soil polluted by the organic arsenic. And curing for 5 days after covering the moisturizing material. Performing leaching toxicity analysis on the soil before and after remediation by referring to a solid waste leaching toxicity leaching method sulfuric acid-nitric acid method (HJ/T299-2007); measuring the total arsenic concentration in the leachate by referring to atomic fluorescence photometry for measuring arsenic in water (SL 327.1-2005); the concentration of the roxarsone and the arsanilic acid in the soil before and after the restoration is 0.5 mol.L-1H3PO4The extraction was shaken for 16h and then determined by liquid chromatography. The removal of organic arsenic and the fixation of arsenic were measured and shown in Table 2.
Table 2 removal of organic arsenic from soil and fixation of arsenic by the treatment method described in example 2
As can be seen from example 1, the chemical stabilizer prepared by the invention has a certain repairing effect on organic arsenic-polluted soil; however, as can be seen from example 2, for the organoarsenic contaminants, Fe accelerates the decomposition of the organoarsenic due to lack of high temperature2+The efficiency of coprecipitation with arsenic is low, high-temperature immobilization is not generated, and the overall treatment effect is not ideal. Therefore, the method of adopting the combined treatment of chemical stabilization and high-temperature immobilization for the organic arsenic polluted soil can shorten the treatment timeThereby improving the treatment efficiency.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, and the scope of the appended claims is intended to be protected.
Claims (10)
1. The chemical stabilization/high temperature immobilization remediation method for organic arsenic contaminated soil in breeding industry is characterized in that after the organic arsenic contaminated soil is pretreated, the organic arsenic contaminated soil is mixed with a stabilizing agent and stirred uniformly, then cracking and high temperature stabilization are carried out through an electric heating rotary kiln device, and after the high temperature treated soil is cooled, water is added for maintenance, so that the qualified treated soil is obtained.
2. The method according to claim 1, characterized in that it comprises in particular the steps of:
(1) adding a stabilizing agent and the pretreated polluted soil into an electric heating rotary kiln device through a sample feeding metering system for chemical stabilization/high-temperature immobilization combined treatment;
(2) and (2) adding water into the soil treated in the step (1) to enable the water content to reach 25-35%, covering a moisturizing material, and maintaining for 5-7 days to obtain the qualified treated soil.
3. The method of claim 2, wherein step (1) is preceded by the further step of pre-processing: and (3) air-drying, removing impurities, crushing and screening the organic arsenic polluted soil by using a screen to obtain the pretreated polluted soil.
4. The method of claim 3, wherein the organic arsenic comprises one or both of 3-nitro-4-hydroxyphenylarsenic acid and p-aminophenylarsenic acid.
5. The method according to claim 2, wherein the stabilizing agent comprises the following components and the addition amount of each component in the organic arsenic-contaminated soil is as follows: FeSO4·7H25-10% of O; 0.5 to 2 percent of CaO; 10-20% of water; the preparation method of the stabilizing agent comprises the step of taking FeSO4·7H2O, CaO and water, mixing and stirring, and dispersing.
6. The method as claimed in claim 2, wherein in the step (1), the rotation speed of the electric heating rotary kiln is 5-10 r/min.
7. The method as claimed in claim 2, wherein in the step (1), the temperature of the electrically heated rotary kiln is set at 350 ℃ and the retention time of the contaminated soil in the kiln is 30-60 min.
8. The method according to claim 2, wherein the qualified soil obtained in step (2) has a pH value of 5.5-9 and an arsenic leaching concentration of less than 0.05 mg/L.
9. A stabilizing agent is characterized by comprising the following components in percentage by mass: FeSO4·7H25-10% of O; 0.5 to 2 percent of CaO; 10-20% of water.
10. The use of the stabilizing agent of claim 9 in chemical stabilization/high temperature immobilization remediation of organic arsenic contaminated soil in aquaculture.
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| CN114393020A (en) * | 2021-12-21 | 2022-04-26 | 生态环境部华南环境科学研究所 | Low-energy-consumption and low-carbon-emission arsenic-organic compound contaminated soil remediation method |
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Application publication date: 20210205 |