CN108569686B - Method for removing USEPA PAHs in biochar by Fenton oxidation - Google Patents
Method for removing USEPA PAHs in biochar by Fenton oxidation Download PDFInfo
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Abstract
The invention discloses a method for removing USEPA PAHs in biochar by using a Fenton oxidation reagent, belonging to the technical field of environmental engineering. The method comprises the steps of mixing the biochar with a Fenton reagent according to the proportion of 1(g) to 20(ml), and oscillating for 24 hours in a dark place to remove the USEPA PAHs in the biochar. The method can effectively remove USEPA PAHs in the biochar, reduce the risk of returning the biochar to the field, reduce the harm of the PAHs in the biochar to the environment and the human health, has the removal rate of more than 96 percent, and has the characteristics of environmental protection and high efficiency.
Description
Technical Field
The invention relates to the technical field of environmental protection and environmental protection biochar preparation, in particular to a method for removing USEPA PAHs in biochar by Fenton oxidation.
Background
The biochar is an organic carbonized solid substance which is prepared by highly carbonizing biomass at a certain temperature under the anaerobic or oxygen-limited condition and contains aromatic rings. Research shows that the biochar for agriculture can not only improve crop yield and reduce greenhouse gas emission, but also be used as a fertilizer slow release carrier and a carbon dioxide sealing agent.
However, due to the oxygen starvation or anaerobic environment during the biocoke preparation process, the incomplete combustion of biomass during the biocoke firing process inevitably produces polycyclic aromatic hydrocarbons. Research shows that the biochar contains a large amount of PAHs, and the content of the PAHs is 22 mu g/g (turf) and 5.9 mu g/g (charcoal) respectively (Keiluweit M et al, environ. Sci. Technol,46(17), 9333); research on Freddo A (2012) shows that the content of PAHs in the charcoal obtained by anaerobically baking rosewood, rice straws and bamboo is 0.08-8.7 mg/kg (environ. Pollutit, 2012,171(4): 18-24). The polycyclic aromatic hydrocarbon is difficult to degrade after entering the environment, and belongs to persistent organic pollution of the environment. Biochar is widely applied to farmlands as a soil conditioner at present, PAHs in the biochar can be transferred to soil through a certain soil chemical and physical process, 
M et al (2016) showed an increase in soil PAHs content of 0.287mg/kg and 1.071mg/kg (Chemosphere,2016,146:272-279) when the biochar was added at 30 and 45 tons per hectare, respectively, as compared to no biochar application. PAHs in soil can be absorbed into crops through plant root systems to cause PAHs accumulation in plants, and research on Khan A and the like (2015) The results show that the content of PAHs in the lettuce can be increased by 77.8ng/g to the maximum extent when the lettuce is planted by using the biochar as a medium compared with the lettuce without adding the biochar (J Agric Food Chem,2015,63(5): 1648-57).
According to the search, in the prior art, the method (201510217733.5) for controlling and removing polycyclic aromatic hydrocarbon generated in the biochar preparation process prepares biochar by using organic waste, and then mixes the biochar with functional bacteria with PAHs degradation efficiency. However, the technology does not indicate the removal effect of the PAHs in the biochar, and the prepared biochar has higher pH value, has certain inhibition effect on the growth of microorganisms, and reduces the removal effect of the PAHs in the biochar.
Disclosure of Invention
The invention aims to fill the blank of the application of a method for removing USEPA PAHs in biochar by Fenton oxidation, and aims to provide a method for oxidizing and degrading PAHs in biochar by utilizing the oxidation effect of a Fenton reagent.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
A method for removing USEPA PAHs in biochar by Fenton oxidation comprises the following steps:
Step one, air-drying and crushing plant residual wastes, putting the obtained plant residual crushed material into a crucible, sealing the crucible with tin foil paper, then putting the crucible into a muffle furnace for carbonization under anaerobic conditions, cooling, grinding and sieving to obtain plant residual biochar;
Step two, mixing the biochar and the Fenton reagent according to the proportion of 1g to 20ml, transferring the mixture into a 50ml conical flask, and oscillating the mixture for 24 hours in a dark place;
Centrifuging to remove supernatant, oscillating the solid with water for 15min, adjusting the pH of the biochar to be neutral, and repeating the step for 5 times;
And step four, airing the residual solid to obtain the biochar without the USEPA PAHs.
Further, in the above scheme, the plant residue is any one or a mixture of several of rice straw, wheat straw and corn straw.
Further, in the scheme, after the crucible is placed in the muffle furnace, the temperature of the muffle furnace is quickly increased to 600 ℃, anaerobic pyrolysis is carried out for 4 hours, the power supply is turned off, and after the temperature of the muffle furnace is reduced to room temperature, the crucible is taken out to obtain the plant residual biochar.
Further, in the above scheme, the biochar is biochar which is sieved by a 100-mesh sieve.
further, in the scheme, the Fenton oxidizing agent consists of 10% citric acid solution, 1 mol/L ferrous sulfate and 30% hydrogen peroxide by mass concentration, wherein Fe (II) is H 2O2The (mol: mol) is 1: 10-1: 30, and the three reagents can be directly discharged into the environment after being used as cleaning agents, so that the soil and underground water bodies are not polluted.
Furthermore, the citric acid, the ferrous sulfate and the hydrogen peroxide are all analytically pure.
Preferably, the oscillation conditions in step two are: and (4) avoiding light, wherein the temperature is 25 ℃, the oscillation time is 24h, and the oscillation speed is 200 r/min.
Preferably, the temperature of the water for washing the biochar after Fenton oxidation in the third step is 45 ℃, and the oscillation speed is 100 r/min.
Preferably, the drying of the solid matters in the fourth step is natural air drying.
The invention also provides an application of removing USEPA PAHs in the biochar by Fenton oxidation, wherein the application refers to the simultaneous removal or reduction of the content of 9 or more PAHs in the biochar.
The USEPA PAHs are naphthalene, acenaphthylene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene and benzo [ a ] ]An anthracene compound which is a compound of an anthracene, 
Benzo [ b ] ]Fluoranthene, benzo [ k ] ]Fluoranthene, benzo [ a ] ]Pyrene, dibenzo [ a, h ] ]Anthracene, benzo [ ghi ] ]Perylene and indeno [1,2,3-cd ]Pyrene.
Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
The invention adopts a chemical oxidation mode Oxidizing and removing PAHs in the biochar, and effectively removing naphthalene, acenaphthylene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene and benzo [ a ] in the biochar ]An anthracene compound which is a compound of an anthracene, 
Benzo [ b ] ]Fluoranthene, benzo [ k ] ]Fluoranthene, benzo [ a ] ]Pyrene, dibenzo [ a, h ] ]Anthracene, benzo [ ghi ] ]Perylene and indeno [1,2,3-cd ]Pyrene and PAHs have high removal rate, and the technology has the characteristics of high efficiency, environmental protection and easy operation. The Fenton oxidation reagent used in the invention can remove PAHs in the biochar, ensure the safe application of the biochar in agricultural production, realize the harmless treatment of the biochar, simultaneously reduce the influence of the treatment liquid on the soil environment and the water body, reduce the harm of the biochar to the farmland, reduce the accumulation of PAHs in agricultural products, and is beneficial to ensuring the agricultural production safety and human health.
Drawings
FIG. 1: the removal rates of PAHs in biochar under different treatments, A-F represent examples 1-6, respectively.
FIG. 2: the removal rates of PAHs with different ring numbers in the biochar for each treatment are shown in examples 1-6.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of the invention:
1. Preparing biochar:
Air-drying and crushing rice straws, putting the obtained crushed rice straw into a crucible, sealing the crucible with tin foil paper, then putting the crucible into a muffle furnace, quickly heating the muffle furnace to 600 ℃, carrying out anaerobic pyrolysis for 4 hours, turning off a power supply, cooling the muffle furnace to room temperature, grinding, and sieving with a 100-mesh sieve to obtain the plant residual biochar.
2. And (3) measuring the content of PAHs (polycyclic aromatic hydrocarbons) of the biochar:
putting the prepared biochar sample into a 20m L glass centrifuge tube, adding 10m L dichloromethane, tightly covering, performing ultrasonic extraction in an ultrasonic water bath for 60min at 4000 r.min -1centrifuging for 10min, collecting 3m L supernatant, purifying with chromatography column (upper layer 2g anhydrous sodium sulfate, lower layer 2g silica gel) and eluting with 11m L1: 1 solution of dichloromethane and n-hexane, and filtering collecting the post-column extract and eluent into a rotary evaporation bottle, concentrating the post-column extract and eluent at a constant temperature of 40 ℃ until the extract and the eluent are dry, rinsing the extract and the eluent with methanol until the volume is 2m L, passing the extract and the eluent through an organic phase filter membrane with a pore diameter of 0.22 mu m, and then carrying out HP L C/UV-F L D analysis under the analysis conditions that a chromatographic column is a phi 4.6 × 250mm InertsilODS-PAHs special reverse phase chromatographic column, a mobile phase is methanol-water, a method of gradient elution and series connection of an ultraviolet detector and a fluorescence detector is adopted to separate the PAHs, wavelength switching is adopted for ultraviolet and fluorescence detection, a dual-wavelength detection mode is started by the ultraviolet detector, the flow rate of the mobile phase is 1.0m L/min, the column temperature is 40 ℃, and the sample.
3. Detailed description of the preferred embodiments
Examples 1 to 6, biochar was treated according to the above treatment method, wherein the fenton reagent ratio was the parameters in table 1, the treatment time was 24 hours, and PAHs detection was performed after washing and drying.
The total PAHs removal rate was calculated using the following formula:
TABLE 1 Effect of PAHs removal in biochar after treatment in examples 1-6
The test results are shown in fig. 1.
The biochar adopted in the embodiment is rice straw biochar, the total PAHs content is 7.30mg/kg, the removal rate of PAHs in the biochar can reach more than 80% after treatment in the embodiments 1-6, wherein the effect of the embodiment 4 is the best, the PAHs residual quantity is 0.23mg/kg after treatment for 24 hours, the total removal rate of PAHs is as high as 96% (figure 1), and in addition, the Fenton oxidation reagent is utilized to have a better removal effect (figure 2) on high-ring USEPA PAHs in the biochar so as to ensure the safety of agricultural production after the biochar is returned to the field.
From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of the present invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions. Accordingly, other embodiments are within the scope of the following claims.
Claims (6)
1. A method for removing USEPA PAHs in biochar by Fenton oxidation is characterized by comprising the following steps:
Step one, air-drying and crushing plant residual wastes, putting the obtained plant residual crushed material into a crucible, sealing the crucible with tin foil paper, then putting the crucible into a muffle furnace for carbonization under anaerobic conditions, cooling, grinding and sieving to obtain plant residual biochar;
Step two, mixing the biochar and the Fenton reagent according to the proportion of 1 g to 20 ml, transferring the mixture into a 50 ml conical flask, keeping out of the sun, keeping the temperature at 25 ℃, oscillating for 24 hours and oscillating at the speed of 200 r/min;
Centrifuging to remove supernatant, oscillating the solid with water for 15 min, adjusting the pH of the biochar to be neutral, and repeating the step for 5 times;
Step four, drying the residual solid to obtain the biochar without the USEPA PAHs;
wherein the Fenton reagent consists of 10% citric acid solution, 1 mol/L ferrous sulfate and 30% hydrogen peroxide by mass concentration, and Fe (II) in the Fenton reagent is H 2O2(mol: mol) is 1: 10 to 1: 30.
2. The method for removing USEPA PAHs in biochar by Fenton oxidation according to claim 1, wherein: the plant residue is any one or a mixture of more of rice straw, wheat straw and corn straw.
3. The method for removing USEPA PAHs in biochar by Fenton oxidation according to claim 1, wherein: and after the crucible is placed in a muffle furnace, rapidly heating the muffle furnace to 600 ℃, carrying out anaerobic pyrolysis for 4 hours, turning off a power supply, and taking out the crucible to obtain the plant residual biochar when the temperature of the muffle furnace is reduced to room temperature.
4. The method for removing USEPA PAHs in biochar by Fenton oxidation according to claim 1, wherein: the biochar is the biochar which is sieved by a 100-mesh sieve.
5. The method for removing USEPA PAHs in biochar by Fenton oxidation according to claim 1, wherein: in the third step, the temperature of water for cleaning the biochar after Fenton oxidation is 45 ℃, and the oscillation speed is 100 r/min.
6. The method for removing USEPA PAHs in biochar by Fenton oxidation according to claim 1, wherein: and step four, airing the solid matter into natural air drying.
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