CN112919576A - Method for removing antibiotics in wastewater by using biochar loaded bimetal to promote ionizing irradiation - Google Patents
Method for removing antibiotics in wastewater by using biochar loaded bimetal to promote ionizing irradiation Download PDFInfo
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- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 39
- 238000011282 treatment Methods 0.000 description 30
- IEDVJHCEMCRBQM-UHFFFAOYSA-N trimethoprim Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(N)=NC=2)N)=C1 IEDVJHCEMCRBQM-UHFFFAOYSA-N 0.000 description 22
- 229960001082 trimethoprim Drugs 0.000 description 22
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/307—Treatment of water, waste water, or sewage by irradiation with X-rays or gamma radiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/20—Total organic carbon [TOC]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
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Abstract
The invention provides a method for removing antibiotics in wastewater by biochar-loaded bimetal-promoted ionizing irradiation, which is characterized in that a bimetal composite system is formed by adding two metal elements (Fe and Cu or Fe and Co), so that electron transfer in the system is promoted, Fenton series reactions in an ionizing radiation system are catalyzed, the concentration of active free radicals in the system is increased, and the aim of strengthening the advanced oxidation process is fulfilled. The material is combined with ionizing radiation to treat antibiotic organic pollutants, has obvious and stable effect, improves the removal efficiency of Total Organic Carbon (TOC) in water, obviously mineralizes pollutants, can further improve the quality of effluent water, and ensures the safety of the effluent water.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a method for removing antibiotics in wastewater by biological carbon loaded bimetal promoted ionizing irradiation.
Background
Antibiotics pose a threat to ecosystem and human health due to their biotoxicity, and antibiotics in water are urgently needed for safe disposal. The currently common processing techniques are physical, biological and chemical. Physical methods (such as nanofiltration, adsorption, etc.) can only separate antibiotics from water, and still need further treatment, which cannot fundamentally solve the problem of antibiotic pollution. Because antibiotics are biologically toxic to microorganisms, traditional biological treatment methods have difficulty effectively degrading them. Chemical methods (Fenton oxidation technology, electrochemical oxidation technology and the like) can efficiently remove antibiotics in water, but some chemical methods have the problems of low mineralization rate, increased product toxicity and the like in the process of treating the antibiotics.
The ionizing radiation technology is a unique advanced oxidation technology, and plays an important role in the field of water treatment due to simple and convenient operation, safety and harmlessness. The principle comprises that firstly, high-energy rays are directly acted on pollutant molecules; secondly, high-energy rays are utilized to excite water molecules to generate active particles such as hydroxyl free radicals (OH) and the like, and then the active particles react with pollutants. As with most advanced oxidation techniques, ionizing radiation techniques can achieve efficient removal of organic contaminants, such as antibiotics, if the contaminants are to be completely converted to CO2And H2O, the irradiation dose needs to be larger, so that the energy consumption is higher, and the economic applicability of the radiation dose is influenced. In addition to the generation of hydroxyl free radicals with higher activity in the ionizing radiation technology, H also exists2O2Isooxidative components and eaq -And H, and the like, thereby developing an economical and efficient ionization radiation enhanced degradation technologyThe active particle components in the ionizing radiation system are utilized, which is particularly necessary.
Aiming at the defects of the technology, the invention provides a method for effectively removing antibiotics in water, which can effectively improve the mineralization rate of the antibiotics, simultaneously reduce the larger irradiation dose required by the ionizing radiation technology and realize the harmless treatment of the antibiotic wastewater.
Technical scheme
The invention aims to solve the technical problems that the mineralization rate is low in the existing technology for treating antibiotics in wastewater, and meanwhile, the large irradiation dose required by the ionizing radiation technology is reduced, and provides a method for removing the antibiotics in the wastewater by promoting ionizing radiation through charcoal-loaded bimetal.
The invention provides a method for removing antibiotics in wastewater by using biochar loaded bimetal to promote ionizing radiation, which comprises the following steps:
firstly, preparing a biochar material;
secondly, preparing biochar loaded bimetal;
and thirdly, placing the prepared biochar loaded bimetal in wastewater, uniformly mixing, and performing ionizing radiation to remove antibiotics in the water.
In the first step, the biochar material is prepared from biomass such as sludge, straws, sawdust and the like.
In the first step, the biomass material is cleaned and dried, and is calcined in a muffle furnace under the protection of nitrogen, cleaned and dried for later use.
Wherein, in the second step, the bimetal is a multi-valence metal.
Wherein, in the second step, the bimetal is selected to be iron (Fe)3+) Copper (Cu)+) Bimetallic or iron (Fe)3+) Cobalt (Co)2+) A bimetal.
And the second step of preparation specifically comprises the steps of mixing the bimetal and the biochar prepared in the first step in proportion, adding deionized water, carrying out magnetic stirring impregnation reaction, heating, stirring to evaporate water, drying, and then carrying out high-temperature calcination, cleaning and drying under the protection of nitrogen to form metal oxide attached to the surface of the biochar material.
In the second step, the mass ratio of the bimetal is 2:1-1: 2.
Wherein, in the third step, the ionizing radiation used is performed using gamma rays or a high-energy electron beam.
Wherein, in the third step, the radiation absorbed dose is not more than 1.5 kGy.
In the third step, the adding amount of the biochar loaded bimetal in the wastewater is 0.05-0.2 g/L.
Advantageous effects
The biochar loaded bimetal composite material used in the invention forms a bimetal composite system by adding two metal elements (Fe and Cu or Fe and Co), promotes electron transfer in the system, catalyzes Fenton series reactions in an ionizing radiation system, improves the concentration of active free radicals in the system and achieves the purpose of strengthening the advanced oxidation process. The material is combined with ionizing radiation to treat antibiotic organic pollutants, has obvious and stable effect, improves the removal efficiency of Total Organic Carbon (TOC) in water, obviously mineralizes pollutants, can further improve the quality of effluent water, and ensures the safety of the effluent water.
The material is simple to prepare, low in cost, easy to obtain and reusable. The technology can be used for treating wastewater containing refractory antibiotics such as medical wastewater, effluent of sewage plants and the like, and has huge application potential and market.
Drawings
FIG. 1 shows the removal rate of sulfamethoxazole under different treatment processes;
FIG. 2 shows the removal rate of TOC in sulfamethoxazole solution by irradiation, combined irradiation of biochar and single-metal-doped biochar;
FIG. 3 shows the removal of TOC from sulfamethoxazole under different treatment processes;
FIG. 4 shows the removal rate of trimethoprim under different treatment processes;
FIG. 5 shows the removal rate of TOC of trimethoprim under different treatment processes.
Detailed Description
Gamma rays or high-energy electron beams have high energy due to their high penetrating power and are ionized when they act on a substance, and this irradiation is called ionizing irradiation. The water molecules can generate radiolysis reaction after ionizing radiation to generate a series of high-reactivity particles, such as hydroxyl free radicals (OH) and H2O2And reducing property eaq -And H, which can cause oxidation-reduction reaction with substances in water to change the structure of the substances. The method is applied to the field of wastewater treatment, can decompose organic pollutants in water, and achieves the purposes of removing pollutants and purifying water. The technology is simple and convenient to operate, can be applied in a large scale, and has good development potential in the field of wastewater treatment.
H2O→H·(0.6),eaq -(2.7),·OH(2.8),H2(0.45),H2O2(0.72),H3O+(2.7) (1)
The number in parentheses of the formula (1) represents the yield (G value) of each active particle, and represents the number of particles released per 100eV of energy absorbed, in units of. mu. mol. J-1。
Due to the production of a certain amount of H after the water radiolysis2O2Adding proper amount of Fe2+Can initiate Fenton reaction to generate OH to promote the degradation of organic pollutants in water. And active reducing particles (e) which are generated by introducing metal elements (Fe/Cu or Fe/Co and the like) with different valence states into the system through different metals, metal ions and radiationaq -And H) in the redox reaction (formulas (2) to (5)), enhances electron transfer, promotes the divalent Fe conversion rate, and increases H2O2The efficiency is utilized, the Fenton-like series reaction process is accelerated, the generation of active free radicals such as OH is promoted, and the irradiation degradation mineralization efficiency of organic pollutants is improved.
Fe2++H2O2→Fe3++OH-+·OH (2)
Fe3++Cu+→Fe2++Cu2+ (3)
Fe3++e-→Fe2+ (4)
Fe3++H·→Fe2++H+ (5)
The biochar is formed by high-temperature carbonization of biomass (activated sludge, plant tissues, agricultural and forestry wastes, animal bones and the like) under an anaerobic condition, has a porous structure, a large specific surface area, an aromatic carbon structure and abundant surface groups, and has broad-spectrum adsorption capacity on organic pollutants with different polarities. Although the biochar can adsorb organic pollutants, after adsorption balance is achieved, the ability of continuously removing organic matters in the water body is lost, and the adsorbed biochar still needs to be treated, so the biochar is often used as an auxiliary means in the treatment process of the organic pollutants.
In the invention, waste gas such as sludge, straw and the like is taken as a biomass raw material, bimetal (such as iron and copper bimetal or iron and cobalt bimetal) is loaded on the biomass through adsorption and impregnation, and the bimetal is thermochemically converted into a biochar loaded bimetal material under an anaerobic condition. Under the irradiation condition, bimetal on the surface of the biochar loaded bimetal material generates a Fenton-like effect to generate more active free radicals, and the biochar loaded bimetal material has good adsorption performance, can adsorb antibiotic molecules to the surface of the material to increase the concentration of local antibiotic, and the synergistic effect of the two can promote the degradation and mineralization of the antibiotic in the wastewater.
Based on the above, the invention provides a method for removing antibiotics in wastewater by using biochar loaded bimetal to promote ionizing radiation, which comprises the following steps:
firstly, preparing a biochar material;
secondly, preparing biochar loaded bimetal;
and thirdly, placing the prepared biochar loaded bimetal in wastewater, uniformly mixing, and performing ionizing radiation to remove antibiotics in the water.
In the first step, the biochar material is prepared from biomass such as sludge, straws, sawdust and the like.
In the first step, the biomass material is cleaned and dried, and is calcined in a muffle furnace under the protection of nitrogen, cleaned and dried for later use.
In the first step, the calcining temperature is 600-800 ℃, preferably 700 ℃, and the calcining time is 1-3h, preferably 2 h.
In the second step, the bimetal is selected to be iron (Fe)3+) Copper (Cu)+) Bimetallic or iron (Fe)3+) Cobalt (Co)2+) A bimetal.
And the second step is specifically to mix the bimetal and the biochar prepared in the first step in proportion, add deionized water, perform magnetic stirring dipping reaction, perform heating stirring to evaporate water, dry, and then perform high-temperature calcination, cleaning and drying under the protection of nitrogen to form metal oxide attached to the surface of the biochar material.
In the second step, the mass ratio of the bimetal is preferably 2:1-1:2, more preferably 1:1, and the mass ratio of the biochar material prepared in the first step to the bimetal is 5:1-10:1, more preferably 5: 1.
In the second step, the calcining temperature is 600-800 ℃, preferably 700 ℃, and the calcining time is 1-3h, preferably 2 h.
In the third step, the ionizing radiation used is carried out using gamma rays or a high-energy electron beam.
In the third step, if gamma-rays are used, the gamma-rays are derived from the radioisotope60Co or137The Cs decays.
In the third step, the absorbed radiation dose is not more than 1.5 kGy.
In the third step, the addition amount of the biochar loaded bimetal in the wastewater is 0.05-0.2g/L, and preferably 0.1 g/L.
The following embodiments are described in detail to solve the technical problems by applying technical means to the present invention, and the implementation process of achieving the technical effects can be fully understood and implemented.
Comparative example 1 pure biochar material was combined with ionizing radiation to remove antibiotics from wastewater.
Preparing a biochar material:
centrifuging the activated sludge in an aerobic pool of a sewage plant to remove supernatant, repeatedly washing the activated sludge with deionized water for 4 times, and drying the activated sludge at the temperature of 80 ℃. Heating to 700 ℃ in a muffle furnace at a heating rate of 10 ℃/min under the protection of nitrogen, and calcining for 2 h. After natural cooling, the obtained material is washed by water and ethanol and dried for standby use at 70 ℃.
Dissolving a certain amount of sulfamethoxazole in deionized water to prepare an antibiotic sulfamethoxazole solution, wherein the initial concentration is 20mg/L, and the pH value is 5.4. Then adding 0.1g/L sludge biochar and mixing uniformly. Placing the mixed solution of the antibiotics and the biochar into an irradiation container, and adopting 60Co gamma rays (the radiation activity is 3.6 multiplied by 10)14Bq) is irradiated, and the dosage rate is about 30 Gy/min. Absorbed doses were controlled to 0.2, 0.4, 0.6, 0.8, 1.0 and 1.5kGy by adjusting irradiation time. After the irradiation is finished, the solution is centrifugally precipitated to recover biochar, and the supernatant is filtered by a 0.45-micron filter membrane to detect the sulfamethoxazole and TOC concentration. The solution without added biochar was irradiated simultaneously for comparison.
Sulfamethoxazole concentration was determined by high performance liquid chromatography (HPLC, Agilent 1200 series, Agilent, USA). The Total Organic Carbon (TOC) content in the aqueous solution was determined by TOC/TN 2100 analyzer (Analytik Jena AG Corporation). The pH of the reaction solution was measured using a Mettler S220-K desk type pH meter.
Sulfamethoxazole (SMX) removal under different treatment procedures is shown in Table 1
TABLE 1 removal of SMX under different treatment processes
When the sulfamethoxazole solution is singly irradiated, the removal rate of sulfamethoxazole is 30%, 44%, 59%, 87%, 96% and 100% when the absorbed dose is 0.2, 0.4, 0.6, 0.8, 1.0, 1.2 and 1.5 kGy; after the sludge biochar is added, the removal rate of sulfamethoxazole under the same dosage is 43%, 56%, 69%, 92%, 100% and 100%, and the removal rate is obviously improved.
The removal of TOC under irradiation and biochar-irradiation treatment is shown in FIG. 1. After the sludge biochar is added, the removal rate of TOC under the same absorbed dose is much higher than that under the irradiation alone. When the irradiation absorbed dose is 0.4, 1.0 and 1.5kGy respectively, the removal rate of TOC is 4.9%, 10.2% and 12.6% respectively when sulfamethoxazole solution is irradiated alone, and the removal rate of TOC can be respectively improved to 12.5%, 16.8% and 18.7% when sludge biochar is added and the sludge biochar is irradiated.
Comparative example 2 removal of antibiotics from wastewater by biochar-supported single metal material in combination with ionizing irradiation.
Preparing a biochar loaded single metal material:
centrifuging the activated sludge in an aerobic pool of a sewage plant to remove supernatant, repeatedly washing the activated sludge with deionized water for 4 times, and drying the activated sludge at the temperature of 80 ℃. According to the mass ratio of 10:1 and 10:2 (mud: Fe) and respectively weighing the sludge and the metal salt (FeCl)3) Mixing the mixture in a certain amount of deionized water, and carrying out soaking reaction for 6 hours under magnetic stirring. Then, the mixture is heated and stirred to evaporate water, and is dried at 80 ℃. Heating to 700 ℃ in a muffle furnace at a heating rate of 10 ℃/min under the protection of nitrogen, and calcining for 2 h. After natural cooling, the obtained material is dried for standby after being cleaned at 80 ℃.
Dissolving a certain amount of sulfamethoxazole in deionized water to prepare an antibiotic sulfamethoxazole solution, wherein the initial concentration is 20mg/L, and the pH value is 5.4. Then adding 0.1g/L sludge biochar and mixing uniformly. Placing the mixed solution of the antibiotic and the charcoal in an irradiation container, and adopting gamma rays (the radiation activity is 3.6 multiplied by 10)14Bq) is irradiated, and the dosage rate is about 30 Gy/min. Absorbed doses were controlled to 0.2, 0.4, 0.6, 0.8, 1.0 and 1.5kGy by adjusting irradiation time. After the irradiation is finished, the solution is centrifugally precipitated to recover biochar, and the supernatant is filtered by a 0.45-micron filter membrane to detect the sulfamethoxazole and TOC concentration. The detection method was the same as in comparative example 1.
The removal of Sulfamethoxazole (SMX) under different treatment processes is shown in Table 2.
TABLE 2 SMX removal under different treatment processes
When the sulfamethoxazole solution is singly irradiated, the removal rate of sulfamethoxazole is 30%, 44%, 59%, 87%, 96% and 100% when the absorbed dose is 0.2, 0.4, 0.6, 0.8, 1.0, 1.2 and 1.5 kGy; after a sludge biochar loaded single metal material (sludge: Fe is 10:1) is added, the removal rate of sulfamethoxazole under the same dosage is 45%, 58%, 69%, 93%, 100% and 100%, and compared with single irradiation, the removal rate is improved; when pure biochar is added for combined irradiation (table 1), the removal rate under the same absorbed dose is 43%, 56%, 69%, 92%, 100% and 100%, so that the removal rate of sulfamethoxazole is not obviously improved by using a biochar-loaded single metal material compared with a pure biochar material. In addition, the material with different mud and Fe ratios has no obvious change on the removal effect of antibiotics.
The removal of TOC by irradiation combined with the irradiation treatment process of biochar-supported single metal material is shown in fig. 2. After the sludge biochar loaded with a single metal material is added, the removal rate of TOC under the same absorbed dose is much higher than that under the condition of independent irradiation. When the irradiation absorbed dose is 0.4, 1.0 and 1.5kGy respectively, the removal rate of TOC is 4.9%, 10.2% and 12.6% respectively when the sulfamethoxazole solution is irradiated alone, and the removal rate of TOC can be respectively increased to 11.5%, 17.7% and 20.8% (mud: Fe: 10:1) and 12.5%, 17.5% and 21.7% (mud: Fe: 10:2) after the sludge biochar is added and the single metal material is loaded. However, compared with the single biochar combined irradiation treatment process in the comparative example 1, the removal of TOC organisms by the biochar loaded single metal combined irradiation system is only slightly improved, and can be improved by about 3 percent (1.5kGy) to the maximum extent. The method shows that the removal of TOC of the antibiotic solution by the irradiation system can be improved after a single metal element is added into the biochar, but the improvement performance is weaker and needs to be further enhanced.
Example 1 removal of the antibiotic sulfamethoxazole in wastewater by a biochar-supported bimetallic material in combination with ionizing irradiation.
Preparing a biochar loaded bimetallic material:
get the active dirty of the aerobic pool of sewage plantCentrifuging the mud to remove supernatant, repeatedly washing with deionized water for 4 times, and oven drying at 80 deg.C. According to the mass ratio of 10: 1:1 (mud: Fe: Cu) and respectively weighing mud and metal salt (FeCl)3And (Cu)2SO4) Mixing the mixture in a certain amount of deionized water, and carrying out soaking reaction for 6 hours under magnetic stirring. Then, the mixture is heated and stirred to evaporate water, and is dried at 80 ℃. Heating to 700 ℃ in a muffle furnace at a heating rate of 10 ℃/min under the protection of nitrogen, and calcining for 2 h. After natural cooling, the obtained material is dried for standby after being cleaned at 80 ℃.
Dissolving a certain amount of sulfamethoxazole in deionized water to prepare an antibiotic sulfamethoxazole solution, wherein the initial concentration is 20mg/L, and the pH value is 5.4. Then adding 0.1g/L sludge biochar loaded bimetallic material, and mixing uniformly. Placing the mixed solution of the antibiotic and the charcoal in an irradiation container, and adopting gamma rays (the radiation activity is 3.6 multiplied by 10)14Bq) is irradiated, and the dosage rate is about 30 Gy/min. Absorbed doses were controlled to 0.2, 0.4, 0.6, 0.8, 1.0 and 1.5kGy by adjusting irradiation time. After the irradiation is finished, the supernatant is filtered by a filter membrane of 0.45 mu m, and then the sulfamethoxazole and TOC concentration are detected.
In addition, the TOC concentration of sulfamethoxazole was tested under 5kGy irradiation alone.
The detection method was the same as in comparative example 1.
The removal of SMX by irradiation and biochar-loaded bimetallic combined irradiation treatment process is shown in table 3.
TABLE 3 removal of SMX under irradiation and biochar-loaded bimetallic combined irradiation
The results show that the removal efficiency of sulfamethoxazole is obviously increased after the irradiation treatment after the addition of the biological activated carbon loaded bimetal, and the removal rates of sulfamethoxazole are respectively 30%, 44%, 59%, 87%, 96% and 100% under a single irradiation system and when the absorbed doses are 0.2, 0.4, 0.6, 0.8, 1.0, 1.2 and 1.5 kGy; as can be seen in Table 1, under the same dosage, the removal rate of the sulfamethoxazole under the condition without bimetal load is 43%, 56%, 69%, 92%, 100% and 100%, and the removal rate of the antibiotic under the combined irradiation system of the bimetal-doped biochar is obviously improved; in table 2, the removal rates of sulfamethoxazole were 44%, 59%, 70%, 93%, 100%, and 100% at the same dosage after adding the single metal-doped sludge biochar (sludge: iron: 10:2), while in table 3, the removal rates of sulfamethoxazole were 45%, 57%, 73%, 98%, 100%, and 100% at the same dosage after adding the double metal-doped sludge biochar, respectively, indicating that the removal rates were further improved compared with those of the single metal system.
The removal of TOC under different treatment processes is shown in fig. 3. After the biological activated carbon loaded bimetallic material is added, the removal of TOC by the system is also obviously increased under the same irradiation dose, when the irradiation absorbed doses are respectively 0.4, 1.0 and 1.5kGy, the removal rates of TOC are respectively 4.9%, 10.2% and 12.6% when sulfamethoxazole solution is irradiated independently, and after the sludge biological carbon is added, the removal rates of TOC are respectively improved to 12.5%, 16.8% and 18.7% when the sludge biological carbon is irradiated; adding sludge biochar loaded with a single metal material, and irradiating to remove 11.5%, 17.7% and 20.8% of TOC (mud: iron: 10: 1); the removal rates of TOC after adding the metal-biochar are respectively 13.5%, 22.1% and 28.8%, the data are much higher than those of the data in independent irradiation treatment and the data are also much higher than the TOC in biochar adding and single metal doped biochar adding, which shows that the performance of removing TOC in an irradiation system is further improved after doping the biochar with double metals, and the double metal doped biochar has a better promotion effect on the performance of removing antibiotics in the irradiation system.
In addition, as can also be seen from fig. 3, under a single irradiation system, when the dosage is high (5.0kGy), the TOC removal rate of the system to the antibiotic solution is about 23%, which is similar to the TOC removal rate of the bimetal-doped biochar combined irradiation system when the dosage is 1.0kGy, which indicates that the bimetal-doped biochar combined irradiation system can not only effectively improve the mineralization rate of the antibiotic, but also reduce the relatively large irradiation dosage required when the ionizing radiation technology is used for treating the pollutants alone.
Example 2 removal of the antibiotic trimethoprim in wastewater by biochar-supported bimetallic material in combination with ionizing irradiation.
Dissolving a certain amount of trimethoprim in deionized water to prepare an antibiotic trimethoprim solution, wherein the initial concentration is 50mg/L, and the pH value is 7.2. Then 0.1g/L of the bimetal-sludge biochar prepared in example 1 is added and mixed evenly. Placing the mixed solution of the antibiotics and the biochar into an irradiation container, and adopting 60Co gamma rays (the radiation activity is 3.6 multiplied by 10)14Bq) is irradiated, and the dosage rate is about 30 Gy/min. Absorbed doses were controlled to 0.2, 0.4, 0.6, 0.8, 1.0 and 1.5kGy by adjusting irradiation time. After the irradiation is finished, the solution is centrifugally precipitated to recover biochar, and after supernatant is filtered by a 0.45-micrometer filter membrane, the concentrations of trimethoprim and TOC are detected.
The concentration of trimethoprim was determined by high performance liquid chromatography (HPLC, Agilent 1200 series, Agilent, usa). The HPLC equipped detector was a diode array detector, the column was a C18 reverse phase column (250 mm. times.4.6 mm; 5 μm) and the detection column temperature was 30 ℃. The Total Organic Carbon (TOC) content in the aqueous solution was determined by TOC/TN 2100 analyzer (Analytik Jena AG Corporation). The pH of the reaction solution was measured using a Mettler S220-K desk type pH meter.
The removal and mineralization of trimethoprim by different treatments are shown in tables 4 and 5.
TABLE 4 removal of trimethoprim by different treatments
TABLE 5 removal of TOC during treatment of trimethoprim with different treatment procedures
According to results, the removal efficiency of the trimethoprim and the removal rate of TOC by irradiation treatment after adding the biochar or the bimetal-biochar are obviously increased compared with the removal rate of the trimethoprim by irradiation treatment alone, and the removal rates of the trimethoprim are respectively 25%, 38%, 67%, 77%, 88% and 100% under a single irradiation system and the absorbed doses of 0.2, 0.4, 0.6, 0.8, 1.0, 1.2 and 1.5 kGy; when the biochar plus irradiation treatment is adopted, the removal rates of the trimethoprim are respectively 33%, 45%, 76%, 87%, 98% and 100%; after the bimetallic doped sludge biochar is added, the removal rates of trimethoprim under the same dosage are 34%, 50%, 88%, 97%, 100% and 100% respectively.
In addition, after the bimetal-biochar material is added, the removal rate of the TOC of the system is also obviously increased under the same irradiation dose, when the irradiation absorbed doses are respectively 0.4, 1.0 and 1.5kGy, and when the trimethoprim solution is irradiated independently, the removal rates of the TOC are respectively 4.9%, 10.2% and 12.6, and after the sludge biochar is added, the removal rates of the TOC are respectively increased to 12.5%, 16.8% and 18.7% by irradiation; after the metal-biochar is added, the removal rate of TOC is respectively 13.5%, 22.1% and 28.8%, and the data are much higher than that of the data obtained by independent irradiation treatment and higher than that of the data obtained by adding the biochar, which shows that the performance of removing TOC in an irradiation system is further improved after the biochar is subjected to bimetallic doping.
Example 3
Taking the agricultural and forestry waste rice field straws, drying and smashing. According to the mass ratio of 10: 1:1 (straw: Fe: Co) and respectively weighing straw and metal salt (FeCl)3And Co (NO)3)2) Mixing with a certain amount of deionized water, and carrying out soaking reaction for 6 hours under magnetic stirring. Then, the mixture is heated and stirred to evaporate water, and is dried at 80 ℃. Heating to 700 ℃ in a muffle furnace at a heating rate of 10 ℃/min under the protection of nitrogen, and calcining for 2 h. After natural cooling, the obtained material is dried for standby after being cleaned at 80 ℃.
Dissolving a certain amount of trimethoprim in deionized water to prepare an antibiotic sulfamethoxazole solution, wherein the initial concentration is 50mg/L, and the pH value is 7.2. Then theAdding 0.1g/L straw biochar loaded bimetal, and mixing uniformly. Placing the mixed solution of the antibiotic and the charcoal in an irradiation container, and adopting gamma rays (the radiation activity is 3.6 multiplied by 10)14Bq) is irradiated, and the dosage rate is about 30 Gy/min. The absorbed dose was controlled to 1.0kGy by adjusting the irradiation time. And after the irradiation is finished, detecting the concentrations of trimethoprim and TOC.
The detection method is the same as that of the comparative example.
The removal of trimethoprim and TOC by irradiation and irradiation combined with straw biochar treatment is shown in figures 4 and 5.
According to results, when the trimethoprim is treated by single irradiation, straw biochar combined irradiation and biochar loaded iron-cobalt bimetallic material combined irradiation (irradiation dose is 1.0kGy), the removal rates of the antibiotics trimethoprim and TOC are 77%, 91% and 100%, and 10.2%, 18.8% and 27.1%, respectively, which shows that the straw biochar loaded iron-cobalt bimetallic material combined irradiation has better degradation and mineralization removal effects on the trimethoprim. The straw biochar loaded iron-cobalt bimetallic material has a good catalytic promotion effect on removing organic pollutants such as antibiotics in water by ionizing irradiation.
All of the above mentioned intellectual property rights are not intended to be restrictive to other forms of implementing the new and/or new products. Those skilled in the art will take advantage of this important information, and the foregoing will be modified to achieve similar performance. However, all modifications or alterations are based on the new products of the invention and belong to the reserved rights.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (10)
1. A method for removing antibiotics in wastewater by using biochar loaded bimetal to promote ionizing radiation is characterized by comprising the following steps:
firstly, preparing a biochar material;
secondly, preparing biochar loaded bimetal;
and thirdly, placing the prepared biochar loaded bimetal in wastewater, uniformly mixing, and performing ionizing radiation to remove antibiotics in the water.
2. The method for removing antibiotics in wastewater by using biochar-loaded bimetal through promoting ionizing radiation as claimed in claim 1, wherein the method comprises the following steps: in the first step, the biochar material is prepared from biomass such as sludge, straws, sawdust and the like.
3. The method for removing antibiotics in wastewater by using biochar-loaded bimetal through promoting ionizing radiation as claimed in claim 2, wherein the method comprises the following steps: in the first step, the biomass material is cleaned and dried, and is calcined in a muffle furnace under the protection of nitrogen, cleaned and dried for later use.
4. The method for removing antibiotics in wastewater by using biochar-loaded bimetal through promoting ionizing radiation as claimed in claim 1, wherein the method comprises the following steps: in the second step, the bimetal is a multi-valence metal.
5. The method for removing antibiotics in wastewater by using biochar-loaded bimetal through promoting ionizing radiation as claimed in claim 4, wherein the method comprises the following steps: in the second step, the bimetal is selected to be iron (Fe)3+) Copper (Cu)+) Bimetallic or iron (Fe)3+) Cobalt (Co)2+) A bimetal.
6. The method for removing antibiotics in wastewater by using biochar-loaded bimetal promoted by ionizing radiation as claimed in claim 1 or 4, characterized in that: and the second step is specifically to mix the bimetal and the biochar prepared in the first step in proportion, add deionized water, perform magnetic stirring dipping reaction, perform heating stirring to evaporate water, dry, and then perform high-temperature calcination, cleaning and drying under the protection of nitrogen to form metal oxide attached to the surface of the biochar material.
7. The method for removing antibiotics in wastewater by using biochar-loaded bimetal promoted by ionizing radiation as claimed in claim 1 or 4, characterized in that: in the second step, the mass ratio of the bimetal is 2:1-1: 2.
8. The method for removing antibiotics in wastewater by using biochar-loaded bimetal through promoting ionizing radiation as claimed in claim 1, wherein the method comprises the following steps: in the third step, the ionizing radiation used is carried out using gamma rays or a high-energy electron beam.
9. The method for removing antibiotics in wastewater by using biochar-loaded bimetal promoted by ionizing radiation as claimed in claim 1 or 8, which is characterized in that: in the third step, the absorbed radiation dose is not more than 1.5 kGy.
10. The method for removing antibiotics in wastewater by using biochar-loaded bimetal promoted by ionizing radiation as claimed in claim 1 or 8, which is characterized in that: in the third step, the adding amount of the biochar loaded bimetal in the wastewater is 0.05-0.2 g/L.
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