CN113233573A - Treatment method of BPA-containing sewage and ball-milling modified magnetic biochar composite material - Google Patents
Treatment method of BPA-containing sewage and ball-milling modified magnetic biochar composite material Download PDFInfo
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Images
Classifications
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- 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
- C02F2101/345—Phenols
Abstract
The invention discloses a treatment method of BPA-containing sewage, a ball-milling modified magnetic biochar composite material and a preparation method thereof, wherein the treatment method comprises the following steps: A) preparation of Fe3O4@ MBC; B) obtaining a BPA-containing sewage sample and measuring the concentration of BPA; C) detecting the pH value of the sewage; D) PDS is added, and Fe with different proportional dosage is added3O4@ MBC, obtaining the optimal feeding proportion; E) according to the optimal feeding proportion, adding Fe3O4The @ MBC is added into the BPA-containing sewage, PDS is catalyzed by the MBC, and the MBC and the PDS jointly complete the degradation and removal of the BPA in the water body. The invention also discloses a ball-milling modified magnetic biochar composite material which is prepared by loading Fe on the surface of ball-milling biochar3O4And (3) a flaky black solid powder composite material obtained by layering. The invention also discloses a preparation method of the material. The material adopted by the invention has a unique load structure, good sewage treatment effect and low cost.
Description
Technical Field
The invention belongs to the technical field of sewage treatment and magnetic composite materials, and particularly relates to a treatment method of BPA-containing sewage and a ball-milling modified magnetic biochar composite material.
Background
Bisphenol A, also known as BPA, is an organic compound having the formula C15H16O2. Bisphenol a is used industrially to synthesize materials such as Polycarbonate (PC) and epoxy resin. For the past 60 years, have been used to manufacture plastic (milk) bottles, drinking cups for infants, and can inner coatings for food and beverage (milk powder).
Bisphenol A is one of the most widely used industrial compounds in the world, and is mainly used for producing various high polymer materials such as polycarbonate, epoxy resin, polysulfone resin, polyphenyl ether resin, unsaturated polyester resin and the like. And can also be used for producing fine chemical products such as plasticizers, flame retardants, antioxidants, heat stabilizers, rubber antioxidants, pesticides, coatings and the like.
In the manufacturing process of plastic products, bisphenol A is added to enable the plastic products to have the characteristics of colorless transparency, durability, lightness, outstanding impact resistance and the like, and particularly to prevent acidic vegetables and fruits from corroding metal containers from the inside, so that the bisphenol A is widely used in the manufacturing process of packages of canned foods and beverages, sealing glue for feeding bottles, water bottles and tooth fillers, spectacle lenses and other hundreds of daily necessities.
BPA is ubiquitous and has its silhouette from mineral water bottles, medical devices, and into food packaging. Every year, 2700 million tons of BPA-containing plastics are produced worldwide. BPA can also cause endocrine dysregulation, threatening the health of fetuses and children. Cancer and obesity caused by metabolic disorders are also considered to be associated therewith.
Bisphenol A is harmful to human health and has been proven in various tests. The existing research shows that bisphenol A belongs to a low-toxicity chemical substance. Animal experiments show that the bisphenol A has the effect of simulating estrogen, and can enable the animals to have the effects of premature females, reduced sperm count, increased prostate gland and the like even with very low dose. In addition, the data show that bisphenol A has certain embryotoxicity and teratogenicity, and can obviously increase the occurrence of cancers such as animal ovarian cancer, prostatic cancer, leukemia and the like. Meanwhile, researches show that bisphenol A is associated with asthma of mice, and preliminary human experiments show that the influence of bisphenol A on pregnant women in early pregnancy can cause infants to be infected with asthma.
BPA is mainly added into a product in a simple physical adding mode, enters the environment in modes of volatilization, leaching, abrasion and the like in the production and use of the product, and has caused serious pollution to the water environment. BPA in water body may generate toxic and endocrine disturbing effects such as liver and kidney, nerves and the like to human body, and the monitoring of human is seriously influenced. In 2017, the world health organization international agency for research on cancer listed it as a class 2A carcinogen. Therefore, how to effectively remove BPA in water environment has been widely concerned by domestic and foreign research.
The existing method for removing BPA in sewage mainly comprises a physical degradation method, a biological degradation method, a catalytic oxidation method and the like. The existing research finds that the porous carbon material is considered to be an excellent remover of hydrophobic organic pollutants due to the large specific surface area and high hydrophobicity. The porous carbon material is widely applied to the treatment of organic wastewater due to the characteristics of low price, high degradation amount, easy separation and the like. For example, Li and the like utilize sewage sludge to prepare porous biochar to degrade BPA, and the degradation is mainly homogeneous and chemical processes, but the degradation effect is greatly influenced by the change of the pH value of an environmental factor and soluble organic matter (DOM). Shao et al, a porous carbon microsphere prepared from waste butts has good degradation performance on bisphenol A (BPA), the maximum degradation amount is 865 mg/g, but the degradation speed is slow, the efficiency is low, and the porous carbon microsphere is also easily influenced by changes of environmental factor pH and soluble organic matter (DOM).
In order to solve the problems, the Chinese patent application No. 201810234261.8 discloses a method for removing endocrine disrupters in water by using a carbon-based magnetic metal composite material to catalyze and activate peroxydisulfate, belonging to the field of chemical treatment of polluted wastewater. The invention aims to solve the problems of high cost, poor removal effect, complex process and the like of the existing method for removing endocrine disruptors in water. The method comprises the following steps: firstly, mixing peroxydisulfate with pretreated water; secondly, adjusting the pH value of the reaction; thirdly, preparing a carbon-based magnetic metal composite material; fourthly, adding a carbon-based magnetic multi-element metal material; and fifthly, separating the magnetic material by adopting an external magnetic field, namely completing the method for removing endocrine disrupters in water by using the carbon-based magnetic metal composite material to catalyze and activate the peroxydisulfate. The efficiency of removing endocrine disruptors in water by using the method of the invention can reach 80-97%.
However, the above patent solutions have the following disadvantages: firstly, the cation exchange resin is adopted as a raw material for preparing the carbon-based material, so that the cost is high; secondly, the limitation of environmental conditions is large, the removal effect of pollutants is obviously influenced by pH, the adaptive pH value range is narrow in the process of removing the pollutants, the pH value of the wastewater is usually required to be adjusted, and the process is complex; thirdly, various metal cations are doped in the carbon-based material, so that the difficulty and the cost of preparing the material are increased on one hand, and the doped cobalt element is listed as a 2B class carcinogen by the international cancer research institution of the world health organization in 2017 on the other hand, so that the ecological health safety risk exists and the price is high; fourthly, the catalytic stability of the material is low when the material is stored in the air atmosphere for a long time.
In addition, at present, the modification of the porous carbon material comprises methods such as acid/alkali modification and chemical oxidation, and because the ball-milling modified material prepared by the mechanical ball-milling method has large surface crushing degree and complex manufacturing process, the mechanical ball-milling modification method is not adopted.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention provides a new method for treating BPA-containing wastewater, which uses ball milling to modify magnetic biochar composite material Fe3O4@ MBC is taken as a removing agent of BPA-containing sewage, and is specifically modified by ball millingThe material is low in cost, high in catalysis and degradation efficiency and stable in degradation effect, and is slightly influenced by the pH value, anions and dissolved organic matters of the wastewater in the process of removing the BPA (bisphenol A) in the wastewater, so that the limitation of environmental conditions is overcome, the treatment efficiency and effect of the sewage are improved, and the treatment cost is reduced;
the invention also provides a ball-milling modified magnetic biochar composite material and a preparation method thereof, and the material is modified by synchronously improving the surface shape and structure of the biochar and the mechanical ball-milling preparation process, so that a compound with stable quality and low breakage rate is obtained; the material can improve the removal efficiency of BPA in a water body, and reduce the influence of the change of the pH value of wastewater, metal ions and soluble organic matters (DOM) on the removal effect; the preparation method has the advantages of simple process, stable quality of the biochar, small breakage rate, high controllability of the reaction process and easy industrialization.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a method for treating BPA-containing sewage is characterized by comprising the following steps:
A) preparation of ball-milling modified magnetic biochar composite Fe as BPA-containing sewage remover3O4@MBC；
B) Obtaining a BPA-containing sewage sample, and measuring the concentration of BPA by using high performance liquid chromatography;
C) detecting whether the pH value of the sewage is in the range of 3-9, if not, adjusting the pH value of the BPA sewage to 3-9;
D) PDS is added to reach the concentration of 5mM in the sewage sample, and then ball-milling modified magnetic biochar composite Fe with different proportional dosage is taken3O4@ MBC, respectively adding the materials into BPA-containing sewage samples, and testing to obtain and verify the BPA removal performance and the optimal feeding proportion of the materials:
E) according to the optimal feeding proportion obtained by the test, the ball-milling modified magnetic biochar composite material Fe3O4The @ MBC is added into the BPA-containing sewage and catalyzes PDS, and the @ MBC and the PDS jointly complete the degradation and removal of the BPA in the water body: a large amount of Fe attached to the surface of the ball-milled biochar3O4After a series of catalytic reactions with peroxydisulfate, ∙ OH and SO with high oxidation activity are generated4 ∙-，∙O2 -And1O2active substances which degrade BPA in the water body and finally mineralize it to harmless CO2And H2O。
F) Regeneration and reuse: using used ball-milling modified magnetic biochar composite material Fe3O4The method comprises the following steps of @ MBC centrifugal separation and recovery, repeated washing with ultrapure water and ethanol, and vacuum drying in a vacuum drying oven at 50 ℃ for 12 h to recover the BPA removal capacity of the vacuum drying oven; collecting the dried material, and repeating the steps B) to E) to carry out next cycle of degradation and removal of BPA in the water body;
G) and F) repeating the step F), completing multiple degradation-regeneration-degradation cycles, and removing the BPA in the water body.
The step C) also comprises the following steps:
c-1) adding 0.1-0.5M acid or alkaline compound containing metal cation into the sewage sample solution to adjust the pH of the sewage sample to 3-9, cooperating with Fe3O4The material of @ MBC catalyzes PDS to remove BPA in the water body.
The ball-milling modified magnetic biochar composite material for the BPA-containing sewage treatment method is characterized in that Fe is loaded on the surface of ball-milling biochar3O4Flaky black solid powder composite Fe obtained by lamellar3O4@ MBC, Fe therein3O4The crystal lattice has a trans-spinel structure, and the lattice spacing of each lamella is 0.2-0.3 nm; iron oxide loaded on the surface of the ball-milled biochar exists in the form of ferrous iron and ferric iron at the same time; wherein the ball-milled biochar is of an amorphous carbon and graphitic carbon structure; said Fe3O4The surface of @ MBC has C-O, C = O, O-C = O oxygen-containing functional group which is used as an electron donor acceptor to directly degrade organic pollutants on one hand and is used as an electron shuttle to mediate the degradation of organic pollutants BPA on the other hand.
According to mass percent, the Fe3O4The surface carbon content of the @ MBC is 40-45%, the oxygen content is 30-40%, and the iron content is 15-30%.
The ball-milling modified magnetic biochar composite material Fe3O4The @ MBC has strong paramagnetism and can be smoothly separated in a liquid phase by an external magnet.
The ball-milling modified magnetic biochar composite material Fe3O4The @ MBC has stronger thermal stability, and the mass loss is not more than 10% before the temperature is heated to 780 ℃.
The ball-milling modified magnetic biochar composite material Fe3O4The @ MBC material has a mesoporous structure, the average pore diameter is 10 nm, and the specific surface area is not less than 140 m2G, Raman peak area ratio ID/IGNot less than 1.10, and the surface of the material has rich defect sites, and the material has strong catalytic capability on PDS.
The preparation method of the ball-milling modified magnetic biochar composite material is characterized by comprising the following steps:
s1: preparing the biochar: drying the wood chip biomass in an oven at 60 ℃, grinding and crushing the wood chip biomass, putting the wood chip biomass into a corundum boat, putting the corundum boat into a tubular furnace, heating to 800 ℃, keeping the temperature for 2 hours, cooling to 75 ℃, and obtaining the charcoal powder, and taking out the charcoal powder for later use;
s2: preparing ball-milling modified biochar: putting the charcoal powder and the grinding balls into a ball milling tank according to the proportion of 1:100, and carrying out ball milling for 6-12 h;
s3: preparation of ball-milled modified magnetic biochar composite Fe3O4@MBC：
FeCl is added in a molar ratio of 2:13And FeSO4·7H2O is isolated from air at room temperature and stirred until dissolved; adding a corresponding amount of ball-milling modified biochar into the solution according to the mass ratio of 1:1, stirring at room temperature, continuously dropwise adding 10M NaOH into the solution until the pH value is 10-11, and generating black precipitates successively; stirring at room temperature until the precipitate is complete, standing, and separating the black precipitate by magnet or suction filtration to obtain scale-shaped ball-milling modified magnetic biochar composite Fe3O4@MBC；Fe3O4The generation process comprises the following steps:Fe2+ + 2Fe3+ + 8OH- → Fe3O4 + 4H2O。
the step S1 specifically includes: drying the pine sawdust biomass in an oven at 60 ℃, grinding and crushing the pine sawdust biomass through a sieve of 250 mu m, putting a certain amount of sieved biomass in a corundum boat and placing the corundum boat in a tubular furnace, wherein the temperature rising program of the tubular furnace is as follows: heating from room temperature to 800 ℃ at 10 ℃/min, keeping at 800 ℃ for 2 h, cooling from 800 ℃ to 75 ℃ at 10 ℃/min to obtain biochar, and taking out for later use;
the step S2 specifically includes: placing the prepared biochar and grinding balls in a ball milling tank in a ratio of 1:100, rotating clockwise for 3 hours at a rotating speed of 300 r/min, stopping running for 30 minutes, then rotating anticlockwise for 3 hours at a rotating speed of 300 r/min to form a ball milling process, and repeating the process twice to obtain ball milling modified biochar;
the step S3 specifically includes: FeCl is added in a molar ratio of 2:13And FeSO4·7H2Placing the O in a three-neck flask with air exhausted, and stirring at room temperature until the O is dissolved to obtain a mixed solution; placing the ball-milling modified biochar into the mixed solution according to the mass ratio of 1:1, stirring for 30 min at room temperature, continuously dropwise adding 10M NaOH into the mixed solution until the pH value is 10-11, and continuously generating black precipitates; continuously stirring for 1 h at room temperature of 50 r/min until the precipitate is complete, standing for 3-4 h at room temperature, and separating the black precipitate by using a magnet or suction filtration to obtain Fe3O4@ MBC; separating the separated Fe3O4@ MBC was washed 5 times with ultrapure water, 3 times with absolute ethanol, and dried under vacuum for future use.
Compared with the prior art, the invention has the advantages that:
1. the method for treating the BPA-containing sewage provided by the invention does not need to adopt cation exchange resin as a raw material for preparing a carbon-based material, but adopts Fe which has a unique structure, is cheap and can be repeatedly used3O4The @ MBC and the PDS cooperatively finish the degradation of BPA in the water body, the degradation efficiency is high, the degradation effect is stable, the influence of the pH value, the anions and the dissolved organic matters of the wastewater and the like in the treatment process is small, and the environmental conditions are overcomeLimitation, and the application range is widened; in most cases, the pH value of the wastewater is not required to be adjusted, the treatment process is simplified, the treatment cost is reduced, and the method is favorable for large-area popularization.
2. The invention provides a method for treating BPA-containing sewage, which is characterized in that a large amount of Fe attached to the surface of ball-milled biochar through a unique load structure3O4Activating (catalyzing) peroxydisulfate, and generating ∙ OH, SO with high oxidation activity through a series of reactions4 ∙-，∙O2 -And1O2isoactive species degrade BPA and mineralize it ultimately to CO2And H2And O. The material is proved by experiments to be Fe3O4The removal process of the @ MBC to BPA is less influenced by the pH value of the water body, the metal cations in the water body and the change of soluble organic matters (DOM), the adaptability of environmental conditions is greatly improved, and the method has a wide application prospect.
3. The invention provides a treatment method and a ball-milling modified magnetic biochar composite Fe3O4@ MBC, enhancing the Fe-to-biochar by modifying the surface of the ball mill3O4The ability to adhere to, and the ability to catalyze PDS, thus improving BPA removal performance. The ball milling modification can obviously change the surface structure, physical and chemical characteristics of the biochar: compared with an unmodified biochar material, the modified biochar material has the advantages that the surface defect sites, the specific surface area, the pore volume, the surface functional group content, the thermal stability and the dispersibility are increased, so that the catalytic capability of the modified biochar material on PDS and the BPA removal capability are enhanced, and the catalytic capability and the BPA removal capability of the modified biochar material are improved by 3 times compared with the unmodified biochar material.
4. The invention provides a ball-milling modified magnetic biochar composite Fe3O4The main raw material adopted by the method is agricultural and forestry waste, and a plurality of metal cations do not need to be doped in the carbon-based material, so that the cost of the prepared material is reduced on the basis of realizing the resource utilization of the waste; greatly simplify Fe3O4The process for preparing the @ MBC is characterized in that the Fe content of the conventional biochar can be greatly improved by carrying out ball milling under specific process conditions through improving the process3O4Load ofAn amount; and the compound obtained after ball milling has stable quality and small breakage rate, and is easy to realize industrialization.
Drawings
FIG. 1(a) and FIG. 1(b) show Fe of an embodiment of the present invention3O4An ultra-high resolution transmission electron micrograph of @ MBC;
FIG. 1(c) shows Fe in an example of the present invention3O4The XRD pattern of @ MBC;
FIG. 2(a) shows Fe3O4XPS element distribution profile of @ MBC;
FIG. 2(b) shows Fe in example of the present invention3O4C1s partial peak plot of @ MBC;
FIG. 3(a) examples of the present invention Fe3O4The VSM plot of @ MBC;
FIG. 3(b) shows Fe in example of the present invention3O4Thermogravimetric mapping of @ MBC;
FIG. 3(c) shows Fe in example of the present invention3O4N of @ MBC2Adsorption and desorption curves;
FIG. 3(d) examples of the present invention Fe3O4Raman spectrogram of @ MBC;
FIG. 4 shows Fe in example 1 of the present invention3O4The removal rate of @ MBC to BPA in the water body is shown schematically;
FIG. 5 shows Fe in example 2 of the present invention3O4The removal rate of @ MBC to BPA in the water body is shown schematically;
FIG. 6 shows Fe in example 3 of the present invention3O4The removal rate of @ MBC to BPA in the water body is shown schematically;
FIG. 7 shows Fe in example 4 of the present invention3O4The removal rate of @ MBC to BPA in the water body is shown schematically;
FIG. 8 shows Fe in example 5 of the present invention3O4The removal rate of @ MBC to BPA in the water body is shown schematically;
FIG. 9 shows Fe in example 6 of the present invention3O4The removal rate of @ MBC to BPA in the water body is shown schematically;
FIG. 10 shows Fe in example 7 of the present invention3O4The removal rate of @ MBC to BPA in the water body is shown schematically;
FIG. 11 shows an embodiment of the present inventionFe in 83O4The removal rate of @ MBC to BPA in the water body is shown schematically.
Detailed Description
The invention is explained in detail below with reference to the figures and examples:
example 1
The treatment method of the BPA-containing sewage provided by the embodiment comprises the following steps:
A) preparation of ball-milling modified magnetic biochar composite Fe as BPA-containing sewage remover3O4@MBC；
B) Obtaining a BPA-containing sewage sample, and determining the concentration of BPA in the sewage sample to be 20mg/L by using high performance liquid chromatography;
C) detecting that the pH value of the solution of the sewage is 6.62 and is within the range of 3-9, and the pH value of the solution does not need to be adjusted;
D) PDS is added to reach the concentration of 5mM in the sewage sample, and then ball-milling modified magnetic biochar composite Fe with different proportional dosage is taken3O4@ MBC, adding the materials into BPA-containing sewage samples respectively, oscillating the materials in a shaking table for reaction for 3 hours, and finding that the removal rates corresponding to different addition concentrations of the materials can change, wherein the removal rates are changed along with Fe3O4The amount of addition of @ MBC was varied; PDS concentration was 5mM when Fe3O4When the addition amount of @ MBC reaches the concentration of 0.6g/L, the shaking table is vibrated to react for 3h, the removal process and the result are shown in FIG. 4, and the final removal rate of BPA is 98.45%. In the embodiment of the invention, Fe with different proportions is respectively added3O4The test of @ MBC found when Fe3O4When the addition amount of @ MBC is not less than 0.4 g/L, the BPA can be effectively removed, and the removal rate is more than 92%; comprehensively considering the preparation cost of the material, selecting the optimal Fe3O4The dosage of @ MBC is 0.5 g/L, and the maximum removal rate is 98.17 percent;
E) according to the optimal feeding proportion of 0.5 g/L obtained by testing, ball-milling the modified magnetic biochar composite material Fe3O4The @ MBC is added into the BPA-containing sewage and catalyzes PDS, and the @ MBC and the PDS jointly complete the degradation and removal of the BPA in the water body: a large amount of Fe attached to the surface of the ball-milled biochar3O4With a peroxydisulfate salt, and a salt of,∙ OH and SO with high oxidation activity are generated after a series of catalytic reactions4 ∙-，∙O2 -And1O2active substances which degrade BPA in the water body and finally mineralize it to harmless CO2And H2O。
In the examples of the present invention, Fe3O4The chemical reaction mechanism for removing BPA in the water body by the aid of the combination of @ MBC and PDS is as follows:
Fe3+ + H2O → Fe2+ + ∙OH + H+
S2O8 2- + 2H2O → 2 HSO4 - + H2O2
H2O2 + Fe2+ → Fe3+ + OH- + ∙OH
Fe2+ + S2O8 2- →Fe3+ +SO4 ∙- + SO4 2-
SO4 ∙- + H2O →SO4 2- + ∙OH+ H+
S2O8 2- + ∙OH →HSO4 - + 0.5O2 +SO4 ∙-
O2 + e-(Fe3O4) →∙O2 -
∙OH + ∙O2 - → OH- + 1O2
BPA + ∙OH / SO4 ∙- / ∙O2 - / 1O2 → CO2 +H2O
the ball-milling modified magnetic biochar composite material for the BPA-containing sewage treatment method is prepared by loading Fe on the surface of ball-milling biochar3O4Flaky black solid powder composite Fe obtained by lamellar3O4@ MBC, Fe therein3O4Having a trans-spinel structure, the lattice spacing of the lamellae0.2-0.3 nm; iron oxide loaded on the surface of the ball-milled biochar exists in the form of ferrous iron and ferric iron at the same time; wherein the ball-milled biochar is of an amorphous carbon and graphitic carbon structure; said Fe3O4The surface of @ MBC has C-O, C = O, O-C = O oxygen-containing functional group which is used as an electron donor acceptor to directly degrade organic pollutants on one hand and is used as an electron shuttle to mediate the degradation of organic pollutants BPA on the other hand.
According to mass percent, the Fe3O4The surface carbon content of @ MBC is 40%, the oxygen content is 30%, and the iron content is 30%.
The ball-milling modified magnetic biochar composite material Fe3O4The @ MBC has strong paramagnetism and can be smoothly separated in a liquid phase by an external magnet.
The ball-milling modified magnetic biochar composite material Fe3O4The @ MBC has stronger thermal stability, and the mass loss is not more than 10% before the temperature is heated to 780 ℃.
The ball-milling modified magnetic biochar composite material Fe3O4The @ MBC material has a mesoporous structure, the average pore diameter is 10 nm, and the specific surface area is not less than 140 m2G, Raman peak area ratio ID/IGNot less than 1.10, and the surface of the material has rich defect sites, and the material has strong catalytic capability on PDS.
The preparation method of the ball-milling modified magnetic biochar composite material comprises the following steps:
s1: preparing the biochar: drying the wood chip biomass in an oven at 60 ℃, grinding and crushing the wood chip biomass, putting the wood chip biomass into a corundum boat, putting the corundum boat into a tubular furnace, heating to 800 ℃, keeping the temperature for 2 hours, cooling to 75 ℃, and obtaining the charcoal powder, and taking out the charcoal powder for later use;
s2: preparing ball-milling modified biochar: putting the charcoal powder and the grinding balls into a ball milling tank according to the proportion of 1:100, and carrying out ball milling for 6-12 h;
s3: preparation of ball-milled modified magnetic biochar composite Fe3O4@MBC：
FeCl is added in a molar ratio of 2:13And FeSO4·7H2O is isolated from air at room temperature and stirred until dissolved; adding a corresponding amount of ball-milling modified biochar into the solution according to the mass ratio of 1:1, stirring at room temperature, continuously dropwise adding 10M NaOH into the solution until the pH value is 10-11, and generating black precipitates successively; stirring at room temperature until the precipitate is complete, standing, and separating the black precipitate by magnet or suction filtration to obtain scale-shaped ball-milling modified magnetic biochar composite Fe3O4@MBC；Fe3O4The generation process comprises the following steps: fe2+ + 2Fe3+ + 8OH- → Fe3O4 + 4H2O。
As can be seen from the observation of the ultra-high resolution transmission electron micrograph of FIG. 1(a), a large number of iron oxide lamellae are loaded on the surface of the scaly ball-milled biochar; further analysis from FIG. 1(b) revealed that the lattice spacing of these sheets was 0.292 nm, 0.251 nm and 0.205 nm, respectively with Fe3O4The (220) plane, (311) plane and (400) plane of the crystal correspond to each other.
As can be seen from fig. 1(b), iron supported on the surface of the ball-milled biochar exists in divalent (710.5 eV) and trivalent (710.5 eV), indicating that iron oxide with co-existing di-trivalent iron may be formed after the support.
FIG. 1(c) XRD spectrum shows, Fe3O4Diffraction peak of @ MBC and Fe having trans-spinel structure3O4(JCPDS No. 88-0315) perfect match, where it appears at 2θThe crystal planes of (111), (220), (311), (400), (422), (511), (440) and (533) are respectively corresponding to degrees 18.3, 30.1, 35.5, 43.2, 53.5, 57.1, 62.7 and 74.2. The above characteristics all indicate that the ball-milling biochar is loaded with Fe3O4I.e. Fe is successfully prepared3O4@ MBC material.
XPS analysis of FIG. 2(a) shows that Fe was produced3O4@ MBC surface carbon content 44.64%, oxygen content 36.34%, iron content 16.24%, and no Fe loading3O4The ball-milled biochar has an oxygen content of 15.35% and an iron content of only 0.48%, which indicates that the balls are loadedGrinding the biochar surface forms a large amount of iron oxide.
FIG. 2(b) Fe was found by peaking XPS C1s3O4The surface of @ MBC has a large number of oxygen-containing functional groups, mainly in the form of C-O, C = O, O-C = O and the like.
Fe was found by peak separation of XPS C1s and O1s positions in FIGS. 2(a) and 2(b)3O4The surface of @ MBC has a large number of oxygen-containing functional groups, which mainly exist in the forms of C-O, C = O, O-C = O and the like, and the oxygen-containing functional groups can be used as electron donor and acceptor to directly degrade organic pollutants on one hand and can be used as electron shuttles to mediate the degradation of the organic pollutants on the other hand.
As shown by the hysteresis loop characteristics of FIG. 3(a), Fe was prepared3O4The @ MBC has strong paramagnetism, and can ensure that the material is successfully separated by an external magnet in a liquid phase.
Fig. 3(b) thermogravimetric analysis shows that the material has strong thermal stability and only has mass loss of about 10% before being heated to 780 ℃.
As shown in FIG. 3(c), Fe was measured by nitrogen adsorption and desorption3O4The pore structure, pore size distribution and specific surface area of @ MBC, the sample exhibited a type IV adsorption isotherm and had a type H3 hysteresis loop, indicating Fe3O4The @ MBC has a mesoporous structure, the average pore diameter is 10.82 nm, and the specific surface area is 146.26 m2(ii) in terms of/g. Generally speaking, the mesoporous structure can promote mass transfer and diffusion between reactants and active oxygen, and is beneficial to the catalytic reaction. And a larger specific surface area indicates that the material has more catalytically active sites and adsorption sites.
FIG. 3(d) the Raman spectrum shows that at 1339.59 cm-1And 1588.22 cm-1D-band characteristic peak and G-band characteristic peak are formed respectively, which shows that Fe3O4@ MBC has an amorphous carbon structure and a graphitic carbon structure. The formation of the D band is mainly related to disordered vibrations caused by structural defects or edge breaks of the SP3 hybrid carbon, and therefore, the relative strengths of the D and G bands (I)D/IG) Can reflect the carbon structure defect degree and the peak area ratio I of the materialD/IG=1.11, indicates Fe3O4The @ MBC has rich defect sites, and is favorable for enhancing the catalytic capability of the material.
Example 2
Referring to the attached figure 5, the BPA-containing sewage treatment method and the ball-milling modified magnetic biochar composite Fe provided by the embodiment of the invention3O4@ MBC and a method for its preparation, substantially the same as in example 1, except that:
obtaining a sewage sample with BPA concentration of 20mg/L, wherein the pH value of the sample is 6.62, and firstly adding Fe3O4The concentration of @ MBC is 0.5 g/L, a certain amount of PDS is added into the sample to ensure that the concentration of the PDS in the sample is continuously changed, and the mixture is vibrated in a shaking table for reaction for 3 hours, so that BPA is effectively removed; when PDS was added at a concentration of 5mM, the removal process and effect was as shown in FIG. 5; in this example, through experimental tests of continuously changing the addition concentration of PDS, it was found that when the PDS concentration is 3 mM-9 mM, BPA can be effectively removed, the removal rate is more than 91%, the optimal PDS concentration is 5mM, and the maximum removal rate is 98.17%.
According to mass percent, the Fe3O4The surface carbon content of @ MBC is 42%, the oxygen content is 35%, and the iron content is 23%.
Ball-milling modified magnetic biochar composite Fe3O4The preparation method of @ MBC specifically comprises the following steps:
step S1: drying the pine sawdust biomass in an oven at 60 ℃, grinding and crushing the pine sawdust biomass through a sieve of 250 mu m, putting a certain amount of sieved biomass in a corundum boat and placing the corundum boat in a tubular furnace, wherein the temperature rising program of the tubular furnace is as follows: heating from room temperature to 800 ℃ at 10 ℃/min, keeping at 800 ℃ for 2 h, cooling from 800 ℃ to 75 ℃ at 10 ℃/min to obtain biochar, and taking out for later use;
s2: placing the prepared biochar and grinding balls in a ball milling tank in a ratio of 1:100, rotating clockwise for 3 hours at a rotating speed of 300 r/min, stopping running for 30 minutes, then rotating anticlockwise for 3 hours at a rotating speed of 300 r/min to form a ball milling process, and repeating the process twice to obtain ball milling modified biochar;
s3: FeCl is added in a molar ratio of 2:13And FeSO4·7H2Placing the O in a three-neck flask with air exhausted, and stirring at room temperature until the O is dissolved to obtain a mixed solution; placing the ball-milling modified biochar into the mixed solution according to the mass ratio of 1:1, stirring for 30 min at room temperature, continuously dropwise adding 10M NaOH into the mixed solution until the pH value is 10-11, and continuously generating black precipitates; continuously stirring for 1 h at room temperature of 50 r/min until the precipitate is complete, standing for 3-4 h at room temperature, and separating the black precipitate by using a magnet or suction filtration to obtain Fe3O4@ MBC; separating the separated Fe3O4@ MBC was washed 5 times with ultrapure water, 3 times with absolute ethanol, and dried under vacuum for future use.
Example 3
Referring to the attached figure 6, the BPA-containing sewage treatment method and the ball-milling modified magnetic biochar composite Fe provided by the embodiment of the invention3O4@ MBC and its preparation method are basically the same as examples 1 and 2, except that:
the step C) also comprises the following steps:
c-1) when the measured pH value of the sewage sample solution is not in the range of 3-9, adding 0.1-0.5M acid (such as acetic acid, etc.) or alkali compound containing metal cation (such as NaOH, etc.) to the sewage sample solution to adjust the pH value of the sewage sample to 3-9, cooperating with Fe3O4The material of @ MBC catalyzes PDS to remove BPA in the water body.
Specifically, a sewage sample with BPA concentration of 20mg/L is obtained, the pH value of the sample is 11, and Fe is added3O4The concentration of @ MBC is 0.5 g/L, the concentration of PDS is 5mM, then a pH regulator (acid or alkali) is added to regulate the pH value to continuously change, and the shaking table vibrates for reaction for 3 hours to effectively remove BPA; when the pH value of the solution is adjusted to 6.6, the removal process and the effect are shown in figure 6; in this example, through the experiment of continuously adjusting the pH value, it was found that when the pH was between 3 and 9, the effective removal of BPA could be achieved, the removal rate was all above 90%, the optimum pH was 6.62, and the maximum removal rate was 98.187%. Namely, Fe produced3O4@ MBC activation of PDS to remove BPA can be applied over a wide pH range.
According to mass percentageFe3O4The surface carbon content of @ MBC is 43%, the oxygen content is 36%, and the iron content is 21%.
Example 4
Referring to the attached figure 7, the BPA-containing sewage treatment method and the ball-milling modified magnetic biochar composite Fe provided by the embodiment of the invention3O4@ MBC and its preparation method are substantially the same as examples 1, 2 and 3, except that:
preparing a sample solution of wastewater with BPA concentration of 20mg/L, adding 2.5-10 mM Na+、Ca2+、Mg2+Adjusting the pH value of the solution to 6.62, and adding Fe3O4The concentration of @ MBC was 0.5 g/L, the concentration of PDS was 5mM, the shaking reaction was carried out in a shaker for 3 hours, the BPA removal rate was 88.24-94.04%, as shown in FIG. 7.
The experiment proves that: test cation species and concentration vs. Fe3O4@ MBC activation of PDS to a lesser extent to remove BPA, i.e., Fe3O4The ability of @ MBC to activate PDS to remove BPA is not limited by the type and concentration of cations in the solution.
According to mass percent, the Fe3O4The surface carbon content of @ MBC is 44%, the oxygen content is 37%, and the iron content is 19%.
Example 5
The embodiment of the invention provides a treatment method of BPA-containing sewage and a ball-milling modified magnetic biochar composite Fe3O4@ MBC and the preparation method thereof are basically the same as in examples 1-4, except that:
preparing a sample solution of wastewater with BPA concentration of 20mg/L, adding 2.5-10 mM Cl into the solution-、HCO3 -、H2PO3 -Adjusting the pH value of the solution to 6.62, and adding Fe3O4The concentration of @ MBC was 0.5 g/L, the concentration of PDS was 5mM, the shaking reaction was carried out in a shaker for 3 hours, and the change in the BPA removal rate was 66.74-68.54%, as shown in FIG. 8.
This example demonstrates that: the tested anion inhibits Fe3O4@ MBC activates the ability of PDS to remove BPA, howeverThe effect is related to the anion species, independent of the anion concentration.
According to mass percent, the Fe3O4The surface carbon content of @ MBC is 41%, the oxygen content is 38%, and the iron content is 21%.
Example 6
The embodiment of the invention provides a treatment method of BPA-containing sewage and a ball-milling modified magnetic biochar composite Fe3O4@ MBC and method of making same, essentially identical to examples 1-5, except that Fe was verified3O4@ MBC activates the BPA removal performance of PDS at different concentrations of Dissolved Organic Matter (DOM).
Preparing sewage sample solution with BPA concentration of 20mg/L, adding 2.5-10 mM DOM into the solution, adjusting the pH value of the solution to be 6.62, and adding Fe3O4The concentration of @ MBC was 0.5 g/L and the concentration of PDS was 5mM, and the reaction was carried out in a shaker for 3 hours with shaking, and the BPA removal rate was 90.45-94.68% as shown in FIG. 9. This example demonstrates that: fe3O4The ability of @ MBC to activate PDS is affected to a lesser extent by dissolved organic matter in the system.
According to mass percent, the Fe3O4The surface carbon content of @ MBC is 45%, the oxygen content is 40%, and the iron content is 15%.
Example 7
The embodiment of the invention provides a treatment method of BPA-containing sewage and a ball-milling modified magnetic biochar composite Fe3O4@ MBC and method of making same, essentially identical to examples 1-6, except that Fe was verified3O4@ MBC cycle regeneration activates the BPA removal performance of PDS.
The treatment method of the BPA-containing sewage provided by the embodiment of the invention further comprises the following steps:
F) regeneration and reuse: using used ball-milling modified magnetic biochar composite material Fe3O4The method comprises the following steps of @ MBC centrifugal separation and recovery, repeated washing with ultrapure water and ethanol, and vacuum drying in a vacuum drying oven at 50 ℃ for 12 h to recover the BPA removal capacity of the vacuum drying oven; collecting the dried material, and repeating the stepsB) E), carrying out next cycle of degradation and removing BPA in the water body;
G) and F) repeating the step F), completing multiple degradation-regeneration-degradation cycles, and removing the BPA in the water body.
The specific operation steps are as follows:
when in first use: obtaining a solution of a sewage sample with BPA of 20mg/L, adjusting the pH value of the solution to be 6.62, and adding Fe3O4The concentration of @ MBC is 0.5 g/L, the concentration of PDS is 5mM, and shaking reaction is carried out in a shaking table for 3 h; and (3) regeneration and utilization: fe to be used3O4@ MBC centrifugal separation, repeated washing with ultrapure water and ethanol, vacuum drying in a vacuum drying oven at 50 ℃ for 12 h, collecting the dried material, performing the next cycle of cycle removal experiment, wherein the removal rate of BPA is shown in FIG. 10, and the removal rates of BPA by the first cycle and the second cycle are respectively 92.67% and 88.35%, which proves that Fe3O4The @ MBC has better regeneration capacity and can be recycled for many times in the sewage treatment process.
Example 8
The embodiment of the invention provides a treatment method of BPA-containing sewage and a ball-milling modified magnetic biochar composite Fe3O4@ MBC and process for its preparation, substantially identical to examples 1-7, except that different levels of air aged Fe were verified3O4@ MBC activates BPA-removing properties of PDS.
Prepared Fe3O4@ MBC was placed in a storage bottle and allowed to age naturally in a dry air atmosphere for two months, and samples after 1 day, 7 days, 14 days, 21 days, 28 days, 42 days and 56 days of aging were taken for BPA removal test. The test conditions were: the concentration of BPA in the sewage sample solution is 20mg/L, the pH value of the solution is 6.62, and the added Fe3O4The concentration of @ MBC is 0.5 g/L, the concentration of PDS is 5mM, the shaking reaction is carried out in a shaking table for 3h, the removal rate of BPA is shown in FIG. 11, and the removal rate of BPA is as follows: 94.33-98.17 percent. This example demonstrates that: fe3O4The @ MBC still can keep higher catalytic activity after being stored in the air atmosphere for a long time, and has very strong catalytic stability.
It should be noted that, in other embodiments of the present invention, different schemes obtained by specifically selecting steps, components, ratios, and process parameters described in the present invention can achieve the technical effects described in the present invention, and therefore, the present invention is not listed one by one.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Those skilled in the art can make numerous possible variations and modifications to the present invention, or modify equivalent embodiments, using the methods and techniques disclosed above, without departing from the scope of the present invention. All equivalent changes in the components, proportions and processes according to the present invention are intended to be covered by the scope of the present invention.
Claims (10)
1. A method for treating BPA-containing sewage is characterized by comprising the following steps:
A) preparation of ball-milling modified magnetic biochar composite Fe as BPA-containing sewage remover3O4@MBC；
B) Obtaining a BPA-containing sewage sample, and measuring the concentration of BPA by using high performance liquid chromatography;
C) detecting whether the pH value of the sewage is in the range of 3-9, if not, adjusting the pH value of the BPA sewage to 3-9;
D) PDS is added to reach the concentration of 5mM in the sewage sample, and then ball-milling modified magnetic biochar composite Fe with different proportional dosage is taken3O4@ MBC, respectively adding the materials into BPA-containing sewage samples, and testing to obtain and verify the BPA removal performance and the optimal feeding proportion of the materials:
E) according to the optimal feeding proportion obtained by the test, the ball-milling modified magnetic biochar composite material Fe3O4The @ MBC is added into the BPA-containing sewage and catalyzes PDS, and the @ MBC and the PDS jointly complete the degradation and removal of the BPA in the water body: a large amount of Fe attached to the surface of the ball-milled biochar3O4After a series of catalytic reactions with peroxydisulfate, ∙ OH and SO with high oxidation activity are generated4 ∙-，∙O2 -And1O2active substances which degrade BPA in the water body and finally mineralize it to harmless CO2And H2O。
2. The method for treating BPA-containing wastewater according to claim 1, further comprising the steps of:
F) regeneration and reuse: using used ball-milling modified magnetic biochar composite material Fe3O4The method comprises the following steps of @ MBC centrifugal separation and recovery, repeated washing with ultrapure water and ethanol, and vacuum drying in a vacuum drying oven at 50 ℃ for 12 h to recover the BPA removal capacity of the vacuum drying oven; collecting the dried material, and repeating the steps B) to E) to carry out next cycle of degradation and removal of BPA in the water body;
G) and F) repeating the step F), completing multiple degradation-regeneration-degradation cycles, and removing the BPA in the water body.
3. A method for treating BPA-containing effluent as claimed in claim 1, wherein step C) further comprises the steps of:
c-1) adding 0.1-0.5M acid or alkaline compound containing metal cation into the sewage sample solution to adjust the pH of the sewage sample to 3-9, cooperating with Fe3O4The material of @ MBC catalyzes PDS to remove BPA in the water body.
4. A ball-milling modified magnetic biochar composite material for the BPA-containing sewage treatment method of any one of claims 1 to 3, which is characterized in that Fe is loaded on the surface of ball-milling biochar3O4Flaky black solid powder composite Fe obtained by lamellar3O4@ MBC, Fe therein3O4The crystal lattice has a trans-spinel structure, and the lattice spacing of each lamella is 0.2-0.3 nm; iron oxide loaded on the surface of the ball-milled biochar exists in the form of ferrous iron and ferric iron at the same time; wherein the ball-milled biochar is of an amorphous carbon and graphitic carbon structure; said Fe3O4@ MBC surface Presence of C-O, C = O, O-C= O oxygen-containing functional group which, on the one hand, acts as electron donor acceptor directly degrading the organic contaminant and, on the other hand, acts as electron shuttle mediating the degradation of the organic contaminant BPA.
5. The ball-milling modified magnetic biochar composite material as claimed in claim 4, wherein the Fe is present in a mass percentage3O4The surface carbon content of the @ MBC is 40-45%, the oxygen content is 30-40%, and the iron content is 15-30%.
6. The ball-milling modified magnetic biochar composite material as claimed in claim 4, wherein the ball-milling modified magnetic biochar composite material is Fe3O4The @ MBC has strong paramagnetism and can be smoothly separated in a liquid phase by an external magnet.
7. The ball-milling modified magnetic biochar composite material as claimed in claim 4, wherein the ball-milling modified magnetic biochar composite material is Fe3O4The @ MBC has stronger thermal stability, and the mass loss is not more than 10% before the temperature is heated to 780 ℃.
8. The ball-milling modified magnetic biochar composite material as claimed in claim 4, wherein the ball-milling modified magnetic biochar composite material is Fe3O4The @ MBC material has a mesoporous structure, the average pore diameter is 10 nm, and the specific surface area is not less than 140 m2G, Raman peak area ratio ID/IGNot less than 1.10, and the surface of the material has rich defect sites, and the material has strong catalytic capability on PDS.
9. A preparation method of the ball-milling modified magnetic biochar composite material according to any one of claims 4 to 8 is characterized by comprising the following steps:
s1: preparing the biochar: drying the sawdust biomass in an oven at 60 ℃, grinding and crushing the sawdust biomass, putting the sawdust biomass in a corundum boat, placing the corundum boat in a tubular furnace, heating to 800 ℃, keeping for 2 hours, cooling to 75 ℃, preparing charcoal powder, and taking out for later use;
s2: preparing ball-milling modified biochar: putting the charcoal powder and the grinding balls into a ball milling tank according to the proportion of 1:100, and carrying out ball milling for 6-12 h;
s3: preparation of ball-milled modified magnetic biochar composite Fe3O4@MBC：
FeCl is added in a molar ratio of 2:13And FeSO4·7H2O is isolated from air at room temperature and stirred until dissolved; adding a corresponding amount of ball-milling modified biochar into the solution according to the mass ratio of 1:1, stirring at room temperature, continuously dropwise adding 10M NaOH into the solution until the pH value is 10-11, and generating black precipitates successively; stirring at room temperature until the precipitate is complete, standing, and separating the black precipitate by magnet or suction filtration to obtain scale-shaped ball-milling modified magnetic biochar composite Fe3O4@MBC；Fe3O4The generation process comprises the following steps: fe2+ + 2Fe3+ + 8OH- → Fe3O4 + 4H2O。
10. The preparation method of the ball-milling modified magnetic biochar composite material as claimed in claim 9,
the step S1 specifically includes: drying the pine sawdust biomass in an oven at 60 ℃, grinding and crushing the pine sawdust biomass through a sieve of 250 mu m, putting a certain amount of sieved biomass in a corundum boat and placing the corundum boat in a tubular furnace, wherein the temperature rising program of the tubular furnace is as follows: heating from room temperature to 800 ℃ at 10 ℃/min, keeping at 800 ℃ for 2 h, cooling from 800 ℃ to 75 ℃ at 10 ℃/min to obtain biochar, and taking out for later use;
the step S2 specifically includes: placing the prepared biochar and grinding balls in a ball milling tank in a ratio of 1:100, rotating clockwise for 3 hours at a rotating speed of 300 r/min, stopping running for 30 minutes, then rotating anticlockwise for 3 hours at a rotating speed of 300 r/min to form a ball milling process, and repeating the process twice to obtain ball milling modified biochar;
the step S3 specifically includes: FeCl is added in a molar ratio of 2:13And FeSO4·7H2Placing the O in a three-neck flask with air exhausted, and stirring at room temperature until the O is dissolved to obtain a mixed solution; placing the ball-milling modified biochar into the mixed solution according to the mass ratio of 1:1, stirring for 30 min at room temperature, continuously dropwise adding 10M NaOH into the mixed solution until the pH value is 10-11, and continuously generating black precipitates; continuously stirring for 1 h at room temperature of 50 r/min until the precipitate is complete, standing for 3-4 h at room temperature, and separating the black precipitate by using a magnet or suction filtration to obtain Fe3O4@ MBC; separating the separated Fe3O4@ MBC was washed 5 times with ultrapure water, 3 times with absolute ethanol, and dried under vacuum for future use.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113620370A (en) * | 2021-10-14 | 2021-11-09 | 生态环境部华南环境科学研究所 | Method for efficiently removing bisphenol pollutants in water body and compound biochar material |
| CN113998771A (en) * | 2021-12-30 | 2022-02-01 | 生态环境部华南环境科学研究所 | TPhP degradation method, biochar-inorganic mineral complex material and preparation method thereof |
| CN114452967A (en) * | 2022-01-19 | 2022-05-10 | 武汉理工大学 | Acetic acid and ball-milling modified sludge biochar applied to synergistic electrochemical activation of peroxymonosulfate for efficient degradation of imidacloprid in water |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109266950A (en) * | 2018-10-26 | 2019-01-25 | 河南富莱格超硬材料有限公司 | Cubic boron nitride enhances steel-based composite material and preparation method thereof |
| CN109999811A (en) * | 2019-05-07 | 2019-07-12 | 鲁东大学 | It a kind of preparation of biomass iron carbon composite and degrades bisphenol-A for catalytic activation sodium peroxydisulfate |
| CN112808233A (en) * | 2020-12-30 | 2021-05-18 | 山东大学 | Fe3O4Preparation method of-biochar composite nano material and method for degrading organic pollutants in water body |
-
2021
- 2021-07-12 CN CN202110781557.3A patent/CN113233573B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109266950A (en) * | 2018-10-26 | 2019-01-25 | 河南富莱格超硬材料有限公司 | Cubic boron nitride enhances steel-based composite material and preparation method thereof |
| CN109999811A (en) * | 2019-05-07 | 2019-07-12 | 鲁东大学 | It a kind of preparation of biomass iron carbon composite and degrades bisphenol-A for catalytic activation sodium peroxydisulfate |
| CN112808233A (en) * | 2020-12-30 | 2021-05-18 | 山东大学 | Fe3O4Preparation method of-biochar composite nano material and method for degrading organic pollutants in water body |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113620370A (en) * | 2021-10-14 | 2021-11-09 | 生态环境部华南环境科学研究所 | Method for efficiently removing bisphenol pollutants in water body and compound biochar material |
| CN113620370B (en) * | 2021-10-14 | 2021-12-17 | 生态环境部华南环境科学研究所 | Method for efficiently removing bisphenol pollutants in water body and compound biochar material |
| EP4166509A1 (en) * | 2021-10-14 | 2023-04-19 | South China Institute of Enviromental Science, Ministry of Ecology and Enviroment | Method for efficiently removing bisphenol pollutants from water body and compound biochar material |
| CN113998771A (en) * | 2021-12-30 | 2022-02-01 | 生态环境部华南环境科学研究所 | TPhP degradation method, biochar-inorganic mineral complex material and preparation method thereof |
| CN114452967A (en) * | 2022-01-19 | 2022-05-10 | 武汉理工大学 | Acetic acid and ball-milling modified sludge biochar applied to synergistic electrochemical activation of peroxymonosulfate for efficient degradation of imidacloprid in water |
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