CN113247985A - TBBPA-containing sewage treatment method, porous carbon microsphere material and preparation method - Google Patents

TBBPA-containing sewage treatment method, porous carbon microsphere material and preparation method Download PDF

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CN113247985A
CN113247985A CN202110774843.7A CN202110774843A CN113247985A CN 113247985 A CN113247985 A CN 113247985A CN 202110774843 A CN202110774843 A CN 202110774843A CN 113247985 A CN113247985 A CN 113247985A
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porous carbon
tbbpa
adsorption
ball
carbon microsphere
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于云江
刘畅
李良忠
马瑞雪
常兆峰
阳宸煜
李宗睿
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South China Institute of Environmental Science of Ministry of Ecology and Environment
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
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    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

The invention discloses a TBBPA-containing sewage treatment method, a porous carbon microsphere material and a preparation method thereof, wherein the treatment method comprises the following steps: A) preparing a ball-milling modified porous carbon microsphere material; B) obtaining a TBBPA-containing sewage sample, and determining the concentration of TBBPA; C) adding carbon microsphere materials with different proportional dosages into a sewage sample, and calculating and verifying the optimal feeding proportion of the materials; D) and adding the carbon microsphere material into TBBPA sewage according to the proportion for adsorption. The invention also provides a ball-milling modified porous carbon microsphere material, which is prepared by taking micron-sized porous carbon microspheres as a base material, performing ball milling and nitrogen doping modification on the base material to obtain enhanced porous carbon microsphere black solid powder, wherein the specific surface area of the black solid powder is increased, the dispersibility of the black solid powder is enhanced, the thermal stability of the black solid powder is increased, the average pore diameter of the surface of the porous carbon spheres is increased, the pore diameter of micropores is 0.5-2 nm, the maximum adsorption capacity and the adsorption rate are both remarkably improved, the influence of pH and humic acid is small, and the preparation method of the carbon microsphere material is simple in process, high in controllability of the reaction process and easy to industrialize.

Description

TBBPA-containing sewage treatment method, porous carbon microsphere material and preparation method
Technical Field
The invention belongs to the technical field of sewage treatment materials, and particularly relates to a TBBPA-containing sewage treatment method, a porous carbon microsphere material and a preparation method thereof.
Background
Tetrabromobisphenol a (TBBPA) is currently the most used flame retardant in the world due to its high flame retardant efficiency and superior thermal stability. With the great increase of the production amount of TBBPA, the production of a large amount of TBBPA is shifted to Asian areas, and China becomes a main production base of TBBPA. According to the statistics of the international bromine industry council (BSEF), the annual yield of TBBPA in 2019 is 18 ten thousand tons, with the highest asian consumption of 10.94 ten thousand tons/year. TBBPA is mainly added into a product in a simple physical addition 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. TBBPA in water body may generate toxic and endocrine disturbing effects such as liver and kidney, nerve and the like to human body, and seriously affect the monitoring of human. In 2017, the world health organization international agency for research on cancer listed it as a class 2A carcinogen. Therefore, how to effectively remove TBBPA in water environment has been widely concerned by domestic and foreign research.
The existing method for removing TBBPA in sewage mainly comprises a physical adsorption method, a biodegradation method, a catalytic oxidation method and the like. The existing research finds that the porous carbon material is considered to be an excellent adsorbent for 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 adsorption quantity, easy separation and the like. For example, Li and the like use sewage sludge to prepare porous biochar to adsorb TBBPA, and the adsorption is mainly homogeneous and chemical processes and mainly influenced by pi-pi interaction and hydrogen bonds, but the adsorption effect is greatly influenced by the change of pH of environmental factors and Humic Acid (HA). Shao et al prepared porous carbon microspheres from waste cigarette ends have good adsorption performance on bisphenol A (BPA), the maximum adsorption amount is 865mg/g, but the adsorption speed is slow, the efficiency is low, and the porous carbon microspheres are also easily influenced by the change of environmental factor pH and Humic Acid (HA).
In addition, at present, methods such as acid/alkali modification and chemical oxidation are adopted for modifying the porous carbon microspheres, and a mechanical ball milling modification method is not generally adopted, because the ball milling modification material prepared by the mechanical ball milling method has large surface crushing degree and complex manufacturing process. Therefore, the existing mechanical ball milling process has large crushing degree, complex manufacturing process and low controllability of reaction process, cannot be directly applied to modification of the porous carbon microspheres, is difficult to obtain microspheres with stable quality and small breakage rate, and is difficult to realize industrialization.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a novel method for treating TBBPA-containing sewage, wherein a ball-milling modified porous carbon microsphere material is used as an adsorbent for TBBPA-containing sewage so as to improve the treatment efficiency and effect of the sewage and reduce the treatment cost; the invention also provides a ball-milling modified porous carbon microsphere material and a preparation method thereof, and the components and the structure of the porous carbon microsphere and the mechanical ball-milling preparation process are synchronously improved to modify the porous carbon microsphere, so that the adsorption efficiency and the adsorption quantity of TBBPA in water are improved, and the influence of the change of pH and humic acid (DOM) on the adsorption effect of the TBBPA is reduced; the preparation method has the advantages of simple process, stable quality of the microspheres, 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 TBBPA-containing sewage treatment method is characterized by comprising the following steps:
A) preparing a ball-milling modified porous carbon microsphere material serving as a TBBPA sewage adsorbent;
B) obtaining a TBBPA-containing sewage sample, and measuring the TBBPA concentration by using a high performance liquid chromatography;
C) adding ball-milling modified porous carbon microsphere materials with different proportional dosages into a TBBPA-containing sewage sample respectively, and calculating and verifying the adsorption performance and the optimal feeding proportion of the material to TBBPA according to the following formula:
Figure RE-478994DEST_PATH_IMAGE001
in the formula: q is the solid-phase adsorption concentration (unit mg/g) of the material to TBBPA in adsorption equilibrium, V is the volume of the solution (unit L), C0Is the initial concentration of contaminant (in mg/L), CeThe concentration of the liquid phase at adsorption equilibrium (unit mg/L), m is the mass of the adsorbent (unit g);
D) and adding the ball-milling modified porous carbon microsphere material into TBBPA sewage according to the optimal feeding proportion corresponding to the optimal q value obtained by calculation, and completing the adsorption of TBBPA in the water body.
The step C) also comprises the following steps: C1) through adsorption kinetics experiments, the optimal feeding proportion is calculated and verified, and the method specifically comprises the following steps:
respectively adopting a quasi-first-stage kinetic model and a quasi-second-stage kinetic model to fit the kinetic process of TBBPA adsorption of the modified porous carbon microspheres, wherein the quasi-first-stage kinetic model, the quasi-second-stage kinetic model and the intra-particle diffusion model are respectively expressed as formulas (2), (3) and (4):
Figure RE-355815DEST_PATH_IMAGE002
in the formula:
Figure RE-492398DEST_PATH_IMAGE003
(unit mg/g) and
Figure RE-426856DEST_PATH_IMAGE004
(in mg/g) are the solid phase concentrations at equilibrium and time t, respectively,
Figure RE-122017DEST_PATH_IMAGE005
(unit min)-1）、
Figure RE-17292DEST_PATH_IMAGE006
[ Unit mg/(mg. min)]And k3(unit mg/(g. h)1/2) Are the quasi-first order rate model, the quasi-second order rate model, and the intra-particle diffusion model rate constants, respectively; c (in mg/g) is the intra-particle diffusion constant;
D1) and (3) according to the optimal feeding proportion corresponding to the optimal solution calculated and verified by the quasi-first-stage dynamic model, the quasi-second-stage dynamic model and the particle internal diffusion model, adding the ball-milling modified porous carbon microsphere material into the TBBPA sewage, and completing the adsorption of the TBBPA in the water body.
The step C) also comprises the following steps: C2) determining the optimal feeding proportion through an isothermal adsorption experiment, specifically:
adding a certain amount of adsorbent under different concentration gradients of TBBPA-containing pollutants in the sewage, and putting the conical flask into a constant-temperature shaking incubator, wherein the temperature is 25 ℃, and the rotating speed is controlled at 150 r/min; after adsorption balance, filtering a water sample by using a 0.45 mu m microporous filter membrane, and determining and calculating the liquid-phase equilibrium concentration of the TBBPA and the equilibrium adsorption capacity of the ball-milled modified porous carbon microsphere material on the TBBPA after adsorption balance; the two isothermal adsorption model equations are as follows:
Figure RE-957566DEST_PATH_IMAGE007
in the formula: ce(unit mg/L) is the equilibrium concentration of the liquid phase; q. q.se(unit mg/g) represents the equilibrium concentration of the solid phase; q. q.smax(in mg/g) represents Langmuir maximum adsorption capacity; kL(unit L/mg) is Langmuir constant; kFFreundlich adsorption coefficient; n is notLinear adsorption coefficient;
equilibrium parameter R using Langmuir equationLJudging the adsorption performance of the porous carbon microsphere material to TBBPA with different concentrations, and if 0, determining that the adsorption performance of the porous carbon microsphere material to TBBPA with different concentrations is not higher than 0<RL<1, favorable adsorption; if R isL>1, unfavorable adsorption; if R isL=1, linear adsorption; rL=0, adsorption is irreversible;
Figure RE-746530DEST_PATH_IMAGE008
D2) and calculating the optimal feeding proportion corresponding to the calculated and verified optimal solution according to the two isothermal adsorption models, adding the ball-milling modified porous carbon microsphere material into the TBBPA sewage, and completing the adsorption of the TBBPA in the water body.
The ball-milling modified porous carbon microsphere material adopted by the TBBPA-containing sewage treatment method is characterized in that micron-sized porous carbon microspheres are used as a base material, and are modified and enhanced by ball milling and nitrogen doping to form porous carbon microsphere black solid powder so as to enhance the removal performance of the powder on TBBPA; the porous carbon microsphere base material is repeatedly extruded, deformed and broken in the ball milling process, so that the specific surface area of the porous carbon microsphere base material is increased, the dispersity is enhanced, the thermal stability is increased, the average pore diameter of the surface of the porous carbon microsphere is increased, the pore diameter of a micropore with the diameter of 0.5-2 nm is increased, the content of carboxyl in oxygen-containing functional groups on the surface is increased, and the content of lactone groups and phenolic hydroxyl groups is reduced; the adsorption to TBBPA is uniform adsorption of a monomolecular layer, the adsorption is realized by the interaction of a hydrogen bond and a pi-pi electron acceptor, and the influence of pH and humic acid (DOM) is small.
The ball-milling modified porous carbon microsphere is spherical, has an average particle size of 1 mu m, has a rich microporous structure, and is embedded with narrow slit-shaped pores in small pores.
The preparation method of the ball-milling modified porous carbon microsphere material is characterized by comprising the following steps:
1) dissolving glucose powder in deionized water to prepare a glucose solution, heating and stirring the glucose solution, performing ultrasonic treatment, placing the glucose solution in a stainless steel hydrothermal reaction kettle with a polytetrafluoroethylene lining, and performing hydrothermal reaction under a closed condition for a set time to obtain a mixed solution;
2) cooling the mixed solution to room temperature, performing solid-liquid separation, vacuum drying, placing the mixed solution in a tubular furnace, calcining the mixed solution in a nitrogen atmosphere to obtain micron-level black solid, and drying to obtain porous carbon microspheres;
3) the porous carbon microsphere is taken as a base material, and is put into a planetary ball mill together with NaCl and ball milling substances in a set proportion, and ball milling modification is carried out at a set rotating speed for a set ball milling time, so as to obtain the ball milling modified porous carbon microsphere material.
In the step 1), 10 g-40 g of glucose is dissolved in 50mL of deionized water to prepare a saturated glucose solution.
In the step 1), a stainless steel hydrothermal reaction kettle made of polytetrafluoroethylene is placed into an oven under a closed condition, the reaction temperature is 160-240 ℃, and the hydrothermal reaction time is 6-18 h.
In the step 2), the dried black solid porous carbon microsphere material is placed in a tube furnace in a nitrogen atmosphere, and is calcined at the temperature of 600-1200 ℃ for 0.5-4 h at the nitrogen flow rate of 0.5-2 mL/min, so that porous carbon microsphere powder with the diameter of 2-5 microns is obtained.
In the step 3), the mass ratio of the porous carbon microspheres to NaCl is 50: 1; the mass ratio of the ball milling matter to the porous carbon microspheres is 4.5: 1.
in the step 3), the ball milling is carried out for 0.8 to 2.4 hours by a planetary ball mill at the speed of 300 to 700 r/min.
In the step 3), the rotation direction of the ball milling tank is 0.4-1.2 h clockwise rotation and 0.4-1.2 h anticlockwise rotation in the ball milling process, and the rotation direction are sequentially alternated.
The application of the ball-milling modified porous carbon microsphere material is characterized in that the ball-milling modified porous carbon microsphere material is used as an adsorbent for removing TBBPA in a water body.
Compared with the prior art, the invention has the advantages that:
(1) the sewage treatment method and the ball-milling modified porous carbon microsphere material adopted by the method enhance the removal performance of the porous carbon microsphere on TBBPA through ball milling and nitrogen doping modification, and the ball-milling modification can obviously change the components, the structure and the chemical characteristics of the porous carbon microsphere: compared with an unmodified porous carbon microsphere material, the modified porous carbon microsphere material has the advantages that the specific surface area, the pore volume, the surface functional group content, the thermal stability and the dispersibility are increased, so that the TBBPA removal capacity is enhanced, the adsorption rate accords with a two-stage kinetic model, the adsorption process of the TBBPA by the porous carbon microsphere can be better described through a Langmuir model, the adsorption process is mainly uniform adsorption of a monomolecular layer, the maximum adsorption capacity is 58.35mg/g, and the adsorption capacity is improved by 1.6 times compared with the unmodified material; the adsorption rate is 0.41 mg/(mg-min), which is improved by 2.89 times compared with the unmodified material. The adsorption mechanism is mainly the interaction of hydrogen bonds and pi-pi electron acceptors, and is less influenced by pH and humic acid (DOM), so the limitation of environmental conditions is overcome, and the application range of the composite material is widened.
(2) Compared with the unmodified porous carbon microsphere material, the ball-milling modified porous carbon microsphere material prepared by the invention has great difference in material characterization: small-area damage appears on the surface of the material on the appearance, but the spherical structure is not changed; the specific surface area is increased by 2.6 times; the total pore volume and the average pore diameter in the pore structure are increased, and the pore diameter of micropores is increased; the material surface acidic functional group content and thermal stability are increased, the dispersibility in the solution is good, and the material surface acidic functional group content and thermal stability have good adsorption performance on hydrophobic organic pollutants TBBPA.
(3) The carbon-based material adopted by the ball-milling modified porous carbon microsphere material provided by the invention has various electron orbital characteristics of sp, sp2 and sp3 hybridization and a crystal form caused by the anisotropy of sp2, so that the carbon-based material has various structural forms. The porous carbon microsphere material integrates the advantages of a carbon-based material and a spherical colloid, has a large specific surface area, high hydrophobicity and a special pore structure, and is an excellent adsorbent for hydrophobic organic pollutants. Meanwhile, the porous carbon microsphere can be improved in performance by modifying the porous carbon microsphere, doping heteroatom and graphitizing, and particularly, the adsorption performance of the porous carbon microsphere on hydrophobic organic pollutants such as TBBPA (tert-butyl bisphenol A) and the like is improved.
(4) The preparation method of the ball-milling modified porous carbon microsphere material provided by the invention has the advantages that the process steps are reasonable, the quality of the prepared microsphere is stable, the breakage rate is low, the controllability of the reaction process is high, and the industrialization is easy to realize while the material modification is carried out. Stirring glucose, performing ultrasonic and hydrothermal synthesis, and carbonizing at high temperature in inert gas to obtain porous carbon microspheres; and then placing the porous carbon microspheres, NaCl and the ball milling matter into a planetary ball mill, and obtaining the ball milling modified porous carbon microspheres under the action of external mechanical force.
(5) According to the ball-milling modified porous carbon microsphere material and the preparation method, cheap glucose is used as a unique carbon source, uniformly dispersed micron-sized porous carbon balls are obtained firstly, and are subjected to ball milling by a planetary ball mill, the ball-milling proportion, the ball-milling time, the rotating speed and the rotating direction of the porous carbon microspheres and a ball-milling medium are accurately controlled in the ball-milling process, so that the prepared ball-milling modified porous carbon microsphere material is stable in quality and small in breakage rate; the prepared ball-milling modified porous carbon microsphere material is cheap, quick to prepare, low in overall cost and easy to popularize in a large range.
(6) The preparation method of the ball-milling modified porous carbon microsphere material provided by the invention adopts micron-level porous carbon microspheres as templates, and adjusts different conditions of mechanical ball milling to ensure that the porous carbon microspheres are repeatedly extruded, deformed and broken in the ball milling process, so that the specific surface area is increased (1119.5 m 2/g), the dispersibility is enhanced, the thermal stability is increased, the average pore diameter of the surfaces of the porous carbon spheres is increased, and the pore diameter of micropores and oxygen-containing functional groups on the surfaces are greatly changed (the content of carboxyl is increased, and the content of lactone groups and phenolic hydroxyl groups is reduced).
(7) According to the application of the ball-milling modified porous carbon microsphere material provided by the invention, through an actual test surface, in the adsorption process of tetrabromobisphenol A (TBBPA) as an adsorption hydrophobic organic pollutant, the ball-milling modified porous carbon microsphere (C-ball milling in the figure) is 1.6 times of the maximum adsorption capacity and 2.9 times of the adsorption rate of the unmodified porous carbon microsphere. In addition, the composite material has good resistance to the influence of some common environmental factors, is less influenced by pH and humic acid (DOM), overcomes the adverse influence of environmental condition change on the adsorption effect, and has a wide application prospect.
Drawings
FIG. 1(a) is an SEM image of porous carbon microspheres synthesized by hydrothermal calcination of glucose in example 1 of the present invention;
FIG. 1(b) is an SEM image of ball-milled modified porous carbon microspheres of example 1 of the present invention;
FIG. 2(a) is an SEM photograph of porous carbon microspheres obtained in comparative example 1 of the present invention;
FIG. 2(b) is an SEM photograph of porous carbon microspheres obtained in comparative example 2 of the present invention;
FIG. 2(c) is an SEM image of ball-milled modified porous carbon microspheres prepared in comparative example 4 of the present invention;
FIG. 3 is a schematic diagram of a ball-milling addition ratio test of NaCl and porous carbon microspheres in the embodiment of the invention;
FIG. 4 is a schematic diagram of a ball milling addition ratio test of a ball milling substance and porous carbon microspheres in an embodiment of the invention;
FIGS. 5(a) - (f) are graphs of various characteristics and dispersion behavior in solution of materials before and after modification of porous carbon spheres of examples of the present invention, wherein:
FIG. 5(a) is N for modified and unmodified four materials2Adsorption-desorption curve chart;
FIG. 5(b) is a graph of pore size distribution for four materials, modified and unmodified;
FIG. 5(c) is a FT-IR spectrum of modified and unmodified porous carbon microspheres;
FIG. 5(d) is a Fourier Infrared Spectroscopy XPS plot of modified and unmodified porous carbon microspheres;
FIG. 5(e) is a graph of oxygen content of modified and unmodified porous carbon microspheres, showing that the modification enhances the thermal stability of the carbon material;
FIG. 5(f) shows the dispersibility of the material in the solution after 24 hours before and after modification, with unmodified porous carbon sphere material on the left and modified C-ball milled material on the right;
FIG. 6(a) is a kinetic curve of TBBPA adsorption of the material before and after modification (dotted line is a first order kinetic fit curve; solid line is a second order kinetic fit curve);
FIG. 6(b) is an isotherm of TBBPA adsorption of the material before and after modification (the solid line is a Langmuir-fit curve; the dotted line is a Freundlich-fit curve);
FIG. 6(c) is a graph of the effect of solution pH on adsorption of TBBPA on different materials;
FIG. 6(d) is a graph of the effect of solution Humic Acid (HA) on adsorption of TBBPA on different materials.
In each figure, the modified material prepared by the invention is abbreviated as C-ball milling.
The present invention will be described in detail below with reference to the accompanying drawings and examples.
Detailed Description
Example 1:
referring to the attached drawings 1(a), 1(b), 2(a), 2(b), 2(c), 3 and 4, the method for treating the TBBPA-containing sewage provided by the embodiment comprises the following steps:
A) preparing ball-milling modified porous carbon microsphere material powder serving as a TBBPA sewage adsorbent, wherein the preparation amount is more than 50 mg;
B) obtaining 100ml of TBBPA-containing sewage sample, and determining the TBBPA concentration to be 20mg/L by using high performance liquid chromatography;
C) adding ball-milling modified porous carbon microsphere materials with different adding proportion and dosage (5-30 mg) into a TBBPA-containing sewage sample respectively, and calculating and verifying the adsorption performance of the materials to TBBPA and the optimal feeding proportion according to the following formula:
Figure RE-379637DEST_PATH_IMAGE001
in the formula: q is the solid-phase adsorption concentration (unit mg/g) of the material to TBBPA in adsorption equilibrium, V is the volume of the solution (unit L), C0Is the initial concentration of contaminant (in mg/L), CeThe concentration of the liquid phase at adsorption equilibrium (unit mg/L), m is the mass of the adsorbent (unit g);
v =0.1L, m =0.02g, C in formula (1)0 =0.02 mg/L，Ce=0.0137 mg/L, and q =40.7 mg/g calculated by the formula.
D) And according to the calculated optimal q value, the corresponding optimal feeding proportion is 20mg, namely the optimal feeding proportion of the ball-milling modified porous carbon microsphere material corresponding to the TBBPA concentration in the sewage is 5000: adding the ball-milling modified porous carbon microsphere material into TBBPA sewage, and completing adsorption of TBBPA in a water body.
Referring to the attached drawings, referring to fig. 1(a), fig. 1(b), fig. 2(a), fig. 2(b) and fig. 2(c), the ball-milling modified porous carbon microsphere material adopted by the TBBPA-containing sewage treatment method is a porous carbon microsphere reinforced by ball milling and nitrogen doping, and is a porous carbon microsphere black solid powder reinforced by ball milling and nitrogen doping to enhance the TBBPA removal performance of the material; the porous carbon microsphere base material is repeatedly extruded, deformed and broken in the ball milling process, so that the specific surface area of the porous carbon microsphere base material is increased, the dispersity is enhanced, the thermal stability is increased, the average pore diameter of the surface of the porous carbon microsphere is increased, the pore diameter of a micropore with the diameter of 0.5-2 nm is increased, the content of carboxyl in oxygen-containing functional groups on the surface is increased, and the content of lactone groups and phenolic hydroxyl groups is reduced; the adsorption to TBBPA is uniform adsorption of a monomolecular layer, the adsorption is realized by the interaction of a hydrogen bond and a pi-pi electron acceptor, and the influence of pH and humic acid (DOM) is small.
The ball-milling modified porous carbon microsphere is spherical, has an average particle size of 1 mu m, has a rich microporous structure, and is embedded with narrow slit-shaped pores in small pores.
A preparation method of the ball-milling modified porous carbon microsphere material comprises the following steps:
1) dissolving glucose powder in deionized water to prepare a glucose solution, heating and stirring the glucose solution, performing ultrasonic treatment, placing the glucose solution in a stainless steel hydrothermal reaction kettle with a polytetrafluoroethylene lining, and performing hydrothermal reaction under a closed condition for a set time to obtain a mixed solution; specifically, 10 g-40 g of glucose is dissolved in 50mL of deionized water to prepare a saturated glucose solution; putting a stainless steel hydrothermal reaction kettle of polytetrafluoroethylene into an oven under a closed condition, wherein the reaction temperature is 160-240 ℃, and the hydrothermal reaction time is 6-18 h;
2) cooling the mixed solution to room temperature, performing solid-liquid separation, vacuum drying, placing the mixed solution in a tubular furnace, calcining the mixed solution in a nitrogen atmosphere to obtain micron-level black solid, and drying to obtain porous carbon microspheres; placing a dried black solid porous carbon microsphere material in a tubular furnace in a nitrogen atmosphere, calcining for 0.5-4 h at 600-1200 ℃ and at a nitrogen flow rate of 0.5-2 mL/min to obtain porous carbon microsphere powder with the diameter of 2-5 mu m;
3) the porous carbon microsphere is taken as a base material, and is put into a planetary ball mill together with NaCl and ball milling substances in a set proportion, and ball milling modification is carried out at a set rotating speed for a set ball milling time to obtain a ball milling modified porous carbon microsphere material; wherein the ball milling is carried out for 0.8 to 2.4 hours by a planetary ball mill at the speed of 300 to 700 r/min; in the ball milling process, the rotation direction of the ball milling tank is 0.4-1.2 h clockwise rotation, and 0.4-1.2 h anticlockwise rotation, which are sequentially alternated.
In the embodiment, NaCl (superior grade, particle size <10 mm) with different mass proportions is mixed with porous carbon microspheres and then is subjected to ball milling, wherein the adding ratio of NaCl is 0-200: 1, the test result is shown in fig. 3, in this example, the optimum adding ratio of NaCl is 50: 1.
in the embodiment, ball milling substances with different mass ratios are mixed with NaCl and porous carbon microspheres and then are subjected to ball milling, and the addition ratio of the ball milling substances to the porous carbon microspheres is selected to be 2-10: 1, carrying out the test. The ball milling matter is alumina particles with the particle size not larger than 5mm, the test result is shown in figure 4, in the embodiment, the ball milling matter adding ratio of NaCl is 4.5: 1.
example 2:
the method for treating wastewater containing TBBPA, the ball-milling modified porous carbon microsphere material and the preparation method thereof provided by the embodiment are basically the same as those in the embodiment 1, and the differences are as follows:
the step C) also comprises the following steps: C1) through adsorption kinetics experiments, the optimal feeding proportion is calculated and verified, and the method specifically comprises the following steps:
respectively adopting a quasi-first-stage kinetic model and a quasi-second-stage kinetic model to fit the kinetic process of TBBPA adsorption of the modified porous carbon microspheres, wherein the quasi-first-stage kinetic model, the quasi-second-stage kinetic model and the intra-particle diffusion model are respectively expressed as formulas (2), (3) and (4):
Figure RE-260743DEST_PATH_IMAGE009
in the formula:
Figure RE-67025DEST_PATH_IMAGE003
(mg/g) and
Figure RE-913758DEST_PATH_IMAGE004
(mg/g) is the solid phase concentration at equilibrium and at time t, respectively,
Figure RE-186608DEST_PATH_IMAGE005
(unit min)-1）、
Figure RE-322054DEST_PATH_IMAGE006
[ Unit mg/(mg. min)]And k3(unit mg/(g. h)1/2) Are the quasi-first order rate model, the quasi-second order rate model, and the intra-particle diffusion model rate constants, respectively; c (in mg/g) is the intra-particle diffusion constant;
D1) calculating and verifying optimal solutions according to the quasi-first-stage kinetic model, the quasi-second-stage kinetic model and the intra-particle diffusion model, and using q in the formulas (2), (3) and (4)e=40.7 mg/g，qtAnd (3) =27.3 mg/g, and substituting a formula for t =10 min to calculate the optimal feeding proportion of the ball-milling modified porous carbon microsphere material corresponding to the TBBPA concentration in the sewage to be 5000: adding the ball-milling modified porous carbon microsphere material into TBBPA sewage according to the proportion, and completing the adsorption of TBBPA in the water body.
Example 3:
the method for treating wastewater containing TBBPA, the ball-milling modified porous carbon microsphere material and the preparation method thereof provided by the embodiment are basically the same as those in the embodiments 1 and 2, and have the following differences:
and D), taking sewage near an electronic waste dismantling area in Qingyuan city, Guangdong province, pretreating the sewage to enable the TBBPA concentration to be concentrated to 100mL, wherein the final concentration is 5mg/L, adding ball-milling modified porous carbon microsphere materials in different proportions, and selecting the optimal feeding proportion to adsorb the TBBPA.
Different amounts of ball-milling modified porous carbon microsphere materials are added into sewage of a sewage treatment plant for adsorption, according to the relative optimal q value obtained by instrument detection, the optimal feeding proportion of the ball-milling modified porous carbon microsphere materials corresponding to the TBBPA concentration in the sewage is 3500: adding the ball-milling modified porous carbon microsphere material into TBBPA sewage, and completing adsorption of TBBPA in a water body.
In this embodiment, the optimum addition ratios of NaCl, the ball milling agent and the ball milling modified porous carbon microsphere material in the preparation process obtained through a single control test are respectively as follows: the optimal NaCl adding ratio is 50: 1 and the ball milling mass adding ratio is 4.5: 1.
example 4
The method for treating TBBPA-containing sewage, the ball-milling modified porous carbon microsphere material and the preparation method thereof provided in this embodiment are basically the same as those in embodiments 1 to 3, except that the preparation method of the ball-milling modified porous carbon microsphere material includes the following steps:
1) dissolving 40g of glucose powder in 50mL of deionized water to prepare a saturated glucose solution, heating and stirring the saturated glucose solution, performing ultrasonic treatment, placing the solution in a stainless steel hydrothermal reaction kettle with a polytetrafluoroethylene lining, and performing hydrothermal reaction at 220 ℃ for 14 hours under a closed condition;
2) cooling the mixed solution obtained in the step A to room temperature, performing solid-liquid separation, vacuum drying for 8 hours, and calcining the mixed solution in a tubular furnace at 800 ℃ for 2 hours in a nitrogen atmosphere at the nitrogen flow rate of 1mL/min to obtain micron-grade porous carbon microspheres;
3) putting porous carbon microspheres, NaCl and ball milling substances in a set proportion into a planetary ball mill; specifically, NaCl: the porous carbon microsphere is 50: 1, adding NaCl according to the proportion of ball milling substances: the porous carbon microspheres are 4.5: adding ball milling matter according to the proportion of 1, and carrying out ball milling at the rotating speed of 575r/min for 1.6h (0.8h in the clockwise direction and 0.8h in the anticlockwise direction) to obtain the ball-milling modified porous carbon microsphere material.
Comparative example 1 in the example, 20g of glucose was added to 50mL of deionized water, and the other operations were the same as in the example, and the obtained product was washed and calcined as shown in fig. 1(a) and 1(b), and the porous carbon microspheres had different particle sizes and were adhered to each other.
Comparative example 2 in the example, the hydrothermal reaction product is calcined at 1000 ℃ for 2h in a nitrogen atmosphere at a nitrogen flow rate of 1mL/min, other operations are the same as the example, cracks appear on the surface of the obtained product, and the hole collapse phenomenon appears on the surface of the porous carbon sphere, and the scanning electron microscope results are shown in fig. 2(a), fig. 2(b) and fig. 2 (c);
comparative example 3 the following materials were used in the examples as ball mill: the porous carbon microsphere is 1: 1, and other operations are the same as the embodiment, so that the adsorption performance of the obtained product on hydrophobic organic pollutant TBBPA is hardly improved;
in comparative example 4, the rotation speed of 575r/min and the ball milling time of 1.6h (in the same rotation direction, clockwise direction) in the example are taken, the obtained product has large fragmentation degree, the specific surface area is reduced, the adsorption performance is reduced, and the results of a scanning electron microscope are shown in fig. 2(a), fig. 2(b) and fig. 2 (c).
Comparative example 5 porous carbon microspheres were modified in different ways, and the modification method was nitrogen-doped modification: adding 1 g of acetamide into the saturated glucose solution, and preparing the nitrogen-doped porous carbon microspheres by the rest steps; acid modification: 5 g of prepared porous carbon microspheres were added to 30% H2O2The solution was stirred in a magnetic stirrer at 150 r/min for 1 h at a reaction temperature of 65 ℃. After stirring was complete, the powder was collected and washed to neutrality with deionized water and the washed material was dried at 105 ℃ for 8 h.
The material performance test method comprises the following steps: respectively adopting a scanning electron microscope SEM (Hitachi S4800, SEM) and a specific surface area analyzer (TriStar II 3020) to represent changes of the apparent morphology, the specific surface area and the pore size distribution of the carbon material before and after modification; fourier transform infrared spectroscopy (FTIR; BRUKER TENSOR 27, Germany) and Boehm [24] titration were used to analyze the change characteristics of the surface chemical groups and oxygen-containing functional groups on the porous carbon microspheres; measuring the changes of surface elements and functional groups of the carbon material by using an X-ray photoelectron spectrometer (Thermo ESCALB 250 XI) (XPS); a thermogravimetric analyzer (TGA-50) measures the thermal stability of the sample, and compares the material characterization and adsorption performance of the 2 different modified materials obtained by the modification method, the original porous carbon microspheres and the ball-milled modified porous carbon microspheres of the present invention, and the specific results are shown in fig. 1(a), fig. 1(b), fig. 2(a), fig. 2(b), fig. 2(c), fig. 5(a) -fig. 5(f), and fig. 6(a) -fig. 6 (d).
The ball-milling modified porous carbon microsphere material provided by the invention has the following characteristic changes:
the invention provides a ball-milling modified porous carbon microsphere with surface morphology characteristic change: the surface topography of the carbon microsphere material with different surface modifications is shown in fig. 1(a), fig. 1(b), fig. 2(a), fig. 2(b) and fig. 2(c), and the porous carbon microsphere is a spherical material with smooth surface, 3-5 μm particle size and uniform particle size. C-N, C-H2O2And C-ball milling particle size is reduced, but the spherical structure is not changed; the diameter of the C-N spherulites is 2-3 μm; C-H2O2The particle size is about 2 mu m, and the surface roughness is increased after modification; the C-ball milled particles were about 1 μm in size and some fragments of the spherical particles after breaking were visible around the material.
The ball-milling modified porous carbon microsphere provided by the invention has the following pore structure and specific surface area change: referring to FIG. 3, N of the C-ball milled material prepared according to the present invention2The adsorption-desorption isotherm is inclined to the adsorption-desorption characteristics of the IV-type isotherm, which indicates that the porous carbon microsphere material has a mesoporous structure; the hysteresis loop is of type H4, indicating that the porous carbon microsphere pores are embedded in narrow slit-like pores. C-N, C-H2O2And C-ball milled N2The absorption-desorption curves are basically overlapped and tend to be in a type I, which shows that the porous carbon microsphere material has rich microporous structures, and the adsorption capacity of the C-ball milling is obviously increased. C-ball milling and C-H2O2The material has peaks in the pore diameter ranges of micropores and mesopores, which shows that the pore structure is developed.
The ball milling modification provided by the invention enables the aperture ratio of micropores (0.5-2 nm) and mesopores (2-50 nm) to be increased, and is obviously seen in comparison with the original porous carbon microspheres (see figure 5 (b)), and specifically shown in table 1.
TABLE 1C comparison of specific surface area and pore structure of ball-milled material modified with other 3 materials
Figure RE-666448DEST_PATH_IMAGE010
The invention provides a method for changing the characteristics of functional groups of ball-milling modified porous carbon microspheres, which comprises the following steps:
from FT-IR spectrograms of 4 materials, the porous carbon microspheres are 690 cm-1、1143 cm-1、1650 cm-1、3480 cm -14 absorption peaks are nearby; of which 690 cm-1、3480 cm-1The peak appeared at (A) is mainly caused by the stretching vibration of the hydroxyl group, 1143 cm-1And 1650 cm-1Mainly caused by stretching vibration of the-C-O bond and carbonyl group. At 1729 cm-1A C = O absorption peak is present, possibly with carboxyl or phenolic hydroxyl functional groups. C-H2O2At 2400 cm-1A small stretching peak is nearby, and unsaturated alkyl and an-N-O group exist; C-H2O2And C-ball milling at 1143 cm-1The characteristic absorption peak of C-O is enhanced, which shows that the carboxyl or phenolic hydroxyl functional group is greatly increased. XPS analysis shows that C-N forms a large number of O-N and C-N groups at 398.2 eV and 400.1 eV, and graphite N is formed to increase the active sites; the oxygen content of the C-ball mill was 1.8 times that before the modification. (ii) a The carboxyl content on the surface of the C-ball mill is improved by 1.8 times, but the contents of phenolic hydroxyl and lactone groups are reduced, and the lactone groups and the phenolic hydroxyl groups are oxidized and converted into carboxyl groups in the modification process.
The ball-milling modified porous carbon microsphere provided by the invention has the following changes in thermal stability and dispersibility:
practical tests show that the C-N, C-H is prepared at the same heating temperature2O2The mass loss of the C-ball milling is lower than that of the porous carbon microspheres, wherein the mass loss of the porous carbon microspheres is about 40% at 800 ℃, and the C-H loss is2O2The mass loss of the carbon material is 30 percent, and the mass loss of the C-N and C-ball milling is 20 percent, which shows that the thermal stability of the carbon material is enhanced by modification. Respectively mixing porous carbon microsphere and C-N, C-H2O2And C-ball milling in water for 24H to obtain porous carbon microspheres, C-N and C-H2O2The carbon-containing porous carbon microsphere material is freely settled to the bottom of the bottle, and the C-ball milling is uniformly dispersed, so that a foundation is provided for enhancing the TBBPA adsorption performance of the porous carbon microsphere material.
The change of the adsorption kinetic characteristics of the modified porous carbon microspheres provided by the invention is as follows:
see porous carbon microspheres,C-N、C-H2O2And C-ball milling adsorption TBBPA quasi-first-level dynamics and quasi-second-level dynamics models, wherein the quasi-second-level dynamics fits parameter R20.997, 0.995, 0.998 and 0.990 respectively, higher than the quasi-first order kinetics (see table 2), the quasi-second order equations include adsorption processes such as liquid film diffusion, surface adsorption and intraparticle diffusion, and electron sharing or transfer, while the quasi-first order equations are only applicable to describe the initial stage of adsorption, and therefore, the quasi-second order kinetics model can more reasonably describe the adsorption process and is dominated by chemisorption. C-N, C-H2O2C-ball milled K2Values are increased by 1.5 times, 2.6 times and 2.9 times respectively, which shows that the modification of the invention accelerates the adsorption process of the porous carbon microsphere to TBBPA, and the increase of the specific surface area and the oxygen-containing functional group can improve the adsorption rate of the porous carbon microsphere to TBBPA.
TABLE 2 comparison table of kinetic fitting parameters of TBBPA adsorption of materials before and after modification
Figure RE-872082DEST_PATH_IMAGE011
Note that in the table k1(unit min)-1 )、k2[ Unit g/(mg. min)]Parameters of corresponding quasi-first-stage and quasi-second-stage equations are respectively set; k is a radical ofd[ unit mg/(g.min.)1/2)]Is an intra-particle diffusion equation rate parameter; ci is a constant related to the boundary layer thickness.
The isothermal adsorption characteristic of the ball-milling modified porous carbon microsphere provided by the invention is changed as follows: porous carbon microspheres, C-N, C-H2O2And the maximum adsorption capacity of the C-ball mill to TBBPA is respectively 36.6 mg/g, 43.1 mg/g, 47.4 mg/g and 58.35mg/g, which are respectively improved by 1.2 times, 1.3 times and 1.6 times. C-H2O2The increase of the oxygen-containing functional groups on the surface enhances the capability of forming hydrogen bonds with functional groups such as phenolic hydroxyl groups and the like, and improves the adsorption performance. On one hand, the specific surface area of the carbon material is obviously improved through ball milling, active sites for adsorbing pollutants are increased, and on the other hand, the increased oxygen-containing functional groups enhance the effects of hydrogen bonds and pi-pi electron donor and acceptor. The reason for the improved C-N adsorption performance is the appearance of a large amount of high activity on the surfaceAnd graphite N of high stability, more defect sites are formed.
Porous carbon microspheres, C-N, C-H2O2And Langmuir equation R for TBBPA adsorption by C-ball milling provided by the invention2The adsorption process is respectively 0.994, 0.996, 0.992 and 0.985 which are higher than that of a Freundlich model (table 4), the adsorption process is more consistent with Langmuir isothermal adsorption and is monomolecular layer uniform adsorption, and the fitting parameter N of the Freundlich model is less than 1, which indicates that the adsorption process is synergistic nonlinear adsorption. The balance parameters R of the porous carbon microspheres, C-N, C-H2O2 and C-ball milling are calculated and obtained by the formula (7)L0.27, 0.23, 0.16 and 0.12, respectively, between 0 and 1, indicating that the material after ball milling modification is more favorable for adsorbing TBBPA. See table 3 for details.
TABLE 3 comparison table of isothermal adsorption line fitting parameters of adsorption TBBPA of materials before and after modification
Figure RE-784675DEST_PATH_IMAGE012
Note qmAs theoretical maximum adsorption capacity, mg/g, KL(L/mg)、KF(L/mg) and 1/N are the adsorption constants of the corresponding equations.
Influence of pH on adsorption of TBBPA by the ball-milled modified porous carbon microspheres of the invention:
the pH determines the charge state of the adsorbent and adsorbate molecules, and is one of the important factors influencing the adsorption capacity of the carbon material in the solution. The invention tests the change of the adsorption capacity of the carbon microspheres in the solutions with different pH values on TBBPA, and the result shows that the adsorption capacity is increased and then decreased along with the increase of pH, and the adsorption capacity of 4 kinds of porous carbon microspheres reaches the maximum attached figure 6(c) when the pH = 7; when the pH value is less than 7, the H + in the solution is continuously reduced along with the increase of the pH value, and the adsorption quantity of the TBBPA is gradually increased, which is caused by the fact that the adsorption sites are seized by H + and TBBPA molecules in the solution; when the pH is more than 7, the adsorption amount of the 4 kinds of porous carbon microspheres to TBBPA is reduced, because TBBPA is deprotonated with the increase of the pH and occupies a dominant position in the form of anion, IEPs (isoelectric points) of the carbon-containing adsorbent are lower than 3.4, and the surface of the carbon-containing adsorbent is negatively charged under alkaline conditions to form electrostatic repulsion. With the change of pH, the change degree of the adsorption capacity of the ball milling modified material provided by the invention is smaller than that of the unmodified porous carbon microspheres, and the main reason is that the increased oxygen-containing functional groups (carboxyl) after surface modification play a role in buffering the change of pH, which shows that the ball milling modification performed by the invention widens the pH application range of the porous carbon material for removing TBBPA in water.
The influence of humic acid on the TBBPA adsorption performance of the ball-milling modified porous carbon microspheres disclosed by the invention is as follows:
referring to FIG. 6(d), C-N, C-H was added to the solution after HA was added to the solution in the experiment2O2The reduction range of the adsorption capacity of the C-ball milling is relatively slow, mainly because the specific surface area of the nitrogen-doped and ball-milled modified carbon material is relatively large, more adsorption sites can be provided, and H is2O2The modification greatly increases oxygen-containing functional groups on the surface of the carbon material, enhances the interaction (hydrogen bond, pi-pi electron acceptor) of the carbon material and TBBPA, and strengthens the competitive adsorption of the TBBPA. When the concentration of humic acid is less than 20mg/L, porous carbon microspheres, C-N, C-H2O2The change of the adsorption capacity of the C-ball mill to TBBPA is less than 4 mg/g, when the adsorption capacity is increased to 30mg/L, the adsorption capacity is respectively reduced by 42%, 31%, 41% and 19%, because the polar functional groups on the carbon material and the amino and carboxyl of HA form strong hydrogen bonding effect, and the pi electron conjugated structure of the carbon material further promotes the carbon material to form strong interaction force with the HA, and the HA adsorbed on the surface of the carbon material adsorbs water molecules through the hydrogen bonding effect to form water molecular clusters, so that the adsorption of the carbon material to TBBPA is hindered. However, the ball-milling modified porous carbon microspheres provided by the invention are minimally affected, so that the comprehensive performance of the ball-milling modified porous carbon microspheres is superior to that of other 3 materials.
In other embodiments of the present invention, different specific schemes selected from the range of the 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 in the following.
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 (12)

1. A TBBPA-containing sewage treatment method is characterized by comprising the following steps:
A) preparing a ball-milling modified porous carbon microsphere material serving as a TBBPA sewage adsorbent;
B) obtaining a TBBPA-containing sewage sample, and measuring the TBBPA concentration by using a high performance liquid chromatography;
C) adding ball-milling modified porous carbon microsphere materials with different proportional dosages into a TBBPA-containing sewage sample respectively, and calculating and verifying the adsorption performance and the optimal feeding proportion of the material to TBBPA according to the following formula:
Figure 177783DEST_PATH_IMAGE001
in the formula: q is the solid-phase adsorption concentration of the material to TBBPA in adsorption equilibrium, V is the volume of the solution, C0As initial concentration of contaminant, CeThe concentration of the liquid phase at the time of adsorption equilibrium, m is the mass of the adsorbent;
D) and adding the ball-milling modified porous carbon microsphere material into TBBPA sewage according to the optimal feeding proportion corresponding to the optimal q value obtained by calculation, and completing the adsorption of TBBPA in the water body.
2. The TBBPA-containing wastewater treatment process of claim 1, step C), further comprising the steps of: C1) through adsorption kinetics experiments, the optimal feeding proportion is calculated and verified, and the method specifically comprises the following steps:
respectively adopting a quasi-first-stage kinetic model and a quasi-second-stage kinetic model to fit the kinetic process of TBBPA adsorption of the modified porous carbon microspheres, wherein the quasi-first-stage kinetic model, the quasi-second-stage kinetic model and the intra-particle diffusion model are respectively expressed as formulas (2), (3) and (4):
Figure 783207DEST_PATH_IMAGE002
in the formula: q. q.seAnd q istThe solid phase concentrations at equilibrium and time t, k1、k2And k3The method comprises the following steps of respectively obtaining a quasi-first-stage rate model, a quasi-second-stage rate model and a particle internal diffusion model rate constant; c is the intra-particle diffusion constant;
D1) and (3) according to the optimal feeding proportion corresponding to the optimal solution calculated and verified by the quasi-first-stage dynamic model, the quasi-second-stage dynamic model and the particle internal diffusion model, adding the ball-milling modified porous carbon microsphere material into the TBBPA sewage, and completing the adsorption of the TBBPA in the water body.
3. The TBBPA-containing wastewater treatment process of claim 1, step C), further comprising the steps of: C2) determining the optimal feeding proportion through an isothermal adsorption experiment, specifically:
adding a certain amount of adsorbent under different concentration gradients of TBBPA-containing pollutants in the sewage, and putting the conical flask into a constant-temperature shaking incubator, wherein the temperature is 25 ℃, and the rotating speed is controlled at 150 r/min; after adsorption balance, filtering a water sample by using a 0.45 mu m microporous filter membrane, and determining and calculating the liquid-phase equilibrium concentration of the TBBPA and the equilibrium adsorption capacity of the ball-milled modified porous carbon microsphere material on the TBBPA after adsorption balance; the two isothermal adsorption model equations are as follows:
Figure 389769DEST_PATH_IMAGE003
in the formula: ceThe liquid phase equilibrium concentration; q. q.seRepresents the equilibrium concentration of the solid phase; q. q.smaxRepresents the Langmuir maximum adsorption capacity; kLLangmuir constant; kFFreundlich adsorption coefficient; n is a nonlinear adsorption coefficient;
equilibrium parameter R using Langmuir equationLJudging the adsorption performance of the porous carbon microsphere material to TBBPA with different concentrations, and if 0, determining that the adsorption performance of the porous carbon microsphere material to TBBPA with different concentrations is not higher than 0<RL<1, favorable adsorption; if R isL>1, unfavorable adsorption; if R isL=1, linear adsorption; rL=0, adsorption is irreversible;
Figure 383133DEST_PATH_IMAGE004
D2) and calculating the optimal feeding proportion corresponding to the calculated and verified optimal solution according to the two isothermal adsorption models, adding the ball-milling modified porous carbon microsphere material into the TBBPA sewage, and completing the adsorption of the TBBPA in the water body.
4. A ball-milling modified porous carbon microsphere material adopted by the TBBPA-containing sewage treatment method disclosed by any one of claims 1-3 is characterized in that micron-sized porous carbon microspheres are used as a base material, and are modified and enhanced by ball milling and nitrogen doping to form porous carbon microsphere black solid powder so as to enhance the TBBPA removal performance of the powder; the porous carbon microsphere base material is repeatedly extruded, deformed and broken in the ball milling process, so that the specific surface area of the porous carbon microsphere base material is increased, the dispersity is enhanced, the thermal stability is increased, the average pore diameter of the surface of the porous carbon microsphere is increased, the pore diameter of a micropore with the diameter of 0.5-2 nm is formed, the content of carboxyl groups in oxygen-containing functional groups on the surface is increased, the content of lactone groups and phenolic hydroxyl groups is reduced, the adsorption of the porous carbon microsphere base material on TBBPA is uniform adsorption of a monomolecular layer, the adsorption is realized through the interaction of a hydrogen bond and a pi-pi electron acceptor, and the influence of pH and humic acid is small.
5. The ball-milling modified porous carbon microsphere material according to claim 4, wherein the ball-milling modified porous carbon microspheres are spherical, have an average particle size of 1 μm, have a rich microporous structure, and have narrow slit-shaped pores embedded in the pores thereof.
6. A preparation method of the ball-milling modified porous carbon microsphere material as claimed in any one of claims 4 to 5, which is characterized by comprising the following steps:
1) dissolving glucose powder in deionized water to prepare a glucose solution, heating and stirring the glucose solution, performing ultrasonic treatment, placing the glucose solution in a stainless steel hydrothermal reaction kettle with a polytetrafluoroethylene lining, and performing hydrothermal reaction under a closed condition for a set time to obtain a mixed solution;
2) cooling the mixed solution to room temperature, performing solid-liquid separation, vacuum drying, placing the mixed solution in a tubular furnace, calcining the mixed solution in a nitrogen atmosphere to obtain micron-level black solid, and drying to obtain porous carbon microspheres;
3) the porous carbon microsphere is taken as a base material, and is put into a planetary ball mill together with NaCl and ball milling substances in a set proportion, and ball milling modification is carried out at a set rotating speed for a set ball milling time, so as to obtain the ball milling modified porous carbon microsphere material.
7. The preparation method of claim 6, wherein in the step 1), 10g to 40g of glucose is dissolved in 50mL of deionized water to prepare a saturated glucose solution.
8. The preparation method of the polytetrafluoroethylene composite material according to the claim 6, wherein in the step 1), a stainless steel hydrothermal reaction kettle of polytetrafluoroethylene is placed into an oven under a closed condition, the reaction temperature is 160-240 ℃, and the hydrothermal reaction time is 6-18 h.
9. The preparation method according to claim 6, characterized in that in the step 2), the dried black solid porous carbon microsphere material is placed in a tube furnace in a nitrogen atmosphere, and calcined at 600-1200 ℃ for 0.5-4 h at a nitrogen flow rate of 0.5-2 mL/min to obtain porous carbon microsphere powder with a diameter of 2-5 μm.
10. The preparation method according to claim 6, wherein in the step 3), the mass ratio of the porous carbon microspheres to NaCl is 50: 1; the mass ratio of the ball milling matter to the porous carbon microspheres is 4.5: 1.
11. the preparation method of claim 6, wherein in the step 3), the ball milling is carried out for 0.8-2.4 h at a speed of 300-700 r/min by a planetary ball mill.
12. The preparation method of claim 6, wherein in the step 3), the rotation direction of the ball milling pot in the ball milling process is 0.4 h-1.2 h clockwise rotation and 0.4 h-1.2 h anticlockwise rotation, which are sequentially alternated.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116179529A (en) * 2023-02-24 2023-05-30 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) Method for degrading TBBPA by composting humus microbial agent and application

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103949216A (en) * 2014-05-13 2014-07-30 农业部环境保护科研监测所 Preparation method of carbon material for adsorbing hydrophilic ionic liquid
CN105582888A (en) * 2016-01-21 2016-05-18 西南科技大学 Method for preparing carbon microsphere adsorbent under catalysis of metal salt with low-temperature hydrothermal method
CN108033447A (en) * 2017-12-07 2018-05-15 吉林大学 Preparation method, multiporous biological matter carbon and the application of multiporous biological matter carbon
CN109704320A (en) * 2018-12-28 2019-05-03 新奥石墨烯技术有限公司 Functional carbon material and preparation method thereof, dispersion liquid and its application
CN110065999A (en) * 2019-04-26 2019-07-30 上海大学 The preparation method and applications of mechanical ball mill Modified Iron carbon material
CN111408348A (en) * 2020-04-28 2020-07-14 南阳师范学院 Preparation method of straw-based porous biochar nanospheres

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103949216A (en) * 2014-05-13 2014-07-30 农业部环境保护科研监测所 Preparation method of carbon material for adsorbing hydrophilic ionic liquid
CN105582888A (en) * 2016-01-21 2016-05-18 西南科技大学 Method for preparing carbon microsphere adsorbent under catalysis of metal salt with low-temperature hydrothermal method
CN108033447A (en) * 2017-12-07 2018-05-15 吉林大学 Preparation method, multiporous biological matter carbon and the application of multiporous biological matter carbon
CN109704320A (en) * 2018-12-28 2019-05-03 新奥石墨烯技术有限公司 Functional carbon material and preparation method thereof, dispersion liquid and its application
CN110065999A (en) * 2019-04-26 2019-07-30 上海大学 The preparation method and applications of mechanical ball mill Modified Iron carbon material
CN111408348A (en) * 2020-04-28 2020-07-14 南阳师范学院 Preparation method of straw-based porous biochar nanospheres

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
SEFU OLAITAN AMUSAT ET AL.: "Ball-milling synthesis of biochar and biochar–based nanocomposites and prospects for removal of emerging contaminants", 《JOURNAL OF WATER PROCESS ENGINEERING》 *
STEVENC.PETERSON等: "Increasing biochar surface area: Optimization of ball milling parameters", 《POWDER TECHNOLOGY》 *
周正华: "《纳米材料开发使用及质量检测技术标准应用手册》", 30 April 2005, 银声音像出版社 *
崔大伟: "《绿色环保节镍型不锈钢粉末的制备及其成形技术》", 30 November 2013, 中国环境出版社 *
段菲菲等: "多孔炭纳米球水相吸附四溴双酚A的性能", 《新型炭材料》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116179529A (en) * 2023-02-24 2023-05-30 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) Method for degrading TBBPA by composting humus microbial agent and application
CN116179529B (en) * 2023-02-24 2023-10-31 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) Method for degrading TBBPA by composting humus microbial agent and application

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