CN114160098B - Preparation method of alkali/bimetallic salt water heat activated sludge biochar for removing norfloxacin in water - Google Patents
Preparation method of alkali/bimetallic salt water heat activated sludge biochar for removing norfloxacin in water Download PDFInfo
- Publication number
- CN114160098B CN114160098B CN202111485720.8A CN202111485720A CN114160098B CN 114160098 B CN114160098 B CN 114160098B CN 202111485720 A CN202111485720 A CN 202111485720A CN 114160098 B CN114160098 B CN 114160098B
- Authority
- CN
- China
- Prior art keywords
- norfloxacin
- sludge biochar
- activated sludge
- biochar
- alkali
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/10—Treatment of sludge; Devices therefor by pyrolysis
-
- 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
- C02F2101/36—Organic compounds containing halogen
Abstract
The invention discloses a preparation method of alkali/bimetallic brine heat activated sludge biochar for norfloxacin removal in water, which comprises the steps of placing sludge biochar SBC prepared by pyrolysis in a tubular furnace in a reaction kettle containing potassium hydroxide solution for hydrothermal activation to generate alkali heat activated sludge biochar KSBC, and transferring the KSBC into the reaction kettle containing magnesium chloride and ferric chloride solution for hydrothermal activation treatment to prepare alkali/bimetallic brine heat activated sludge biochar KMSBC. The biochar prepared by the invention has excellent physical and chemical properties, can realize the efficient removal of norfloxacin in water, and has the maximum adsorption capacity of 68.5mg/g for norfloxacin at the reaction temperature of 35 ℃. In addition, the biochar has stronger safety and magnetic separation capability, and can realize high-efficiency magnetic separation from solution and desorption and regeneration of sodium hydroxide after adsorption.
Description
Technical Field
The invention relates to the technical field of biochar preparation and water treatment, in particular to a preparation method of alkali/bimetallic brine heat activated sludge biochar applied to norfloxacin removal in water.
Background
In recent years, fluoroquinolone antibiotics (FQs) have become the most used class of antibiotics in the world, and environmental problems caused by these have also begun to attract attention. Among them, norfloxacin is widely used for treating urinary, respiratory and intestinal diseases caused by sensitive bacteria because it can effectively inhibit the synthesis and replication of gram-positive and gram-negative bacteria DNA, and has become one of the most widely used FQs at present. Notably, human and animal norfloxacin has limited absorption capacity, and about 60-70% of unabsorbed norfloxacin can be expelled through feces and urine into an aqueous environment. The existing sewage treatment plants are not specially equipped with related equipment for removing antibiotics in water, and the removal efficiency of the antibiotics is low, so that a large amount of untreated norfloxacin enters the sludge, the water body and the soil. Norfloxacin has a long half-life and can exist in these environments for a long time, and enrichment by the food chain or production of superbacteria, drug resistance and resistance genes further jeopardizes human health and safety of the entire ecosystem.
The main removal means of norfloxacin at present include: photocatalysis, advanced oxidation, microbial degradation, and the like. Photocatalytic and advanced oxidation are stringent and costly in terms of operating conditions, and more toxic degradation products may be produced during the process, which limits their practical and widespread use. The period required by microbial degradation is long, and drug-resistant genes can be generated, which is unfavorable for large-scale application. The adsorption has the advantages of high cost efficiency, simple operation and environmental protection, and is a promising norfloxacin removal technology. Biochar is a porous adsorption material formed by pyrolysis of agricultural or industrial waste under anoxic or oxygen limiting conditions. Municipal sludge is the main solid waste of municipal sewage plants, and it is reported that the sludge yield in China exceeds 6.0X10 in 2020 8 t, the main treatment means at present are landfill and incineration, which may cause secondary pollution to soil, water and atmosphere. The high organic matter content of municipal sludge makes the municipal sludge potential to be a good raw material for preparing biochar, and can realize the resource utilization of the municipal sludge. The research surface shows that the sludge biochar has a certain adsorption capacity to organic matters (tetracycline, imidacloprid and the like) and inorganic matters (nickel and the like) in water, but the limited adsorption capacity limits the practical and practical applicationAnd (5) large-scale application. Research has shown that potassium hydroxide (KOH) can improve the pore structure of biochar, the kind and quantity of oxygen-containing functional groups, magnesium chloride (MgCl) 2 ) The surface area, the porosity, the ion exchange capacity and the like of the biochar can be remarkably improved, so that the adsorption removal capacity of the biochar on target pollutants is improved. Based on potassium hydroxide (KOH) and magnesium chloride (MgCl) 2 ) And the two are not combined for activating the biochar, the invention combines the two for modifying the sludge biochar. In addition, potassium hydroxide (KOH) and magnesium chloride (MgCl) 2 ) The activation of the biochar is mostly completed by dipping or stirring, and the activation effect on the biochar is limited. The hydrothermal activation method is to put the biochar and the active agent in a closed environment, and the activation effect of the active agent on the biochar can be better ensured through autogenous pressure and a certain temperature condition. After the modified sludge biochar adsorbs the norfloxacin, how to realize the efficient separation and regeneration of the norfloxacin and the water body has important research value and significance for realizing the sustainable removal of the norfloxacin in the water.
Disclosure of Invention
Based on the defects in the prior art, the technical problem solved by the invention is to provide the alkali/bimetallic salt water heat activated sludge biochar capable of efficiently removing norfloxacin in water, and meanwhile, the safety of an adsorbent can be ensured, and separation and regeneration of the biochar and a solution after norfloxacin adsorption can be realized. The treatment technology can realize the resource utilization of municipal sludge and the efficient and sustainable removal of norfloxacin in water.
In order to solve the technical problems, the invention provides a preparation method of alkali/bimetallic brine heat activated sludge biochar for removing norfloxacin in water, which comprises the following steps:
(1) Preparation of sludge biochar: washing municipal sludge with ultrapure water, drying to constant weight, pyrolyzing, grinding and sieving to obtain sludge biochar SBC;
(2) Preparation of alkaline water thermal activated sludge biochar: placing the sludge biochar SBC obtained in the step (1) in KOH solution, performing hydrothermal activation, washing with ultrapure water, centrifuging, drying, grinding and sieving to obtain alkaline water-activated sludge biochar KSBC;
(3) Preparation of a bimetal salt water heat activated sludge biochar: adding the sludge biochar SBC prepared in the step (1) into MgCl containing magnesium chloride 2 Ferric chloride FeCl 3 ·6H 2 Placing the mixed solution of O in a blast drying oven for hydrothermal activation, drying, grinding and sieving to obtain sludge biochar MSBC thermally activated by the bimetallic brine;
(4) Preparation of alkali/bimetallic brine heat activated sludge biochar: adding the KSBC prepared in the step (2) into MgCl containing magnesium chloride 2 Ferric chloride FeCl 3 ·6H 2 And (3) placing the mixed solution of O in a blast drying oven for hydrothermal activation, drying, grinding and sieving to obtain the sludge biochar KMSBC activated by alkali/bimetallic brine.
As the optimization of the technical scheme, the preparation method of the alkali/bimetallic brine heat activated sludge biochar for removing norfloxacin in water, provided by the invention, further comprises part or all of the following technical characteristics:
as an improvement of the technical scheme, in the step (1), the drying temperature is 50-90 ℃; the pyrolysis condition is that the flow rate of nitrogen is 0.3-0.6L/min, the heating rate is 5-15 ℃/min, and the pyrolysis is continuously carried out for 60-120min at 400-800 ℃; grinding, and sieving with 60-200 mesh sieve.
As an improvement of the technical scheme, in the step (2), the mass ratio of potassium hydroxide KOH to sludge biochar SBC=5g:2.5-10 g, and the concentration of KOH solution is 25-200g/L; the hydrothermal activation conditions are: the forced air drying temperature is 200-240 ℃, and the activation time is 600-900min; the drying temperature is 50-90 ℃, and the crushed materials are sieved by a 60-200 mesh sieve.
As an improvement of the technical scheme, in the step (3), the mass of the sludge biochar SBC and the mass of the magnesium chloride MgCl 2 Ferric chloride FeCl 3 ·6H 2 The volume ratio of the O solution is 2.5-10g:50-100mL; at the 50-100mL of MgCl 2 Ferric chloride FeCl 3 ·6H 2 MgCl in solution of O 2 Is 2.5-10g FeCl 3 ·6H 2 The mass of O is 2.5-10g; the hydrothermal activation conditions are: the temperature of the blast drying oven is 200-240 ℃, and the activation time is 600-900min; the drying temperature is 50-90 ℃, and the crushed materials are sieved by a 60-200 mesh sieve.
As an improvement of the technical scheme, in the step (4), the alkaline thermal activated sludge biochar KSBC and the magnesium chloride MgCl 2 Ferric chloride FeCl 3 ·6H 2 The volume ratio of the O solution is 2.5-10g:50-100mL; at the 50-100mL of MgCl 2 Ferric chloride FeCl 3 ·6H 2 MgCl in solution of O 2 Is 2.5-10g FeCl 3 ·6H 2 The mass of O is 2.5-10g; the hydrothermal activation conditions are: the temperature of the blast drying oven is 200-240 ℃, and the activation time is 600-900min; the drying temperature is 50-90 ℃, and the crushed materials are sieved by a 60-200 mesh sieve.
An alkali/bi-metallic brine heat activated sludge biochar made by any of the methods as described above.
An application of alkali/bimetallic brine heat activated sludge biochar in removing norfloxacin in water, comprising the following steps: adding sludge biochar SBC, alkali hydrothermal activated sludge biochar KSBC, bimetal salt water hydrothermal activated sludge biochar MSBC and alkali/bimetal salt water hydrothermal activated sludge biochar KMSBC serving as adsorbents into an aqueous solution containing norfloxacin, and filtering when the concentration of the norfloxacin solution is not changed after the balance is achieved, so as to obtain a purified solution.
As the optimization of the technical scheme, the application of the alkali/bimetallic brine heat activated sludge biochar in removing norfloxacin in water further comprises part or all of the following technical characteristics:
as an improvement of the technical scheme, the concentration of the norfloxacin in the norfloxacin-containing solution is 5-100mg/L, pH and is 2-12; the adding amount of the adsorbent is 0.1-0.4g/L.
As an improvement of the technical scheme, the temperature of the adsorption process is controlled to be 15-35 ℃.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects: the method for efficiently removing the norfloxacin in the water by using the alkali/bimetallic salt water heat activated sludge biochar as the adsorbent can effectively reduce the environmental pollution caused by the norfloxacin and realize the recycling of municipal sludge. Meanwhile, the biochar prepared by the method has stronger safety and stronger magnetic separation capability, and can realize high-efficiency separation and regeneration with water.
(1) The KMSBC has strong norfloxacin removal capacity, and the removal rate of the KMSBC with the dosage of 0.3g/L to norfloxacin with the concentration of 10mg/L is close to 100%. The maximum adsorption capacity of KMSBC to norfloxacin can reach 68.5mg/g at the concentration of 100mg/L and the projection temperature of 35 ℃.
(2) Compared with other technologies (photocatalysis, advanced oxidation, microbial degradation and the like), the method for removing norfloxacin in water by using the alkali/bimetallic brine heat activated sludge biochar as an adsorbent has the advantages of high cost efficiency, simplicity in operation, environmental protection and large-scale application prospect.
(3) The alkali/bimetallic salt water heat activated sludge biochar prepared by the method can realize the resource utilization of municipal sludge and the efficient removal of norfloxacin in water, has high safety and easy separation and regeneration capacity, and has low use cost.
The foregoing description is only an overview of the present invention, and is intended to be implemented in accordance with the teachings of the present invention in order that the same may be more clearly understood and appreciated, as well as the other objects, features and advantages of the present invention, as described in detail below in connection with the preferred embodiments.
Drawings
In order to more clearly illustrate the technical solution of the embodiments of the present invention, the drawings of the embodiments will be briefly described below.
FIG. 1 (a) shows the removal rate of norfloxacin at a dose of 0.3g/L for 0-1440min for 10mg/L in KMSBC;
FIG. 1 (b) shows the relationship between the concentration of norfloxacin and the reaction temperature and the adsorption capacity of KMSBC as an adsorbent;
FIG. 2 (a) is a graph showing adsorption capacity of KMSBC to 10mg/L norfloxacin as a function of pH change of a solution;
FIG. 2 (b) is the effect of NaCl at a concentration of 1-100mmol/L on the ability of KMSBC to adsorb norfloxacin at a concentration of 10 mg/L;
FIG. 2 (c) shows CaCl having a concentration of 1-100mmol/L 2 Influence on the ability of KMSBC to adsorb norfloxacin at a concentration of 10 mg/L;
FIG. 2 (d) is the effect of humic acid at a concentration of 1-10mg/L on the ability of KMSBC to adsorb norfloxacin at a concentration of 10 mg/L;
FIG. 3 (a) shows the leaching concentration of Fe in KMSBC at different pH values;
FIG. 3 (b) shows the ability of KMSBC to regenerate adsorbed norfloxacin;
FIG. 4 (a) is an SEM map of KMSBC;
FIG. 4 (b) is an XRD pattern of KMSBC;
FIG. 4 (c) is a FTIR profile of KMSBC;
FIG. 4 (d) is a Zeta potential diagram of KMSBC;
FIG. 4 (e) is a specific surface area and pore distribution profile of KMSBC;
fig. 4 (f) is a KMSBC hysteresis curve map.
Detailed Description
The following detailed description of the invention, which is a part of this specification, illustrates the principles of the invention by way of example, and other aspects, features, and advantages of the invention will become apparent from the detailed description.
Example one: the municipal sludge is dried in a 70 ℃ oven to constant weight and then transferred into a high temperature tube furnace (N) 2 The flow rate is 0.5L/min, the heating rate is 10 ℃/min), pyrolyzing for 120min at 700 ℃, grinding and sieving with a 100-mesh sieve to obtain the sludge biochar SBC. Transferring SBC (mass is 5.0 g) into a reaction kettle containing 60mL of KOH with 2.5g dissolved therein, performing hydrothermal activation at 220 ℃ for 720min, drying in a 70 ℃ oven until the weight is constant, grinding, and sieving with a 100-mesh sieve to obtain the alkali hydrothermal activated sludge biochar KSBC. SBC with a mass of 5.0g was charged with MgCl containing 60mL 2 (mass 10 g) and FeCl 3 ·6H 2 O (mass 5 g) mixed solution in a reaction kettle, at 220 DEG CAnd performing hydrothermal activation for 720min under the piece, then placing the piece in a 70 ℃ oven for drying to constant weight, grinding and sieving with a 100-mesh sieve to obtain the bimetal brine heat activated sludge biochar MSBC. And taking KSBC as a precursor, and performing other operations in the same way as the preparation process of MSBC to obtain the alkali/bimetallic brine heat activated sludge biochar KMSBC.
Example two: KMSBC (KMSBC) of 0.3g/L was added to norfloxacin solution of 100mL and 10mg/L concentration, adsorption experiments were performed in a constant temperature shaking oven (160 rmp) of 25 ℃ and samples were taken at a set time (0-1440 min), the residual concentration of norfloxacin was measured at λ=273 nm using an ultraviolet spectrophotometer, and the removal rate of norfloxacin at different times was calculated.
As can be seen from FIG. 1 (a), KMSBC can realize rapid and efficient removal of the norfloxacin, the removal rate of the norfloxacin exceeds 80% in 40min, and the highest removal rate of the norfloxacin can reach 94.8% in 1440 min.
Example three: KMSBC at a dose of 0.3g/L was added to norfloxacin solutions having volumes of 100mL and concentrations of 5, 10, 20, 40, 60, 80 and 100mg/L, respectively, and then placed in a constant temperature shaking oven (160 rmp) at 15 ℃, 25 ℃ and 35 ℃, and at equilibrium, the residual concentration of norfloxacin was determined at λ=273 nm using an ultraviolet spectrophotometer.
As can be seen from fig. 1 (b), the adsorption capacity of norfloxacin by KMSBC increases with increasing concentration of norfloxacin and increasing reaction temperature. The maximum adsorption capacity of norfloxacin at 35 ℃ can reach 68.5mg/g.
Example four: KMSBC with the dosage of 0.3g/L is added into norfloxacin solution with the volume of 100mL, the concentration of 10mg/L and the pH value of 2-11 (the pH value of the solution is regulated by using 0.1mol/L HCl/NaOH), the solution is placed in a constant temperature shaking box (160 rmp) at 25 ℃ for adsorption experiments, and at the time of adsorption balance, the residual concentration of the norfloxacin is measured at the lambda=273 nm by using an ultraviolet spectrophotometer, the leaching concentration of Fe is measured by using an atomic absorption spectrophotometer, and the adsorption capacity of the KMSBC on the norfloxacin and the safety of biochar are explored under different pH conditions.
As can be seen from FIG. 2 (a), the adsorption capacity of KMSBC was not greatly affected at a pH of 2-8, and was maximized at a pH of 5 (32.9 mg/g). KMSBC's ability to adsorb norfloxacin is significantly inhibited when the solution pH is > 9. From fig. 3 (a), it can be known that only when the pH of the solution is 2, the leaching concentration of Fe in KMSBC is higher than the limit value of GB 5749-2006, and under other pH conditions, the leaching concentration of Fe is far lower than the limit value of GB 5749-2006, which indicates that the alkali/bimetallic brine heat activated sludge biochar prepared by the present invention has higher safety.
Example five: KMSBC was added at a dose of 0.3g/L to 100mL of a concentration of 10mg/L and containing NaCl (1-100 mmol/L) and CaCl, respectively 2 And (2) placing the norfloxacin solution (1-100 mmol/L) and humic acid (1-10 mg/L) in a constant temperature shaking box (160 rmp) at 25 ℃ for adsorption experiments, and measuring the residual concentration of the norfloxacin at lambda=273 nm by using an ultraviolet spectrophotometer when adsorption is balanced, so as to evaluate the influence of coexisting inorganic ions and organic matters on the norfloxacin adsorption capacity of KMSBC.
As can be seen from FIGS. 2 (b) -2 (d), naCl and CaCl 2 Inhibition of KMSBC's ability to adsorb norfloxacin increases with increasing concentration, wherein inhibition of NaCl is substantially negligible, caCl 2 Has a stronger inhibitory effect than NaCl. Humic acid has a certain enhancement effect on the ability of KMSBC to adsorb norfloxacin.
Example six: KMSBC at a dose of 0.3g/L was added to a norfloxacin solution having a volume of 500mL and a concentration of 10mg/L, and adsorption experiments were performed in a constant temperature shaking oven at 25℃and absorbance of norfloxacin was measured at λ=273 nm using an ultraviolet spectrophotometer at the time of reaction equilibrium. The KMSBC having reached the adsorption equilibrium was magnetically separated, regenerated with ultrasonic waves (500W) and NaOH (0.1 mol/L) for 120min, treated with ultrapure water in a control group, and repeatedly performed 5 times, and the regeneration adsorption capacity of KMSBC was measured.
As can be seen from fig. 3 (b), naOH treatment can maintain a stable adsorption capacity (up to 99.2% or more of the initial use) of KMSBC during subsequent recycling, as compared to ultrapure water and ultrasonic treatment.
The SEM profile of KMSBC of fig. 4 (a) shows that it presents a rough surface and a distinct branching structure, which can provide a more abundant active site for norfloxacin adsorption.
From the XRD pattern of fig. 4 (b), it can be seen that KMSBC presents characteristic peaks of amorphous carbon near 2θ=20°, and KMSBC has a high graphitization degree to facilitate pi-pi conjugation with norfloxacin, and magnetic γ -Fe 2 O 3 The formation of (2) is favorable for complexation with norfloxacin and recovery and regeneration after adsorption, and the appearance of magnesium hydroxide diffraction peaks indicates that magnesium is loaded on the surface of KMSBC.
From the FTIR spectrum of fig. 4 (C), the functional groups on the KMSBC surface mainly include-OH, c= C, C-O, fe-O and Mg-O, confirming that Fe and Mg are loaded on the KMSBC surface in accordance with XRD analysis. These functional groups on the surface of KMSBC are capable of hydrogen bonding, pi-pi conjugation and complexation with norfloxacin to enhance its adsorption of norfloxacin.
As can be seen from the nitrogen adsorption and desorption isotherm and the pore distribution in FIG. 4 (d), the pores of KMSBC are mainly of mesoporous structure, which is beneficial to the transportation and adsorption of macromolecular norfloxacin.
As can be seen from the zeta potential of fig. 4 (e), the zeta potential of KMSBC decreases with increasing pH, with a zero potential point of ph=2.27. When the solution pH is <2.27, KMSBC surfaces are protonated and positively charged; when the solution pH >2.27, KMSBC surfaces were negatively charged.
From the hysteresis curves of fig. 4 (f), KMSBC has certain magnetic sensitivity, and after adsorption, magnetic separation from water can be achieved, and after NaOH regeneration, the KMSBC can be used for continuously removing norfloxacin in water.
The present invention can be realized by the respective raw materials listed in the present invention, and the upper and lower limits and interval values of the respective raw materials, and the upper and lower limits and interval values of the process parameters (such as temperature, time, etc.), and examples are not listed here.
While the invention has been described with respect to the preferred embodiments, it will be understood that the invention is not limited thereto, but is capable of modification and variation without departing from the spirit of the invention, as will be apparent to those skilled in the art.
Claims (5)
1. The preparation method of the alkali double-metal salt water heat activated sludge biochar for removing norfloxacin in water is characterized by comprising the following steps of:
(1) Preparation of sludge biochar: washing municipal sludge with ultrapure water, drying to constant weight, pyrolyzing, grinding and sieving to obtain sludge biochar SBC;
(2) Preparation of alkaline water thermal activated sludge biochar: placing the sludge biochar SBC obtained in the step (1) in KOH solution, performing hydrothermal activation, washing with ultrapure water, centrifuging, drying, grinding and sieving to obtain alkaline water-activated sludge biochar KSBC;
(3) Preparation of a bimetal salt water heat activated sludge biochar: adding the sludge biochar SBC prepared in the step (1) into MgCl containing magnesium chloride 2 Ferric chloride FeCl 3 ·6H 2 Placing the mixed solution of O in a blast drying oven for hydrothermal activation, drying, grinding and sieving to obtain sludge biochar MSBC thermally activated by the bimetallic brine;
(4) Preparation of alkali/bimetallic brine heat activated sludge biochar: adding the KSBC prepared in the step (2) into MgCl containing magnesium chloride 2 Ferric chloride FeCl 3 ·6H 2 Placing the mixed solution of O in a blast drying oven for hydrothermal activation, drying, grinding and sieving to obtain alkali/bimetallic brine heat activated sludge biochar KMSBC;
in the step (1), the drying temperature is 50-90 ℃; the pyrolysis condition is that the flow rate of nitrogen is 0.3-0.6L/min, the heating rate is 5-15 ℃/min, and the pyrolysis is continuously carried out for 60-120min at 400-800 ℃; grinding and sieving with 60-200 mesh sieve; in the step (2), the mass ratio of potassium hydroxide KOH to sludge biochar SBC=5g:2.5-10 g, and the concentration of KOH solution is 25-200g/L; the hydrothermal activation conditions are: the forced air drying temperature is 200-240 ℃, and the activation time is 600-900min; drying at 50-90deg.C, grinding, and sieving with 60-200 mesh sieve; in the step (3), the mass of the sludge biochar SBC and the mass of the magnesium chloride MgCl 2 Ferric chloride FeCl 3 ·6H 2 The volume ratio of the O solution is 2.5-10g:50-100mL; at the 50-100mL of MgCl 2 Ferric chloride FeCl 3 ·6H 2 MgCl in solution of O 2 Is 2.5-10g FeCl 3 ·6H 2 The mass of O is 2.5-10g; the hydrothermal activation conditions are: the temperature of the blast drying oven is 200-240 ℃, and the activation time is 600-900min; drying at 50-90deg.C, grinding, and sieving with 60-200 mesh sieve; in the step (4), the alkaline water thermally activated sludge charcoal KSBC and the magnesium chloride MgCl 2 Ferric chloride FeCl 3 ·6H 2 The volume ratio of the O solution is 2.5-10g:50-100mL; at the 50-100mL of MgCl 2 Ferric chloride FeCl 3 ·6H 2 MgCl in solution of O 2 Is 2.5-10g FeCl 3 ·6H 2 The mass of O is 2.5-10g; the hydrothermal activation conditions are: the temperature of the blast drying oven is 200-240 ℃, and the activation time is 600-900min; the drying temperature is 50-90 ℃, and the crushed materials are sieved by a 60-200 mesh sieve.
2. An alkali/bimetallic brine heat activated sludge biochar, characterized in that: the alkali/bi-metallic salt water heat activated sludge biochar is prepared by the method of claim 1.
3. The application of the alkali/bimetallic brine heat activated sludge biochar in removing norfloxacin in water is characterized by comprising the following steps: adding sludge biochar SBC, alkali hydrothermal activated sludge biochar KSBC, bimetal salt water hydrothermal activated sludge biochar MSBC and alkali/bimetal salt water hydrothermal activated sludge biochar KMSBC serving as adsorbents into an aqueous solution containing norfloxacin, filtering after the concentration of the norfloxacin is not changed any more until the adsorption process reaches equilibrium, and obtaining a purified solution.
4. Use of an alkali/bimetallic brine heat activated sludge biochar in the removal of norfloxacin in water as claimed in claim 3, characterized in that: the concentration of norfloxacin in the norfloxacin-containing solution is 5-100mg/L, pH and is 2-12; the adding amount of the adsorbent is 0.1-0.4g/L.
5. Use of the alkali/bimetallic brine heat activated sludge biochar in the removal of norfloxacin in water as claimed in claim 4, characterized by: the temperature of the adsorption process is controlled to be 15-35 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111485720.8A CN114160098B (en) | 2021-12-07 | 2021-12-07 | Preparation method of alkali/bimetallic salt water heat activated sludge biochar for removing norfloxacin in water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111485720.8A CN114160098B (en) | 2021-12-07 | 2021-12-07 | Preparation method of alkali/bimetallic salt water heat activated sludge biochar for removing norfloxacin in water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114160098A CN114160098A (en) | 2022-03-11 |
| CN114160098B true CN114160098B (en) | 2023-09-19 |
Family
ID=80484045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111485720.8A Active CN114160098B (en) | 2021-12-07 | 2021-12-07 | Preparation method of alkali/bimetallic salt water heat activated sludge biochar for removing norfloxacin in water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114160098B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114797811A (en) * | 2022-04-18 | 2022-07-29 | 武汉理工大学 | MoS applied to tetracycline removal in water 2 Preparation method of hydrothermal activated sludge biochar |
| CN115722194A (en) * | 2022-12-07 | 2023-03-03 | 江汉大学 | Nitric acid modified lotus leaf carbon adsorption material and preparation method and application thereof |
| CN116440866B (en) * | 2023-03-13 | 2023-09-22 | 武汉工程大学 | Preparation method and application of three-dimensional spongy porous heavy metal ion adsorbent based on activated eggshells |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106277166A (en) * | 2016-08-31 | 2017-01-04 | 昆明理工大学 | A kind of modification biological charcoal is utilized to remove the method for antibiotic in breeding wastewater |
| CN110227416A (en) * | 2019-06-24 | 2019-09-13 | 武汉理工大学 | A kind of preparation and its application in fluoroquinolone antibiotics removal in water of iron zinc and phosphoric acid modification sludge organism charcoal |
| CN110801811A (en) * | 2019-11-27 | 2020-02-18 | 湖南大学 | Mg/Fe oxide modified biochar nanocomposite and preparation method thereof |
| CN111871369A (en) * | 2020-07-10 | 2020-11-03 | 武汉理工大学 | Preparation method of potassium hydroxide modified magnetic corncob biochar composite material applied to removal of imidacloprid in water |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190099743A1 (en) * | 2017-10-04 | 2019-04-04 | Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College | Catalyst Composition Including a Biochar, and Related Methods |
-
2021
- 2021-12-07 CN CN202111485720.8A patent/CN114160098B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106277166A (en) * | 2016-08-31 | 2017-01-04 | 昆明理工大学 | A kind of modification biological charcoal is utilized to remove the method for antibiotic in breeding wastewater |
| CN110227416A (en) * | 2019-06-24 | 2019-09-13 | 武汉理工大学 | A kind of preparation and its application in fluoroquinolone antibiotics removal in water of iron zinc and phosphoric acid modification sludge organism charcoal |
| CN110801811A (en) * | 2019-11-27 | 2020-02-18 | 湖南大学 | Mg/Fe oxide modified biochar nanocomposite and preparation method thereof |
| CN111871369A (en) * | 2020-07-10 | 2020-11-03 | 武汉理工大学 | Preparation method of potassium hydroxide modified magnetic corncob biochar composite material applied to removal of imidacloprid in water |
Non-Patent Citations (2)
| Title |
|---|
| 张涵瑜 ; 王兆炜 ; 高俊红 ; 朱俊民 ; 谢超然 ; 谢晓芸 ; .芦苇基和污泥基生物炭对水体中诺氟沙星的吸附性能.环境科学.(第02期),全文. * |
| 彭小明等.竹炭表面改性对两种抗生素吸附性能的影响.东南大学学报（自然科学版）.2014,第44卷(第6期),第1271-1277页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114160098A (en) | 2022-03-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114160098B (en) | Preparation method of alkali/bimetallic salt water heat activated sludge biochar for removing norfloxacin in water | |
| Foroutan et al. | Cadmium ion removal from aqueous media using banana peel biochar/Fe3O4/ZIF-67 | |
| Yin et al. | Novel melamine modified metal-organic frameworks for remarkably high removal of heavy metal Pb (II) | |
| Liu et al. | Cerium-doped MIL-101-NH2 (Fe) as superior adsorbent for simultaneous capture of phosphate and As (V) from Yangzonghai coastal spring water | |
| Cui et al. | Removal of nitrate and phosphate by chitosan composited beads derived from crude oil refinery waste: Sorption and cost-benefit analysis | |
| CN111203180B (en) | Magnetic biochar composite adsorbent and preparation method and application thereof | |
| Yin et al. | Sulfur-functional group tunning on biochar through sodium thiosulfate modified molten salt process for efficient heavy metal adsorption | |
| He et al. | N-doped activated carbon for high-efficiency ofloxacin adsorption | |
| Bishayee et al. | Strategic management of nitrate pollution from contaminated water using viable adsorbents: An economic assessment-based review with possible policy suggestions | |
| CN108079949B (en) | Method for removing lead in water body by using magnetic pig manure biochar | |
| CN112169755A (en) | Preparation method of hydrothermally synthesized zinc chloride activated magnetic sludge biochar applied to tetracycline removal in water | |
| Doan et al. | Comparative study on adsorption of cationic and anionic dyes by nanomagnetite supported on biochar derived from Eichhornia crassipes and Phragmites australis stems | |
| CN113634228B (en) | Sludge biochar loaded magnesium-iron oxide composite material for removing lead and cadmium in water and preparation method and application thereof | |
| Nirmala et al. | Removal of toxic metals from wastewater environment by graphene-based composites: A review on isotherm and kinetic models, recent trends, challenges and future directions | |
| CN105289529A (en) | Preparation method of MOF type efficient cheap adsorbent | |
| Elkhlifi et al. | Lanthanum hydroxide engineered sewage sludge biochar for efficient phosphate elimination: Mechanism interpretation using physical modelling | |
| CN113145068A (en) | Rice straw biochar impregnated with zinc chloride and preparation method thereof | |
| Gao et al. | Preparation of spiramycin fermentation residue derived biochar for effective adsorption of spiramycin from wastewater | |
| CN114768779A (en) | Preparation method of nitrogen-doped magnetic iron sludge biochar applied to tetracycline removal in water | |
| Ren et al. | Enhanced removal of ammonia nitrogen from rare earth wastewater by NaCl modified vermiculite: Performance and mechanism | |
| CN109304143B (en) | Preparation method of iron-loaded mesoporous carbon material, product and application thereof | |
| Isaac et al. | Sequestration of Ni (II) and Cu (II) using FeSO4 modified Zea mays husk magnetic biochar: Isotherm, kinetics, thermodynamic studies and RSM | |
| Wu et al. | Electrified nanohybrid filter for enhanced phosphorus removal from water | |
| CN105217715B (en) | A kind of method that absorbent charcoal material removes processing antibiotic sulfacetamide | |
| Bai et al. | Synthesis of microporous aromatic framework with scholl-coupling reaction for efficient uranium (VI) capture |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |