CN115212847A - Preparation method of novel adsorbent for synchronously removing heavy metals and antibiotics - Google Patents

Preparation method of novel adsorbent for synchronously removing heavy metals and antibiotics Download PDF

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CN115212847A
CN115212847A CN202210023281.7A CN202210023281A CN115212847A CN 115212847 A CN115212847 A CN 115212847A CN 202210023281 A CN202210023281 A CN 202210023281A CN 115212847 A CN115212847 A CN 115212847A
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concentration
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mixed solution
heavy metal
antibiotics
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陈波
李娟�
潘学军
冯翔
蓝珊琳
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Kunming University of Science and Technology
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • 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
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
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    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/34—Organic compounds containing oxygen
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/345—Phenols
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    • C02F2101/36—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen

Abstract

The invention discloses a preparation method of a novel adsorbent for synchronously removing heavy metals and antibiotics, relates to the field of water treatment, and aims to solve the problem that the conventional novel adsorbent for synchronously removing heavy metals and antibiotics cannot be well removed. The following scheme is proposed, which comprises the following steps: first, fe is prepared 3 O 4 : 2g of FeCl was weighed 2 ·4H 2 O，5.2gFeCl 3 ·6H 2 O in a three-neck flask, 25mL of deionized water is added, the solution is stirred at normal temperature to be transparent for standby, 0.85mL of concentrated hydrochloric acid is added, and 250mL1.5molL-1 NaOH is added into the three-neck flask by a separating funnel under the stirring condition. The invention is non-toxic and environment-friendly, and prepares Fe through simple mixing and crosslinking 3 O 4 /GO‑SA‑Fe 3 The functional material corresponds to specific adsorption sites aiming at different pollutants, and is beneficial to removing the composite pollutants in the water body.

Description

Preparation method of novel adsorbent for synchronously removing heavy metals and antibiotics
Technical Field
The invention relates to the field of water treatment, in particular to a preparation method of a novel adsorbent for synchronously removing heavy metals and antibiotics.
Background
At present, most of adsorption researches only focus on the removal effect of a single pollutant in a water body, and only a few researches report the application of an adsorption method in antibiotic and heavy metal combined pollution. However, most of the environmental problems are caused by a plurality of pollutants together, and different from single pollution, the environmental problems caused by compound pollution can be more complicated and serious, and because the feed of the farm contains antibiotics and trace elements which are simultaneously used as growth promoters, the compound pollution condition of the antibiotics and heavy metals needs to be considered in the process of treating the culture wastewater.
Fe 3 O 4 Magnetic nanoparticles are a novel functional material and are of great interest to people due to their good biocompatibility, remarkable magnetic properties, good mechanical properties, high surface activity and low cost, fe 3 O 4 The nano particles have strong specific surface area and super magnetic compliance, fe 3 O 4 The Fe-based adsorption material can be used as a carrier of a plurality of functional structures, and meanwhile, the magnetic separation performance of the Fe-based adsorption material can realize the rapid separation of the adsorbent and the water body, thereby avoiding the high energy consumption caused by the solid-liquid separation of the adsorbent and the polluted water body, avoiding the secondary pollution caused by the difficulty in recycling the adsorbent after being put into the water body, and being not negligible and being bare Fe 3 O 4 The magnetic nanoparticles are easily oxidized in air and, moreover, due to Fe 3 O 4 The magnetic nano particles have high surface energy and are easy to agglomerate, and Fe 3 O 4 Once the magnetic nano particle aggregate is formed, the total specific surface area is sharply reduced, and the adsorption efficiency is reduced, however, scientific researches show that the surface modified Fe is 3 O 4 The nanoparticles will have higher dispersibility and stability, and the presence of phenolic beta-diketones in the molecular structure of antibiotics can be related to Fe reported in the past for the treatment of antibiotic-containing wastewater 3 O 4 Fe (III) in (A) forms stable complexes.
Graphene oxide, as a graphene derivative, not only maintains a thin-layer two-dimensional nanostructure and a large theoretical specific surface area of graphene, but also has a large number of oxygen-containing functional groups such as hydroxyl groups, epoxy groups and carboxyl groups on a base surface and edges, which provides a large number of active sites for the modification of GO and the adsorption of pollutants, and meanwhile, GO has the characteristics of surface hydrophobicity, pi-pi interaction, good hydrophilicity, high negative charge density, and easy large-scale synthesis from a large number of natural graphites through an oxidation method and a stripping method, so GO is considered to be the most promising adsorbent for adsorbing heavy metal ions and organic pollutants.
Sodium alginate is a linear natural polysaccharide high-molecular polymer, which is composed of beta-D-mannuronic acid (M section) and alpha-L-guluronic acid (G section) connected by 1-4 glycosidic bonds and by homo-block structures (MM and GG sections) and/or hetero-block structures (MG and GM sections) in different proportions, is more and more concerned by people due to good biocompatibility, nontoxicity and biodegradability and is widely applied to food, medicine, cosmetics, printing and dyeing, paper making, mining, rubber and other fields, each sugar monomer of a sodium alginate molecular chain contains free carboxyl, has active property, can exchange with metal ions and has Fe ion exchange effect 3+ And Cu 2+ The selective exchange function of the sodium alginate gel balls and the spinning fibers is particularly outstanding, so the calcium alginate gel balls and the spinning fibers can be prepared by utilizing the crosslinking function, the sodium alginate is one of anionic polyelectrolytes, and free carboxyl in a sugar monomer can be complexed with metal ions, so that the metal ions or organic dyes in a wastewater solution can be adsorbed by utilizing the characteristic, and the sodium alginate has important application value in the aspect of wastewater treatmentTherefore, the alginic acid composite material is prepared, and specific adsorption sites corresponding to two different pollutants are introduced, so that competitive adsorption is avoided, and the two pollutants can be adsorbed on the surface of the adsorbent synchronously; meanwhile, the interaction between the two pollutants can improve the mutual loading capacity, thereby achieving the purpose of 'synergy'.
Therefore, how to well remove the novel adsorbents of heavy metals and antibiotics simultaneously is a technical problem which needs to be solved by the technical personnel in the field at present.
Disclosure of Invention
Objects of the invention
In view of the above, the present invention aims to provide a preparation method of a novel adsorbent for synchronously removing heavy metals and antibiotics, so as to achieve the three purposes: first aim at comparing Fe 3 O 4 -SA-Fe 3+ 、GO-SA-Fe 3+ 、Fe 3 O 4 /GO-SA-Fe 3+ Determining the optimal material by the adsorption effect of the three materials; the second purpose is to provide an optimum ratio of Fe 3 O 4 /GO-SA-Fe 3+ A material preparation method; the third objective is to explore Fe 3 O 4 /GO-SA-Fe 3+ The material being in a monomer system (TC, cu) 2+ Solution) and composite systems (TC-Cu) 2+ 、Cu 2+ -TC solution) and the influence of initial concentration and pH on the adsorption.
(II) technical scheme
In order to achieve the technical purpose, the invention provides a preparation method of a novel adsorbent for synchronously removing heavy metals and antibiotics, which comprises the following steps:
the first object of the present invention is a process for the preparation of a composition comprising the following steps:
first, fe is prepared 3 O 4 : weighing 2gFeCl 2 ·4H 2 O，5.2gFeCl 3 ·6H 2 Adding 25mL of deionized water into a three-neck flask, stirring the solution at normal temperature to be transparent for standby, then adding 0.85mL of concentrated hydrochloric acid, adding 250mL1.5mol of L-1 NaOH into the three-neck flask by using a separating funnel under the condition of stirring, wherein the process is carried out in a water bath kettle at the temperature of 80 ℃, and continuously stirringStirring for 30min, cooling the solution, and separating Fe with the aid of magnet 3 O 4 Washing the granules with deionized water, measuring pH of the supernatant, when neutral, washing, and drying in a cooling dryer for 2 days to obtain dry Fe 3 O 4 ；
Then respectively weighing a certain amount of GO and sodium alginate, uniformly dispersing the GO and sodium alginate in deionized water by ultrasonic to obtain a solution 1 and a solution 2, and weighing a certain amount of the prepared Fe 3 O 4 Pouring into the solution 1, continuing to perform ultrasonic treatment to uniformly mix the solution to obtain a solution 3, and then weighing a certain amount of the prepared Fe 3 O 4 Uniformly dispersing the sodium alginate powder in deionized water by ultrasonic to obtain a solution 4, then respectively weighing a certain amount of sodium alginate powder, pouring the sodium alginate powder into the solutions 2, 3 and 4, and mechanically stirring for 24 hours to obtain a uniformly mixed solution.
Respectively preparing FeCl with certain concentration 3 ·6H 2 O solution to obtain solutions 5, 6 and 7, dripping the solutions 2, 3 and 4 into the solutions 5, 6 and 7 respectively by using a syringe, standing for 24h, performing crosslinking, and washing excessive Fe by using deionized water 3+ And placing the mixture in a freeze dryer to dry the mixture for later use to obtain a target material: fe 3 O 4 /GO-SA-Fe 3+ 、GO-SA-Fe 3+ 、Fe 3 O 4 -SA-Fe 3+ 。
Preferably, fe 3 O 4 /GO-SA-Fe 3+ Fe added in material preparation 3 O 4 And GO is 0.1g and 0.05g respectively; GO-SA-Fe 3+ The mass of GO added in the preparation of the material is 0.05g; fe 3 O 4 -SA-Fe 3+ Fe added in material preparation 3 O 4 The mass was 0.1g.
Preferably, 1g of sodium alginate powder is weighed to prepare a 1% sodium alginate solution.
Preferably, feCl 3 ·6H 2 Weighing 2g of O to prepare Fe with the volume concentration of 2 percent 3+ And (3) solution.
The second object of the present invention is achieved by a process for obtaining Fe 3 O 4 /GO-SA-Fe 3+ The optimal material proportion is realized by adopting a variable control method, and the application is the adsorption of the material in monomer system antibiotics or heavy metal copper ion water bodies.
Firstly, preparing tetracycline hydrochloride solution with a certain concentration to be treated and heavy metal copper ion solution.
The effect of the amount of GO on the adsorption experiment was explored: fixation of Fe 3 O 4 The mass of the catalyst is 0.1g, the adding mass of GO is respectively changed into 0g, 0.05g, 0.1g, 0.2g and 0.3g according to the requirement, the volume percentage concentration of SA is 1 percent, and Fe 3+ 2% by volume.
Exploration of Fe 3 O 4 Effect of amount on adsorption experiments: the fixed GO has a mass of 0.1g, and Fe is changed according to requirements 3 O 4 0g, 0.05g, 0.1g, 0.2g, 0.3g of SA, a F volume percentage concentration of 1%, fe 3+ 2% by volume.
The effect of SA on adsorption experiments was explored: the mass of fixed GO is 0.1g 3 O 4 0.1g, by changing SA (0.5, 1, 1.5% w/V), 2% by volume of Fe 3+ 。
Exploration of Fe 3+ Effect on adsorption experiments: the fixed GO mass is 0.1g 3 O 4 Has a mass of 0.1g, a volume percentage concentration of SA of 0.5%, fe 3+ The volume percentage concentrations of (A) are respectively 1%, 2%, 3%, 4% and 5%.
And adding 0.01g of the prepared material into a tetracycline hydrochloride solution or a heavy metal copper ion solution with a certain concentration to be treated to form suspended matters, adjusting the pH value to be 6, adjusting the volume of the solution to be 30mL, and oscillating the solution in a shaking table for several hours to ensure that the surface of the material achieves adsorption balance for pollutants in water.
The third object of the present invention is achieved by the following method, resulting in optimized Fe 3 O 4 /GO-SA-Fe 3+ Materials, investigating TC-Cu at different concentrations 2+ 、Cu 2+ -TC solution and adsorption effect at different pH, comprising the steps of:
in a tetracycline hydrochloride solution with a certain concentration to be treated0.01g of Fe was added 3 O 4 /GO-SA-Fe 3+ The material forms suspended matters, and after the pH value is adjusted to the required value, the suspended matters are vibrated for a plurality of hours in a shaking table, so that the surface of the material can achieve adsorption balance for pollutants in water.
Adding 0.01g of Fe into a heavy metal solution with a certain concentration to be treated 3 O 4 /GO-SA-Fe 3+ The material forms suspended matters, and after the pH value is adjusted to the required value, the suspended matters are vibrated for a plurality of hours in a shaking table, so that the surface of the material can achieve adsorption balance for pollutants in water.
Adding 0.01g of Fe into a composite solution of tetracycline hydrochloride and heavy metal copper with a certain concentration to be treated 3 O 4 /GO-SA-Fe 3+ The material forms suspended matter, after the pH value is adjusted to the required value, the suspended matter is vibrated in a shaking table for a plurality of hours, so that the surface of the material can achieve adsorption balance for pollutants in water.
Preferably, the concentration of tetracycline hydrochloride in the monomer system is 15mg/L, and the volume is 30mL;
preferably, the concentration of heavy metal copper in the monomer system is 20mg/L, and the volume is 30mL;
preferably, the concentration of the tetracycline hydrochloride is 15mg/L, the concentration of the heavy metal copper is 20mg/L, and the volume is 30mL.
According to the technical scheme, the method has the following beneficial effects:
1: the invention is non-toxic and environment-friendly, and prepares Fe through simple mixing and crosslinking 3 O 4 /GO-SA-Fe 3+ The functional material corresponds to specific adsorption sites aiming at different pollutants, is beneficial to removing the composite pollutants in the water body, and utilizes the complexation between the tetracycline hydrochloride and the heavy metal copper, thereby improving the adsorption quantity of the tetracycline hydrochloride and the heavy metal copper in the composite system.
2: the invention is through Cu 2+ Complexation with TC promotes the control of Cu 2+ Adsorption of (C), and Cu 2+ The promoting effect and the inhibiting effect exist in the adsorption process at the same time, and finally the two effects are superposed, so that the novel heavy metal and antibiotic adsorbent can be well and synchronously removed.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 shows Fe obtained in the preparation method of the novel adsorbent for synchronously removing heavy metals and antibiotics 3 O 4 /GO-SA-Fe 3+ Preparation of SEM image in comparison with Fe 3 O 4 、SA-Fe 3+ Schematic after SEM picture of (a).
FIG. 2 shows Fe prepared in FIG. 1 3 O 4 /GO-SA-Fe 3+ Preparation of TEM image versus SA-Fe 3+ Schematic after TEM image of (a).
FIG. 3 is a graphical representation of the comparison of the adsorption capacities of different materials.
Fig. 4 is a schematic diagram of the adsorption capacity comparison after material optimization.
FIG. 5 shows Cu remaining under different pH conditions 2+ Adsorption capacity of (2) and Cu 2+ The effect of concentration and initial pH on TC adsorption and the remaining Cu adsorption capacity under different pH conditions are plotted.
Detailed Description
The following description is merely exemplary in nature and is not intended to limit the present disclosure, application, or uses. It should be understood that throughout the drawings, identical or similar reference numerals indicate identical or similar parts and features. The drawings are only schematic representations of the concepts and principles of embodiments of the disclosure, and do not necessarily show specific dimensions and proportions of the various embodiments of the disclosure. Certain features that are part of a particular figure may be exaggerated in order to illustrate relevant details or structures of embodiments of the present disclosure.
Referring to FIGS. 1-5:
example one
A preparation method of a novel adsorbent for synchronously removing heavy metals and antibiotics comprises the following steps:
step one, mixing the medicines, and respectively adding 0.1g of Fe 3 O 4 Dissolving GO in a beaker filled with deionized water, then carrying out ultrasonic dispersion, adding 0.5g of SA powder, and mechanically stirring to uniformly mix the SA powder and the GO to obtain a mixed solution;
step two, weighing 1g FeCl 3 ·6H 2 O powder prepared into 1 volume percent Fe 3+ Solution, dropping the mixed solution into Fe with a syringe 3+ Crosslinking in the solution, and standing the obtained alginic acid composite material at room temperature;
step three, washing redundant Fe by deionized water 3+ Then the mixture is put into a cold dryer for drying for 48 hours to obtain Fe 3 O 4 /GO-SA-Fe 3+ 。
Example two
A preparation method of a novel adsorbent for synchronously removing heavy metals and antibiotics comprises the following steps:
(1) 0.05g of GO and 0.1g of Fe are weighed respectively 3 O 4 Adding a proper amount of deionized water into the two beakers respectively, and performing ultrasonic dispersion;
(2) Respectively weighing 1g of SA, pouring into the solution, and mechanically stirring to uniformly mix to obtain a solution 5 and a solution 6;
(3) Separately weighing 2g of FeCl 3 ·6H 2 O powder, prepared to 2% by volume Fe 3+ Solution 7 and solution 8;
(4) Dripping the solution 5 into the solution 7 by using an injector, dripping the solution 6 into the solution 7, and standing for 24 hours;
(5) Washing the excess Fe with deionized water 3+ Freeze drying for 48h to obtain GO-SA-FeFe 3+ 、Fe 3 O 4 -SA-Fe 3+ A material;
preparing solution with TC concentration of 50mg/L and Cu 2+ The concentration is 50mg/L, and the pH value is adjusted to 6 by 1M NaOH;
weighing the prepared GO-SA-Fe 3+ 、Fe 3 O 4 -SA-Fe 3+ 、Fe 3 O 4 /GO-SA-Fe 3+ Putting 0.01g of each into a 100mL ground conical flask;
30mL of TC having a concentration of 50mg/L or Cu were poured into each ground flask 2+ The concentration is 50mg/L, and the mixture is put into a shaking table, the shaking time is 24h, and the rotating speed is 180r/min;
the experimental result shows that Fe 3 O 4 /GO-SA-Fe 3+ Adsorption effect ratio GO-SA-Fe in monomer system TC solution 3+ 、Fe 3 O 4 -SA-Fe 3+ Good, the adsorption capacity is: 45mg/g; in monomer system Cu 2+ In solution, fe 3 O 4 /GO-SA-Fe 3+ The adsorption advantage of (a) is not significant.
The method for measuring the residual concentration comprises the following steps: filtering the obtained solution, measuring residual TC at 360nm with ultraviolet spectrophotometer or measuring residual Cu with flame atomic absorption 2+ And (4) concentration.
EXAMPLE III
A preparation method of a novel adsorbent for synchronously removing heavy metals and antibiotics comprises the following steps:
(1) Preparing materials: 0.1g of Fe was weighed 3 O 4 Respectively weighing 0g, 0.05g, 0.1g, 0.2g and 0.3g of GO, mixing with 100mL of deionized water, performing ultrasonic treatment to fully disperse the GO in water, adding 1g of SA powder, and mechanically stirring until the mixture is uniform; preparing Fe with the volume percentage concentration of 2% 3+ Dripping the solution after uniform stirring into Fe by a syringe 3+ Standing for 24h, washing excessive Fe with deionized water 3+ And then freeze-drying for 48 hours to obtain the material.
(2) The experimental process comprises the following steps: preparing TC with the concentration of 50mg/L and Cu 2+ The concentration is 20mg/L, and the pH value is adjusted to be 6; weighing materials 0.01g each, placing into 100mL ground conical flask, and pouring TC with concentration of 50mg/L or Cu 2+ The concentration is 20mg/L; shaking at 25 deg.C and 180r/min for 24h.
(3) The experimental results show that: when the mass of GO is 0.1g, the adsorption effect is better.
Exploration of Fe 3 O 4 The effect of (a) on the monomer-based adsorption assay, comprising the steps of:
(1) Preparing materials: weighing 0.1g of GO, and respectively weighing 0, 0.05g, 0.1g, 0.2g and 0.3g of Fe 3 O 4 Mixing with 100mL of deionized water, performing ultrasonic treatment to fully disperse the mixture in water, adding 1g of SA powder, and mechanically stirring the mixture until the mixture is uniform; preparing 2% volume percentage concentration Fe 3+ Dripping the solution into Fe with injector 3+ Standing for 24h, washing excessive Fe with deionized water 3+ And then freeze-drying for 48 hours to obtain the material.
(2) The experimental process comprises the following steps: preparing TC with the concentration of 50mg/L and Cu 2+ The concentration is 20mg/L, and the pH value is adjusted to be 6; weighing 0.01g of the materials, placing into a 100mL ground conical flask, and pouring TC with concentration of 50mg/L or Cu 2+ The concentration is 20mg/L; shaking at 25 deg.C and 180r/min for 24h.
(3) The experimental results show that: when Fe 3 O 4 When the mass of (2) is 0.1g, the adsorption effect is good.
The effect of the amount of SA on the monomer-based adsorption experiments was explored and included the following steps:
(1) Preparing materials: 0.1g of Fe was weighed 3 O 4 0.1g of GO is mixed with 100mL of deionized water, the mixture is fully dispersed in water by ultrasonic treatment, 0.5g of SA powder, 1g of SA powder and 1.5g of SA powder are respectively weighed and added, and the mixture is mechanically stirred until the mixture is uniform; preparing Fe with the volume percentage concentration of 2% 3+ Dripping the solution after uniform stirring into Fe by a syringe 3+ Standing for 24h, washing excessive Fe with deionized water 3+ And then freeze-drying for 48 hours to obtain the material.
(2) The experimental process comprises the following steps: preparing TC with the concentration of 50mg/L and Cu 2+ The concentration is 20mg/L, and the pH value is adjusted to be 6; weighing materials 0.01g each, placing into 100mL ground conical flask, and pouring TC with concentration of 50mg/L or Cu 2+ The concentration is 20mg/L; shaking at 180r/min for 24h at 25 ℃.
(3) The experimental results show that: when the volume percentage concentration of the SA is 0.5%, the adsorption effect is better.
Exploration of Fe 3+ The effect of the concentration of (a) on the monomer-based adsorption assay, comprising the steps of:
(1) Preparing materials:0.1g of Fe was weighed 3 O 4 0.1g of GO is mixed with 100mL of deionized water, the mixture is fully dispersed in water by ultrasonic treatment, 0.5g of SA powder is added, and the mixture is mechanically stirred until the mixture is uniform; respectively preparing 1%, 2%, 3%, 4% and 5% Fe by volume percentage concentration 3+ Dripping the solution after uniform stirring into Fe by a syringe 3+ Standing for 24h, washing excessive Fe with deionized water 3+ And then freeze-drying for 48 hours to obtain the material.
(2) The experimental process comprises the following steps: preparing TC with the concentration of 50mg/L and Cu 2+ The concentration is 20mg/L, and the pH value is adjusted to be 6; weighing 0.01g of the materials, placing into a 100mL ground conical flask, and pouring TC with concentration of 50mg/L or Cu 2+ The concentration is 20mg/L; shaking at 25 deg.C and 180r/min for 24h.
(3) The experimental results are as follows: when Fe 3+ When the volume percentage concentration of (A) is 1%, the adsorption effect is better.
(4) The method for measuring the residual concentration comprises the following steps: filtering the obtained solution, measuring residual TC at wavelength of 360nm with ultraviolet spectrophotometer or measuring residual Cu with flame atomic absorption 2+ And (4) concentration.
Example four
A preparation method of a novel adsorbent for synchronously removing heavy metals and antibiotics comprises the following steps:
(1) The concentration of the prepared solution is that the concentration of TC is 15mg/L and TC-Cu 2+ The concentration is 15mg/L +5mg/L, TC-Cu 2+ The concentration is 15mg/L +10mg/L, TC-Cu 2+ The concentration is 15mg/L +20mg/L, TC-Cu 2+ The concentration is 15mg/L +50mg/L, and the pH is adjusted by 1M NaOH and 1M HCl, and the pH range is 3 to 6;
(2) Fe obtained in example 1 was weighed 3 O 4 /GO-SA-Fe 3+ Putting 0.01g of each material into a ground conical flask, and respectively arranging two parallel samples under the conditions of different concentrations and different pH values;
(3) Pouring 30mL of the solution in the step (1) into the step (2), placing the solution in a shaking table, shaking for 24 hours, and rotating at the speed of 180r/min;
the experimental results show that: cu 2+ Promoting TC adsorption, and removing Cu2+ concentration in the range of 0-20mg/LRatio and Cu 2+ There is a positive correlation in concentration.
The residual concentration determination method comprises determining TC and Cu 2+ The specific measurement contents of (1) are as follows:
(1) Filtering the obtained monomer system solution, and measuring the residual TC by using an ultraviolet spectrophotometer at the wavelength of 360 nm;
(2) Filtering the obtained composite system solution, acidifying, and measuring the residual TC at the wavelength of 270 nm;
(3) Residual Cu determination by flame atomic absorption 2+ And (4) concentration.
EXAMPLE five
A preparation method of a novel adsorbent for synchronously removing heavy metals and antibiotics comprises the following steps:
(1) The concentration of the prepared solution is Cu 2+ The concentration is 20mg/L, cu 2+ TC concentration of 20mg/L +5mg/L, cu 2+ TC concentration of 20mg/L +10mg/L, cu 2+ -TC concentration of 20mg/L +20mg/L, cu 2- The concentration of TC + is 20mg/L +50mg/L, and the pH value is adjusted by 1M NaOH and 1M HCl, and the pH range is (3-6);
(2) Fe obtained in example 1 was weighed 3 O 4 /GO-SA-Fe 3+ Putting 0.01g of each material into a ground conical flask, and respectively arranging two parallel samples under the conditions of different concentrations and different pH values;
(3) Pouring 30mL of the solution in the step (1) into the step (2), placing the solution in a shaking table, shaking for 24 hours, and rotating at the speed of 180r/min;
the experimental results show that: at a TC concentration of 10mg/L, cu 2+ The removal rate of (C) is maximized, when the concentration of TC is higher than 10mg/L, cu is added 2+ The removal rate of (A) is not increased continuously but is decreased, but the whole process shows a promoting effect.
The residual concentration determination method comprises determining TC and Cu 2+ The specific measurement contents of (1) are as follows:
(1) Filtering the obtained monomer solution, and measuring the residual TC by using an ultraviolet spectrophotometer at a wavelength of 360 nm;
(2) Filtering the obtained composite system solution, acidifying, and measuring the residual TC at the wavelength of 270 nm;
(3) Residual Cu determination by flame atomic absorption 2+ And (4) concentration.
The working principle is as follows: as can be seen from fig. 1: FIG. 1a shows Fe 3 O 4 SEM image of (1), well dispersed Fe 3 O 4 The nanoparticles are composed of a plurality of nanocrystals, exhibit regular spheres, have rough surfaces, and are prepared from SA-Fe 3+ Clearly a distinct pore structure (as shown in FIG. 1 c), fe, was observed 3 O 4 /GO-SA-Fe 3+ The material is GO and Fe 3 O 4 The particles were oval, with average μm dimensions (FIG. 1 d). The results show that the iron-based catalyst is similar to the common SA-Fe 3+ In contrast, the cross section and surface of the composite material are embedded with obvious Fe 3 O 4 Particles (FIGS. 1e, 1h and 1 b), in addition, in Fe 3 O 4 /GO-SA-Fe 3+ Some porous structures with more complex structures (fig. 1f and 1 g) were also observed, and their surfaces were also more wrinkled (fig. 1 i), which may be related to the loading of graphene oxide.
As can be seen from fig. 2: TEM images may further investigate Fe 3 O 4 /GO-SA-Fe 3+ As shown in FIG. 2a, fe 3 O 4 MNPs are regular nanoparticles with a good monodispersed state and an average particle size of about 20nm for SA-Fe 3+ Without any material, TEM observed that its overall structure was a network (fig. 2 b), coated with GO and Fe simultaneously, due to the coverage of GO (g) 3 O 4 Fe (b) of 3 O 4 /GO-SA-Fe 3+ The network structure disappears under TEM image, and Fe is partially embedded 3 O 4 The spherical shape of MNPs becomes somewhat blurred (fig. 2 c).
From FIG. 3, it can be seen that: fe 3 O 4 /GO-SA-Fe 3+ Relative to GO-SA-Fe 3+ 、Fe 3 O 4 -SA-Fe 3+ In the monomer system TC, cu 2+ The adsorption effect in the solution is better.
From FIG. 4, it can be seen that: fe 3 O 4 /GO-SA-Fe 3+ The optimal material proportion is Fe 3 O 4 Mass 0.1g, GO 0.1g, volume% of SAThe concentration of the iron is 0.5 percent and the Fe content 3+ Is 1% by volume.
From FIG. 5, it can be seen that: in a composite system, with varying concentrations of Cu 2+ The addition of (2) rapidly improves the removal rate of TC, and Cu 2 + The effect on TC removal is facilitated, and Cu 2+ The concentration is in the range of 0-20mg/L, the removal rate and Cu are 2+ There is a positive correlation in concentration, probably due to Cu 2+ And TC forms a complex that promotes the adsorption of TC. When Cu 2+ When the concentration is 20mg/L, the promotion effect is the maximum, and the TC removal rate reaches the maximum. When Cu 2+ At a concentration of 50mg/L, the removal rate was not increased but rather decreased, probably because of Cu 2+ Increases in concentration of (a), forms a competitive relationship with respect to the adsorption of TC, however, eventually, cu 2+ Still exhibit a promoting effect on TC adsorption. The above phenomena indicate that: cu 2+ Complexation with TC promotes adsorption to TC, while Cu 2+ It is also possible to compete with TC for common adsorption sites simultaneously, and this promotion and inhibition occurs simultaneously during adsorption, and ultimately appears as a superposition of both effects.
From FIG. 5, it can be seen that: presence of TC for adsorption of Cu 2+ Has accelerating effect, especially Cu at TC concentration of 10mg/L 2+ The removal rate of (C) is maximized, when the concentration of TC is higher than 10mg/L, cu 2+ Is not continuously increased but is rather decreased, which may be due to an increase in the TC concentration for Cu 2+ The formation of competitive adsorption is relevant, however, the final TC still appears to be for Cu 2+ Promoting the adsorption.
The above phenomena indicate that: cu 2+ Complexation with TC promotes the control of Cu 2+ Adsorption of (C), and Cu 2+ And TC can compete for a common adsorption site at the same time, and the promotion effect and the inhibition effect exist in the adsorption process at the same time, so that the two effects are finally superposed.
Exemplary embodiments of the proposed solution of the present disclosure have been described in detail above with reference to preferred embodiments, however, it will be understood by those skilled in the art that many variations and modifications may be made to the specific embodiments described above, and that many combinations of the various technical features and structures presented in the present disclosure may be made without departing from the concept of the present disclosure, without departing from the scope of the present disclosure, which is defined by the appended claims.

Claims (8)

1. The preparation method of the novel adsorbent for synchronously removing heavy metals and antibiotics is characterized by comprising the following preparation steps:
step one, mixing the medicines, and respectively adding 0.1g of Fe 3 O 4 Dissolving GO in a beaker filled with deionized water, then carrying out ultrasonic dispersion, adding 0.5g of SA powder, and mechanically stirring to uniformly mix the SA powder and the GO to obtain a mixed solution;
step two, weighing 1g FeCl 3 ·6H 2 O powder prepared to be Fe with a volume concentration of 1% 3+ Solution, dripping the mixed solution into Fe with a syringe 3+ Crosslinking in the solution, and standing the obtained alginic acid composite material at room temperature;
step three, washing redundant Fe by deionized water 3+ And then the mixture is put into a cold dryer for drying for 48 hours to obtain Fe 3 O 4 /GO-SA-Fe 3+ ；
Step four, adding Fe into the solution to be treated 3 O 4 /GO-SA-Fe 3+ The material forms suspended matters and is vibrated for 28 hours in a shaking table, so that the surface of the material is in adsorption balance with pollutants in the water body;
step five, filtering and diluting the adsorbed solution, and measuring the residual TC and Cu 2+ And (4) concentration.
2. The method for preparing the novel adsorbent for synchronously removing heavy metals and antibiotics according to claim 1, wherein the Fe is 3 O 4 And GO is in a mass ratio of 1:1, the amount ratio of the SA powder in the mixed solution is 0.5%.
3. The method for preparing the novel adsorbent for synchronously removing heavy metals and antibiotics according to claim 1, wherein the Fe is 3 O 4 /GO-SA-Fe 3+ The concentration of tetracycline hydrochloride in the mixed solution is 15mg/L, and the concentration of the Fe is 3 O 4 /GO-SA-Fe 3+ The concentration of heavy metal copper in the mixed solution is 5mg/L to 50mg/L, and the Fe 3 O 4 /GO-SA-Fe 3+ The volume of the mixed solution is 30mL, and the volume of the mixed solution is Fe 3 O 4 /GO-SA-Fe 3+ The pH of the mixture was 3 to 6.
4. The method for preparing the novel adsorbent for synchronously removing the heavy metal and the antibiotic according to claim 1, wherein the solution to be treated is a mixed solution of tetracycline hydrochloride and heavy metal copper.
5. The method for preparing the novel adsorbent for synchronously removing the heavy metal and the antibiotic according to claim 4, wherein the heavy metal Cu is contained in the mixed solution of the tetracycline hydrochloride and the heavy metal copper 2+ The concentration of (2) was 20mg/L.
6. The method as claimed in claim 4, wherein the concentration of tetracycline hydrochloride in the mixed solution of tetracycline hydrochloride and heavy metal copper is 5mg/L to 50mg/L.
7. The preparation method of the novel adsorbent for synchronously removing the heavy metal and the antibiotic according to claim 4, wherein the volume of the mixed solution of the tetracycline hydrochloride and the heavy metal copper is 30mL, and the pH of the mixed solution of the tetracycline hydrochloride and the heavy metal copper is 3-6.
8. The method for preparing the novel adsorbent for synchronously removing heavy metals and antibiotics as claimed in claim 1, wherein the Fe is 3 O 4 /GO-SA-Fe 3+ The amount of the added material was 0.01g.
CN202210023281.7A 2022-01-10 2022-01-10 Preparation method of novel adsorbent for synchronously removing heavy metals and antibiotics Pending CN115212847A (en)

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