CN115608335A - Preparation method and application of magnetic sulfonated sodium alginate adsorbing material - Google Patents
Preparation method and application of magnetic sulfonated sodium alginate adsorbing material Download PDFInfo
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- CN115608335A CN115608335A CN202211295887.2A CN202211295887A CN115608335A CN 115608335 A CN115608335 A CN 115608335A CN 202211295887 A CN202211295887 A CN 202211295887A CN 115608335 A CN115608335 A CN 115608335A
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- sodium alginate
- magnetic
- sulfonated
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- deionized water
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical class CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000000463 material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims abstract description 76
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 50
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 50
- 239000000661 sodium alginate Substances 0.000 claims abstract description 50
- 238000001179 sorption measurement Methods 0.000 claims abstract description 42
- 229960003405 ciprofloxacin Drugs 0.000 claims abstract description 38
- 229960003702 moxifloxacin Drugs 0.000 claims abstract description 34
- FABPRXSRWADJSP-MEDUHNTESA-N moxifloxacin Chemical compound COC1=C(N2C[C@H]3NCCC[C@H]3C2)C(F)=CC(C(C(C(O)=O)=C2)=O)=C1N2C1CC1 FABPRXSRWADJSP-MEDUHNTESA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 23
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002351 wastewater Substances 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 8
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 5
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 3
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical class N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
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- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
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- 125000003172 aldehyde group Chemical group 0.000 description 1
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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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
- 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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—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 physical properties
- B01J20/28009—Magnetic properties
-
- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—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
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- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method and application of a magnetic sulfonated sodium alginate adsorbing material, and belongs to the field of wastewater treatment. The method takes sodium alginate, ferroferric oxide, silicon dioxide, glutaraldehyde and sulfamic acid as main raw materials to synthesize the novel modified sodium alginate adsorbing material. The magnetic sulfonated sodium alginate adsorbing material prepared by the invention has strong practicability, the adsorption capacities of the third-generation fluoroquinolone antibiotic ciprofloxacin and the fourth-generation fluoroquinolone antibiotic moxifloxacin can respectively reach 365.66mg/g and 149.57mg/g, the loss after the material is repeatedly used for 5 times is less than 20%, and the material has good antibiotic adsorption capacity and stability. The method provides a thought for glutaraldehyde crosslinking of sodium alginate under acid catalysis, has simple steps, is green and low in cost, does not consume a large amount of carboxyl on a sodium alginate matrix, and has wide application prospects in the aspect of removing various pollutants in wastewater by grafting different groups on the reserved carboxyl.
Description
Technical Field
The invention belongs to the field of wastewater treatment, relates to a sodium alginate-based adsorbent, and particularly relates to a preparation method of a magnetic sulfonated sodium alginate adsorbing material and application of the magnetic sulfonated sodium alginate adsorbing material in removal of fluoroquinolone antibiotics.
Background
Fluoroquinolone antibiotics are widely used for treating various bacterial infections of human and animals in the global range due to the characteristics of wide antibacterial spectrum, long drug effect, quick absorption, small side effect and the like. Currently, fluoroquinolone antibiotics have been upgraded to the fourth generation, with ciprofloxacin being the most widely used fluoroquinolone antibiotic as the third generation, often detected in wastewater. With the expansion of the antibacterial spectrum, the use of fourth generation fluoroquinolone antibiotics is rapidly increasing. However, antibiotics are not completely metabolized in the living body and mainly remain in surface water, sewage treatment plants and underground water, which not only promotes bacteria to generate drug resistance and harm ecological environment, but also causes serious harm to human health even at lower concentration.
The methods for removing antibiotics in water bodies, which have been reported, include adsorption methods, ion exchange methods, chemical oxidation methods, biodegradation methods, membrane filtration methods and the like. Among them, the adsorption method is considered to be one of the most valuable, effective and widespread antibiotic waste treatment technologies due to its advantages of simplicity, reliability, high efficiency, biodegradability and non-toxicity.
Sodium alginate is a linear anionic polysaccharide, has wide sources, strong hydrophilicity, commercial supply and low price, and can be biologically degraded. The molecular chain of the hydrogel contains abundant hydroxyl and carboxyl, and can be chelated with various polyvalent metal ions, so that a complex hydrogel network is formed. Therefore, the research of various sodium alginate-based adsorbents in environmental remediation, particularly water pollution treatment, mainly relates to heavy metal ion adsorption, anion adsorption and organic matter adsorption. In the prior art, for example, CN 105536726A discloses a preparation method of a graphene oxide sodium alginate composite adsorbing material for removing ciprofloxacin in an aqueous solution, and the adsorbing material in the technical scheme has an excellent ciprofloxacin-containing wastewater treatment effect. However, this adsorbent is a non-magnetic adsorbent, is difficult to recover, and passes Ca 2+ Crosslinking into balls consumes carboxyl on the sodium alginate matrix on one hand, and physical crosslinking into bonds is reversible on the other hand, so that the stability of the sodium alginate is controversial in the field of water treatment. Meanwhile, although studies on ciprofloxacin removal have been reported more, adsorption studies based on simultaneous removal of fluoroquinolone antibiotics (ciprofloxacin and moxifloxacin) have been less.
Glutaraldehyde is an effective cross-linking agent, and the molecular structure of the glutaraldehyde cross-linking agent is a straight-chain saturated dialdehyde containing five carbons, and stable chemical cross-linking can be formed through the acetal reaction between terminal aldehyde groups and hydroxyl groups under the catalysis of acid. Glutaraldehyde is far less toxic than other classes of aldehydes and chemical crosslinkers, classified as GRAS by the FDA, and can be used as a food additive in china (GB 2760-2014).
Disclosure of Invention
The invention aims to provide a preparation method and application of a magnetic sulfonated sodium alginate adsorbing material, wherein the magnetic sulfonated sodium alginate adsorbing material crosslinked by glutaraldehyde has stable chemical properties, can quickly realize the recycling of an adsorbent, can effectively remove fluoroquinolone antibiotics in wastewater, and has the advantages of green and environment-friendly application and wide prospect.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a magnetic sulfonated sodium alginate adsorption material comprises the following steps:
step 1) preparation of magnetic nanoparticles
By using
The method for preparing the magnetic nano-particles coated by the silicon dioxide by utilizing the ferroferric oxide and the silicon dioxide comprises the following specific steps:
placing 1.6-2.4 g of nano ferroferric oxide in 600mL of absolute ethyl alcohol, slowly adding 12mL of ammonia water, 200mL of deionized water and 6mL of tetraethoxysilane in sequence after ultrasonic treatment, stirring for 6-10 hours at room temperature, washing to be neutral by the absolute ethyl alcohol and the deionized water, and drying to obtain magnetic nanoparticles;
step 2) glutaraldehyde cross-linked sodium alginate
Adding 1-3 g of sodium alginate into 100mL of deionized water, stirring at room temperature to obtain sodium alginate mixed gel, adding 0.5-0.8 g of magnetic nanoparticles into the sodium alginate mixed gel, stirring at room temperature, dripping into 150mL of glutaraldehyde crosslinking agent, curing for 22-25 hours, washing to neutrality by using absolute ethyl alcohol and deionized water, and drying to obtain glutaraldehyde crosslinked magnetic sodium alginate, wherein: the glutaraldehyde crosslinking agent is a mixed solution consisting of 100mL of acetone, 25mL of glutaraldehyde, 20mL of acetic acid and 5mL of hydrochloric acid;
step 3) magnetic sodium alginate activation
Dissolving 0.25-0.3 g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 0.15-0.2 g of N-hydroxysuccinimide in 30mL of deionized water, adjusting the pH value to 5.5-6.0, adding 0.55-0.75 g of magnetic sodium alginate, and stirring at room temperature to obtain an activated magnetic sodium alginate mixed solution;
step 4) magnetic sodium alginate sulfonation
Dissolving 0.45-0.5 g of sulfamic acid in 30mL of deionized water, adjusting the pH value to 5.5-6.0, transferring the solution into the activated magnetic sodium alginate mixed solution obtained in the step 3), stirring the solution at room temperature, washing the solution with deionized water, and drying the solution to obtain the magnetic sulfonated sodium alginate.
In the steps 1) to 4), the stirring condition is 300 +/-20 r/min; the room temperature is 27 +/-2 ℃; the deionized water is ultrapure water prepared by a water purifier.
The magnetic sulfonated sodium alginate adsorbing material prepared by the method can be used for removing fluoroquinolone antibiotics in wastewater, wherein: the mass-volume ratio of the magnetic sulfonated sodium alginate adsorbing material to the wastewater is 10mg:20mL, wherein the fluoroquinolone antibiotics are ciprofloxacin and moxifloxacin, the content of the ciprofloxacin in the wastewater is 20-400 mg/L, the content of the moxifloxacin is 10-100 mg/L, and the specific method comprises the following steps:
adding 10mg of magnetic sulfonated sodium alginate adsorbent into 20mL of solution containing 20-400 mg/L ciprofloxacin, carrying out oscillation reaction for 24h in a constant-temperature oscillator at the temperature of 25-45 ℃, and adsorbing and removing the ciprofloxacin in the solution;
in the method (2), 10mg of magnetic sulfonated sodium alginate adsorbent is added into 20mL of solution containing 10-100 mg/L of moxifloxacin, and the solution is removed by adsorption after oscillation reaction for 24 hours in a constant-temperature oscillator at the temperature of 25-45 ℃.
Adding 10mg of magnetic sulfonated sodium alginate adsorbent into 20mL of mixed solution containing 100mg/L ciprofloxacin and 1-500 mmol/L sodium chloride, oscillating and reacting for 24h in a constant-temperature oscillator at the temperature of 25 ℃, and adsorbing and removing the ciprofloxacin in the solution.
In the method (4), 10mg of magnetic sulfonated sodium alginate adsorbent is added into 20mL of mixed solution containing 100mg/L of moxifloxacin and 1-500 mmol/L of sodium chloride, and the mixture is subjected to oscillation reaction for 24 hours in a constant-temperature oscillator at the temperature of 25 ℃ to adsorb and remove the moxifloxacin in the solution.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, sodium alginate, ferroferric oxide, silicon dioxide, glutaraldehyde and sulfamic acid are used as main raw materials to synthesize a novel modified sodium alginate adsorbing material, and after ciprofloxacin and moxifloxacin in water are treated by the adsorbing material, rapid recovery can be realized under an external magnetic field, and secondary pollution to the environment can not be caused.
2. The raw materials used for preparing the magnetic sulfonated sodium alginate adsorbent are green, the cost is low, the preparation method and the preparation process are simple, the preparation process is environment-friendly, and the practicability is high.
3. The magnetic sulfonated sodium alginate adsorbent prepared by the invention has the advantages of large adsorption capacity, reusability and stable adsorption effect, has excellent water purification efficiency, has a rough surface after sulfonation, increases the contact area of an adsorption material and antibiotics, and effectively improves the adsorption performance of the adsorbent on third-generation fluoroquinolone antibiotics ciprofloxacin and fourth-generation fluoroquinolone antibiotics moxifloxacin. The result shows that the hydrogen bond, the electrostatic attraction and the n-pi EDA comprehensively dominate the adsorption process of the magnetic sulfonated sodium alginate adsorbent on the ciprofloxacin and the moxifloxacin.
4. The magnetic sulfonated sodium alginate adsorbing material prepared by the invention has strong practicability, the adsorption capacities of the third-generation fluoroquinolone antibiotic ciprofloxacin and the fourth-generation fluoroquinolone antibiotic moxifloxacin can respectively reach 365.66mg/g and 149.57mg/g, the loss after the material is repeatedly used for 5 times is less than 20%, and the material has good antibiotic adsorption capacity and stability.
5. The method provides a thought for glutaraldehyde crosslinking of sodium alginate under acid catalysis, has simple steps, is green and low in cost, does not consume a large amount of carboxyl on a sodium alginate matrix, and has wide application prospects in the aspect of removing various pollutants in wastewater by grafting different groups on the reserved carboxyl.
Drawings
FIG. 1 is a scanning electron micrograph (20.00 KX) of the magnetic nanoparticles prepared in example 1;
FIG. 2 is a scanning electron micrograph (1.00 KX) of magnetic sodium alginate prepared in example 1;
FIG. 3 is a scanning electron micrograph (1.00 KX) of the magnetic sulfonated sodium alginate prepared in example 1;
FIG. 4 is an EDX spectrum test chart of magnetic sodium alginate prepared in example 1;
FIG. 5 is an EDX spectrum test chart of magnetic sulfonated sodium alginate prepared in example 1;
FIG. 6 is a O1s XPS high resolution spectrum of the magnetic sulfonated sodium alginate prepared in example 1 before and after respectively adsorbing ciprofloxacin and moxifloxacin;
FIG. 7 is S2 p XPS high resolution spectra of the magnetic sulfonated sodium alginate prepared in example 1 before and after the adsorption of ciprofloxacin and moxifloxacin, respectively;
FIG. 8 is a graph showing changes in the adsorption capacity for ciprofloxacin with changes in the initial concentration of ciprofloxacin, at 25 deg.C, 35 deg.C, and 45 deg.C, respectively, for the magnetic sulfonated sodium alginate prepared in example 1;
FIG. 9 is a graph showing the change in adsorption capacity for moxifloxacin in response to the change in initial concentration of moxifloxacin at 25 deg.C, 35 deg.C, and 45 deg.C, respectively, for the magnetic sulfonated sodium alginate prepared in example 1;
FIG. 10 is a graph showing the effect of salt ion concentration on ciprofloxacin adsorption by magnetic sodium alginate sulfonate prepared in example 1;
FIG. 11 is a graph showing the effect of salt ion concentration on the adsorption of moxifloxacin by the magnetic sulfonated sodium alginate prepared in example 1;
fig. 12 is a graph showing the adsorption capacity loss of the magnetic sodium sulfonated alginate prepared in example 1 for ciprofloxacin under continuous 5 adsorption-desorption cycles;
fig. 13 is a graph of the loss of adsorption capacity of magnetic sulfonated sodium alginate prepared in example 1 for moxifloxacin under 5 consecutive adsorption-desorption cycles.
Detailed Description
The technical solutions of the present invention are further described below with reference to the following examples, but the present invention is not limited thereto, and any modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Example 1
The embodiment provides a preparation method of a magnetic sulfonated sodium alginate adsorption material for removing fluoroquinolone antibiotics, which comprises the following steps:
step 1): placing 2.4g of nano ferroferric oxide in 600mL of absolute ethyl alcohol to prepare a ferroferric oxide suspension, performing ultrasonic treatment for 10 minutes, sequentially and slowly adding 12mL of ammonia water, 200mL of deionized water and 6mL of tetraethoxysilane, stirring for 8 hours at room temperature, washing for 2 times by using the absolute ethyl alcohol, washing for 5 times by using the deionized water until the solution is neutral, and drying to obtain the magnetic nanoparticles.
Step 2): adding 2g of sodium alginate into 100mL of deionized water to prepare sodium alginate gel with the mass fraction of 2%, adding 0.6g of the magnetic nanoparticles prepared in the step 1) into the sodium alginate mixed gel, stirring at room temperature of 300r/min for 5 hours, dripping into a prepared glutaraldehyde crosslinking agent containing 100mL of acetone, 25mL of glutaraldehyde, 20mL of acetic acid and 5mL of hydrochloric acid, curing for 24 hours, washing for 2 times by absolute ethyl alcohol, washing for 5 times by deionized water to be neutral, and drying to obtain the glutaraldehyde crosslinked magnetic sodium alginate.
Step 3): dissolving 0.2817g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 0.1691g of N-hydroxysuccinimide in 30mL of deionized water, adjusting the pH to about 5.7, adding 0.6g of the magnetic sodium alginate obtained in the step 2), and stirring for 1 hour to obtain an activated magnetic sodium alginate mixed solution;
and step 4): dissolving 0.48g of sulfamic acid in 30mL of deionized water, adjusting the pH to about 5.7, transferring the solution into the activated magnetic sodium alginate mixed solution obtained in the step 3), stirring the solution for 8 hours at room temperature at 300r/min, washing the solution for 5 times by using deionized water, and drying the solution to obtain the magnetic sulfonated sodium alginate.
Scanning electron microscope characterization analysis was performed on the magnetic sulfonated sodium alginate prepared in this example. The scanning electron microscope image of the magnetic sodium alginate is shown in figure 2, and the scanning electron microscope image of the magnetic sulfonated sodium alginate is shown in figure 3, so that the sulfonated material has a rougher surface and a looser structure, and is favorable for adsorption.
The magnetic sulfonated sodium alginate prepared in this example was subjected to EDS spectrum characterization analysis. An EDX spectrum test chart of the magnetic sodium alginate is shown in figure 4, and an EDX spectrum test chart of the magnetic sulfonated sodium alginate is shown in figure 5, and S element appears in figure 5, which indicates that the magnetic sodium alginate is successfully sulfonated.
XPS spectral characterization analysis was performed on the magnetic sulfonated sodium alginate prepared in this example. O1S high-resolution maps of the magnetic sodium alginate before and after the magnetic sodium alginate adsorbs ciprofloxacin and moxifloxacin are shown in figure 6, and S2 p high-resolution maps of the magnetic sodium alginate before and after the magnetic sodium alginate adsorbs ciprofloxacin and moxifloxacin are shown in figure 7, so that the O1S peak position and the S2 p peak position are obviously changed, and the fact that the magnetic sodium alginate prepared in the embodiment participates in the adsorption process of ciprofloxacin and moxifloxacin through a hydrogen bond n-pi EDA and an electrostatic attraction is confirmed.
Example 2
Ciprofloxacin aqueous solutions with concentrations of 20mg/L, 40mg/L, 60mg/L, 80mg/L, 100mg/L, 120mg/L, 140mg/L, 160mg/L, 200mg/L, 240mg/L, 280mg/L, 320mg/L, 360mg/L and 400mg/L were prepared in this order, the pH =7 was adjusted, 10mg of the magnetic sulfonated sodium alginate adsorbent obtained in example 1 was placed in a 20mL brown sample bottle (20 mL) containing a ciprofloxacin sample solution, and the mixture was shaken at 25 ℃, 35 ℃ and 35 ℃ for 24 hours at an oscillation speed of 200 rpm. The adsorbent and sample solution were separated by magnet and the absorbance value of the supernatant was measured at 271nm using an ultraviolet-visible spectrophotometer. The experimental result shows that under the best experimental conditions, the maximum adsorption capacity of the magnetic sulfonated sodium alginate adsorbent obtained in example 1 on ciprofloxacin is 365.66mg/g.
Example 3
Moxifloxacin aqueous solutions with the concentrations of 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L, 60mg/L, 70mg/L, 80mg/L, 90mg/L and 100mg/L are prepared in sequence, the pH value is adjusted to be =7, 10mg of the magnetic sulfonated sodium alginate adsorbent obtained in the embodiment 1 is placed into a 20mL brown sample bottle (20 mL) containing a moxifloxacin sample solution, and the mixture is shaken at the temperature of 25 ℃, 35 ℃ and 35 ℃ for 24 hours at the shaking speed of 200 rpm. The adsorbent and sample solution were separated by magnet and the absorbance value of moxifloxacin supernatant was determined using an ultraviolet-visible spectrophotometer at 289 nm. The experimental result shows that under the optimal experimental conditions, the maximum adsorption capacity of the magnetic sulfonated sodium alginate adsorbent obtained in example 1 on moxifloxacin is 149.57mg/g.
Example 4
100mg/L ciprofloxacin solution and 1mmol/L, 10mmol/L, 50 mmol/L, 100mmol/L and 500mmol/L sodium chloride solution were prepared respectively, pH =7 was adjusted, 20mg of the magnetic sulfonated sodium alginate adsorbent obtained in example 1 was put into a mixed solution (20 mL) containing ciprofloxacin and sodium chloride of different concentrations, and the mixture was shaken at 200rpm for 24 hours. The adsorbent and sample solution were separated by a magnet, and the absorbance value of ciprofloxacin supernatant was measured at 271nm using an ultraviolet-visible spectrophotometer. The experimental result shows that the adsorption amount of ciprofloxacin does not change greatly along with the increase of the concentration of sodium chloride, and the adsorbent prepared in the example 1 can be well applied to a high-concentration salt solution.
Example 5
Preparing 100mg/L moxifloxacin solution and 1mmol/L, 10mmol/L, 50 mmol/L, 100mmol/L and 500mmol/L sodium chloride solution respectively, adjusting the pH value to be =7, putting 20mg of the magnetic sulfonated sodium alginate adsorbent obtained in the example 1 into a mixed solution (20 mL) containing moxifloxacin and sodium chloride with different concentrations, and oscillating at the oscillation speed of 200rpm for 24h. The adsorbent and sample solution were separated by magnet and the absorbance value of moxifloxacin supernatant was determined using an ultraviolet-visible spectrophotometer at 271 nm. The experimental result shows that the adsorption quantity of moxifloxacin does not change greatly along with the increase of the concentration of sodium chloride, and the adsorbent prepared in the example 1 can be well applied to a high-concentration salt solution.
Example 6
Preparing 100mg/L ciprofloxacin solution to perform an adsorption-desorption regeneration experiment of the magnetic sulfonated sodium alginate adsorbent obtained in the embodiment 1, wherein the adsorption temperature is 25 ℃, the adsorption process is the same as that in the embodiment 2, the adsorbent and the sample solution are separated by using a magnet after adsorption, the absorbance of the sample solution is measured, and the corresponding removal rate is calculated; desorbing the adsorbent by using 0.1mol/L hydrochloric acid, absolute ethyl alcohol and hydrochloric acid-absolute ethyl alcohol (the volume ratio is 1:1, the pH value is 1.0), washing the regenerated magnetic sulfonated sodium alginate adsorbent by using deionized water for a plurality of times, drying and continuously repeating for 5 times under the same conditions. The experimental result shows that 0.1mol/L hydrochloric acid and hydrochloric acid-absolute ethyl alcohol both have better desorption effect, and after 5 times of adsorption-desorption, the loss of ciprofloxacin adsorption capacity is less than 20%.
Example 7
Preparing 50mg/L moxifloxacin solution, performing an adsorption-desorption regeneration experiment of the magnetic sulfonated sodium alginate adsorbent obtained in the embodiment 1, wherein the adsorption temperature is 25 ℃, the adsorption process is the same as that in the embodiment 3, separating the adsorbent and the sample solution by using a magnet after adsorption, measuring the absorbance of the sample solution, and calculating the corresponding removal rate; desorbing the adsorbent by using 0.1mol/L hydrochloric acid, absolute ethyl alcohol and hydrochloric acid-absolute ethyl alcohol (the volume ratio is 1:1, the pH value is 1.0), washing the regenerated magnetic sulfonated sodium alginate adsorbent by using deionized water for a plurality of times, drying and continuously repeating for 5 times under the same conditions. Experimental results show that 0.1mol/L hydrochloric acid and hydrochloric acid-absolute ethyl alcohol both have a good desorption effect, and after 5 times of adsorption-desorption, the loss of moxifloxacin adsorption capacity is less than 20%.
From examples 2 to 7, it can be seen that when the magnetic sulfonated sodium alginate adsorbent prepared in example 1 is applied to removal of ciprofloxacin, which is a third-generation fluoroquinolone antibiotic, and moxifloxacin, which is a fourth-generation fluoroquinolone antibiotic, in water, the magnetic sulfonated sodium alginate adsorbent has the advantages of excellent adsorption performance, stable effect, reusability and the like, and the maximum adsorption capacities of ciprofloxacin and moxifloxacin respectively reach 365.66mg/g and 149.57mg/g.
Claims (10)
1. A preparation method of a magnetic sulfonated sodium alginate adsorption material is characterized by comprising the following steps:
step 1) preparation of magnetic nanoparticles
By using
The method comprises the steps of preparing magnetic nanoparticles wrapped by silicon dioxide by utilizing ferroferric oxide and silicon dioxide;
step 2) glutaraldehyde cross-linked sodium alginate
Adding 1-3 g of sodium alginate into 100mL of deionized water, stirring at room temperature to obtain sodium alginate mixed gel, adding 0.5-0.8 g of magnetic nanoparticles into the sodium alginate mixed gel, stirring at room temperature, dripping into 150mL of glutaraldehyde crosslinking agent, curing for 22-25 hours, washing with absolute ethyl alcohol and deionized water to be neutral, and drying to obtain glutaraldehyde crosslinked magnetic sodium alginate;
step 3) magnetic sodium alginate activation
Dissolving 0.25-0.3 g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 0.15-0.2 g of N-hydroxysuccinimide in 30mL of deionized water, adjusting the pH to 5.5-6.0, adding 0.55-0.75 g of magnetic sodium alginate, and stirring at room temperature to obtain an activated magnetic sodium alginate mixed solution;
step 4) magnetic sodium alginate sulfonation
Dissolving 0.45-0.5 g of sulfamic acid in 30mL of deionized water, adjusting the pH value to 5.5-6.0, transferring the solution into the activated magnetic sodium alginate mixed solution obtained in the step 3), stirring the solution at room temperature, washing the solution with deionized water, and drying the solution to obtain the magnetic sulfonated sodium alginate.
2. The preparation method of the magnetic sulfonated sodium alginate adsorbing material according to claim 1, wherein the specific steps of the step 1) are as follows:
placing 1.6-2.4 g of nano ferroferric oxide in 600mL of absolute ethyl alcohol, slowly adding 12mL of ammonia water, 200mL of deionized water and 6mL of tetraethoxysilane in sequence after ultrasonic treatment, stirring for 6-10 hours at room temperature, washing to be neutral by the absolute ethyl alcohol and the deionized water, and drying to obtain the magnetic nanoparticles.
3. The preparation method of the magnetic sulfonated sodium alginate adsorbing material according to claim 1, wherein the glutaraldehyde crosslinking agent is a mixed solution composed of 100mL of acetone, 25mL of glutaraldehyde, 20mL of acetic acid and 5mL of hydrochloric acid.
4. The preparation method of the magnetic sulfonated sodium alginate adsorbing material according to claim 1 or 2, wherein the stirring conditions are all 300 ± 20r/min, and the room temperature conditions are all 27 ± 2 ℃.
5. The method for preparing the magnetic sulfonated sodium alginate adsorbing material according to claim 1, wherein the deionized water is ultrapure water prepared by a water purification machine.
6. A magnetic sulfonated sodium alginate adsorbing material prepared by the method of any one of claims 1 to 5.
7. The application of the magnetic sulfonated sodium alginate adsorbing material prepared by the method of any one of claims 1 to 5 in removing fluoroquinolone antibiotics in wastewater.
8. The application of the magnetic sulfonated sodium alginate adsorbing material in the removal of fluoroquinolone antibiotics in wastewater according to claim 7, wherein the mass-to-volume ratio of the magnetic sulfonated sodium alginate adsorbing material to the wastewater is 10mg:20mL.
9. The application of the magnetic sulfonated sodium alginate adsorbing material in the removal of fluoroquinolone antibiotics in wastewater according to claim 7, wherein the fluoroquinolone antibiotics are ciprofloxacin and moxifloxacin.
10. The application of the magnetic sulfonated sodium alginate adsorbing material in removing fluoroquinolone antibiotics in wastewater according to claim 9, wherein the content of ciprofloxacin in wastewater is 20-400 mg/L, and the content of moxifloxacin in wastewater is 10-100 mg/L.
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