CN111111631A - Preparation method of chitosan-based magnetic microsphere adsorbent capable of efficiently adsorbing cationic dye - Google Patents
Preparation method of chitosan-based magnetic microsphere adsorbent capable of efficiently adsorbing cationic dye Download PDFInfo
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Abstract
The invention discloses a preparation method of a chitosan-based magnetic microsphere adsorbent, which comprises the following steps: firstly, adopting carboxymethyl chitosan and Fe3O4Preparing a mixed solution, adding the mixed solution into a cyclohexane oil phase environment containing a dispersant span 80 to form a uniformly dispersed water-oil suspension, and finally preparing the magnetic carboxymethyl chitosan microspheres by an inverse emulsion crosslinking method by taking glutaraldehyde as a crosslinking agent. The chitosan-based magnetic microsphere adsorbent prepared by the method has the advantages of simple operation, short synthesis time and low cost, and is suitable for large-scale industrial productionThe product is used for treating the wastewater containing the cationic dye, has obviously better removal effect than similar products, and has good regenerability and salt resistance.
Description
Technical Field
The invention belongs to the technical field of adsorbent preparation, and particularly relates to a preparation method and application of a chitosan-based magnetic microsphere adsorbent.
Background
Dye wastewater is one of important industrial wastewater, and the water environment safety is seriously threatened. The adsorption method is one of the most promising technologies in dye wastewater treatment. It can remove some organic dyes which are difficult to degrade by biochemical method or organic matters which are difficult to destroy the molecular structure by common oxidation method in the waste water, and can be used for adsorbing materials with wide sources. The Chitosan (CS) is a deacetylated product of chitin and chitin widely existing in nature, has biodegradability, biocompatibility and bioadhesion, is low in cost, does not produce secondary pollution to the environment, and is simple to operate. Therefore, in the field of dye wastewater treatment, chitosan is one of the most promising raw materials for preparing the adsorbent.
However, chitosan molecules have the disadvantages of instability in an acidic medium, easy dissolution to cause loss, low mechanical strength, difficult regeneration and the like, thereby limiting the wide application of the chitosan molecules. In order to stabilize chitosan under acidic conditions and expand the applicable pH range of its adsorption, chitosan is chemically modified with a cross-linking agent. Meanwhile, chitosan is difficult to separate and recover from the solution after adsorbing pollutants in water, and is generally separated from the aqueous solution by adopting methods such as centrifugation or filtration, but the separation methods have high energy consumption and low separation efficiency, and the adsorbent is greatly lost in the separation process, so that the regeneration performance of the separated adsorbent is poor. Compared with the traditional adsorbent separation technology, the magnetic separation technology is more efficient and economical. Meanwhile, the carboxymethyl chitosan coated with the magnetic ferroferric oxide has good wear resistance, high mechanical strength and high reusability. Therefore, improving the stability and the recycling rate is one of the hot spots in the chitosan modification research.
However, the currently reported magnetic chitosan-based adsorbents generally have the defects of complex preparation process, small adsorption capacity, low repeated utilization rate and the like.
Chinese patent document CN108126671A discloses a preparation method of a supported chitosan adsorbent, which comprises the steps of firstly, placing chitosan in a muffle furnace at 420-1300 ℃ for heat treatment modification, and performing heat treatment on the chitosan in 40 mL/min-1Roasting for 4 hours in nitrogen; fully dissolving chitosan into dilute acid; adding the dilute acid solution of chitosan into the suspension of the heat-treated carrier, and fully stirring for 6 hours. The prepared adsorbent has high removal rate, but low adsorption capacity, long preparation process time, complex reaction conditions and difficult application.
Chinese patent document CN106378105A discloses a preparation method of a magnetic chitosan composite adsorbent, which comprises the steps of firstly preparing composite magnetic Fe3O4@Al3O4And then coating chitosan, and simultaneously performing glutaraldehyde crosslinking and thiourea modification on the chitosan to obtain the magnetic adsorbent. The method for preparing the magnetic chitosan adsorbent by coprecipitation is simple and convenient, but can only reach 72.7 percent of the primary adsorption capacity after 5 times of circulation, and the circulation performance needs to be improved.
Compared with the prior art, the preparation method has the advantages of simple operation, mild reaction conditions, no special equipment requirement and the like, and the prepared magnetic chitosan-based adsorbent has large adsorption capacity, is easy to separate from a water body, and has good ecological benefit and economic benefit.
Disclosure of Invention
In view of the above problems, the primary object of the present invention is to provide a method for preparing a magnetic carboxymethyl chitosan adsorbent.
The invention also aims to provide the magnetic carboxymethyl chitosan adsorbent prepared by the method.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a magnetic carboxymethyl chitosan microsphere adsorbent comprises the following steps:
weighing carboxymethyl chitosan and nano ferroferric oxide in water, and stirring for 2-3h by using a magnetic stirrer to obtain a uniformly dispersed mixed solution of the ferroferric oxide and the carboxymethyl chitosan.
Adding cyclohexane serving as a solvent into a three-neck flask to provide an oil phase environment, stirring for 2-10 min, adding span 80 serving as a dispersing agent, continuously stirring for 20-30 min under the constant temperature condition of a water bath at 20-30 ℃, uniformly and quickly adding the prepared mixed solution into the three-neck flask to form a water-oil suspension, heating to 40-60 ℃, stirring for 4-6 h, finally preparing magnetic carboxymethyl chitosan microspheres by using glutaraldehyde serving as a cross-linking agent through an inverse emulsion cross-linking reaction, and adding glutaraldehyde, stirring and reacting for 0.5-1.5 h. After the reaction is finished, separating out the black microspheres under the condition of an external magnetic field, and repeatedly washing by using ethanol and distilled water. And after washing, carrying out vacuum drying on the obtained black microspheres to constant weight to obtain the adsorbent magnetic carboxymethyl chitosan microspheres.
Approximate ranges of reaction temperature, reaction time, mass ratio or volume ratio of materials and reagents to be added are written in the following "preferred" section, and specific amounts are written in the "examples" section
Preferably, carboxymethyl chitosan is mixed with Fe3O4The mass ratio is 2-3: 1. The proportion can ensure that the adsorbent has better magnetism, and simultaneously has more cationic dye adsorption sites, thereby having better adsorption effect on cationic dye.
Preferably, the mass ratio of the carboxymethyl chitosan to the glutaraldehyde is 0.5-1: 1. If the addition proportion of the glutaraldehyde is too low, the crosslinking degree is insufficient, the adsorbent is difficult to form, and if the addition proportion of the glutaraldehyde is too high, the crosslinking degree is too high, the effective active sites of the adsorbent are reduced, and the adsorption effect is influenced.
Preferably, the mass ratio of the carboxymethyl chitosan to the cyclohexane to the span 80 is 1-1.5: 115-135 parts by weight: 1. Because cyclohexane is an oil phase, the oil-to-water ratio cannot be too small. Due to carboxymethyl chitosan and Fe3O4The magnetic microspheres are divided into disperse phases in a reaction environment, if the oil-water ratio is too small, uneven contact is easily caused, and the magnetic microspheres are difficult to sphere. The larger the oil-water ratio is, the smaller the particle size of the magnetic microspheres is, and when the oil-water ratio is too large, the diameter of the magnetic microspheres is too small to be beneficial to sedimentation. Span 80 is an emulsifier and surfactant, whichThe effect is not obvious when the quantity is too small, so that the magnetic microsphere is not beneficial to wrapping magnetic substances and influencing the forming of the magnetic microsphere; too large an amount thereof causes uneven dispersion of the reactants. The mass ratio of the carboxymethyl chitosan to the cyclohexane to the span 80 can be preferably 1.5-165-1.25, wherein the carboxymethyl chitosan is dispersed in water at a concentration of 0.068g/mL, and Fe3O4Dispersed in water at 0.018 g/mL.
Preferably, the crosslinking reaction temperature is 40-60 ℃, and if the reaction temperature is too low, the crosslinking reaction is not easy to occur, the reaction rate is low, the yield is low, and if the temperature is too high, the problem of too large crosslinking degree is easily caused, so that the effective active sites of the product are reduced, and the adsorption effect is influenced.
Principle of the technology
Compared with the prior art, the invention has the following beneficial effects:
1. the method for preparing the magnetic chitosan adsorbing material has the advantages of no need of pH adjustment in the preparation process, simple operation and short synthesis time.
2. The adsorbent prepared by the invention is rich in amino and carboxyl, has stronger adsorption removal capacity on cationic dye under the actual industrial wastewater pH, and the adsorption capacity can reach 1200 mg/g;
3. the adsorbent prepared by the invention has the advantages of uniform appearance, uniform spherical shape, good stability, good salt resistance and regeneration performance.
4. The adsorbent prepared by the invention does not cause secondary pollution, has superparamagnetism, and can be quickly separated and recovered by an external magnetic field.
The magnetic carboxymethyl chitosan composite microspheres have a regular spherical shape, so that the contact area between the adsorbent and the cationic dye is increased, the dispersibility and the flowability of the microspheres are good, the diffusion efficiency of pollutant molecules on the surface of the adsorbent is improved, and the rapid completion of the adsorption process is promoted.
The existing preparation method of the microsphere adsorbent has a plurality of defects. The carboxymethyl chitosan microsphere prepared by the chemical crosslinking method is generally uncontrollable in size, the preparation process of the spray drying method is complex, the required conditions in the preparation process are not easy to control, the preparation process of the suspension polymerization method is simple, and the preparation amount is large. The inverse emulsion crosslinking method is a new technical means combining a directional suspension technology and a crosslinking method, has the advantages of low system viscosity, high reaction rate, good heat dissipation, high product molecular weight, less byproducts, easier realization of continuous production and the like, and is easy to obtain a stable emulsion system. The prepared carboxymethyl chitosan microsphere has high and uniform molecular weight, good dispersibility and good solubility.
The principle of the magnetic separation technology adopted by the invention is magnetic attraction. After the magnetic adsorbent is saturated, the magnetic carboxymethyl chitosan can be quickly separated from the water body by the attraction of an external magnetic field, and then elution and regeneration are carried out. The loss of the adsorbent is small, and the regeneration performance of the separated adsorbent is good.
Drawings
FIG. 1 is an infrared spectrum of carboxymethyl chitosan prepared in example 1 and an absorbent for carboxymethyl chitosan absorbing a cationic dye.
The red curve is the IR spectrum of the carboxymethyl chitosan (OCS) used in example 1, 3447cm-1The peak of the vibration corresponds to-OH and N-H stretching vibration on carboxymethyl chitosan, 1700cm-1The peak at (b) corresponds to C ═ O stretching vibration on methyl chitosan.
The black curve is the IR spectrum, 3447cm, of the magnetic carboxymethyl chitosan adsorbent (MOCS) prepared in example 1-1The peak of (B) corresponds to-OH, N-H stretching vibration on carboxymethyl chitosan, and 1634cm-1The C ═ N group formed by the reaction of the amine group corresponding to carboxymethyl chitosan with the aldehyde group of glutaraldehyde through Schiff's base, indicating that glutaraldehyde has been successfully crosslinked to carboxymethyl chitosan. At the same time, the thickness is 571cm-1The absorption peak at corresponds to Fe3O4Fe-O in (1) vibrates.
Fig. 2 is an XRD diffraction pattern of the carboxymethyl chitosan adsorbent adsorbing the cationic dye prepared in example 1.
Diffraction spectrum peaks appear at 18.3 °, 30.1 °, 35.5 °, 43.1 °, 53.5 °, 57.0 °, and 62.6 ° for Fe, respectively3O4Each of (111), (220), (311), (400), (422), (511) and (440) of (A) and the diffraction peak is sharp, which proves thatThe prepared microspheres mainly contain good-phase-ratio Fe3O4The crystal modification does not change the crystal structure of the ferroferric oxide.
Fig. 3 is a magnetic hysteresis chart of a magnetic carboxymethyl chitosan adsorbent prepared from the magnetic ferroferric oxide nanoparticles used in example 1.
The saturation magnetization of the magnetic ferroferric oxide nano-particles and the magnetic carboxymethyl chitosan adsorbent is respectively 0.22 emu/g and 0.84emu/g, and the magnetic property of the magnetic carboxymethyl chitosan adsorbent is reduced compared with the magnetic ferroferric oxide nano-particles due to the high organic matter content of the magnetic carboxymethyl chitosan adsorbent, but the efficient separation of the adsorbent and the solution can still be realized through an external magnetic field.
Detailed Description
Case 1
1.5g of carboxymethyl chitosan and 0.5g of nano ferroferric oxide are weighed into 22ml of water, and stirred for 3 hours by using a magnetic stirrer to obtain a uniformly dispersed mixed solution of the ferroferric oxide and the carboxymethyl chitosan.
Adding 165ml of cyclohexane serving as a solvent to provide an oil phase environment into a three-neck flask, stirring for 5min, adding 1.25ml of span 80 serving as a dispersing agent, continuously stirring for 25min under the constant temperature condition of a water bath at 25 ℃, then quickly and uniformly adding the prepared mixed solution into the three-neck flask to form a water-oil suspension, heating to 50 ℃, stirring for 5h, finally preparing magnetic carboxymethyl chitosan microspheres by using glutaraldehyde serving as a cross-linking agent through inverse emulsion cross-linking reaction, adding 0.95ml of glutaraldehyde, and stirring for 1 h. After the reaction is finished, separating out the black microspheres under the condition of an external magnetic field, and repeatedly washing by using ethanol and distilled water. And after washing, carrying out vacuum drying on the obtained black microspheres to constant weight to obtain the magnetic carboxymethyl chitosan microsphere adsorbent.
Case 2
The difference between the preparation method of the example and the preparation method of the example 1 is as follows: the mass of the added nanoscale ferroferric oxide is 0.25g, the mass of glutaraldehyde is 0.75g, the mass of cyclohexane is 145g, the mass of span 80 is 1g, and other conditions are the same as those in example 1.
Case 3
The difference between the preparation method of the example and the preparation method of the example 1 is as follows: the mass of the added nanoscale ferroferric oxide is 0.75g, the mass of glutaraldehyde is 1.5g, the mass of cyclohexane is 185g, the mass of span 80 is 1.5g, and other conditions are the same as those in example 1.
Application test
1) Removal rate of crystal violet at different pH
The magnetic adsorbent prepared in example 1 was used for removing crystal violet, and the removal rate of crystal violet was tested.
Preparing 1000mg/L crystal violet simulated wastewater, testing the removal effect of the magnetic adsorbent prepared in example 1 under different pH values, adding 10mg of the adsorbent into 20mL of dye solution each time, shaking for 24h at 25 ℃, magnetically separating the adsorbent, and determining the concentration of the dye solution.
| pH | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 |
| Adsorption capacity mg/g | 350 | 200 | 900 | 1080 | 1000 | 1050 | 1200 | 1200 | 1125 | 1625 |
It can be seen from the table that the magnetic coagulant prepared by the invention can achieve higher adsorption capacity in the range of pH 4 to pH 11, and can achieve the highest adsorption capacity of 1200mg/g when the crystal violet is treated at different pH values.
2) Regeneration and utilization of adsorbent
The adsorbents prepared in the embodiments 1 to 3 are respectively adsorbed with crystal violet, the adsorbents are separated from the water solution under a magnetic field, then 0.1mol/LHCL solution is desorbed by the adsorbents for 24 hours, after the desorption, the adsorbent can be further recycled after being thoroughly washed by ultrapure water, and after the adsorbents are recycled for 5 times, the recycling rate reaches over 90 percent, which shows that the magnetic carboxymethyl chitosan adsorbent has good regeneration and repeated use performance for adsorbing and removing pollutants in water, and the adsorption capacity cannot be obviously reduced after repeated recycling, so that the magnetic carboxymethyl chitosan adsorbent has great application prospect.
Claims (7)
1. A method for preparing a magnetic carboxymethyl chitosan microsphere adsorbent is characterized by comprising the following steps:
s1 weighing carboxymethyl chitosan powder and Fe3O4Dissolving the powder in deionized water, and stirring to obtain a mixed solution;
s2, adding the mixed solution obtained in the step S1 into a mixed solution of cyclohexane and span 80 at a constant speed, and stirring for 0.5-1 h at 20-30 ℃ to obtain a water-oil suspension;
and S3, adding glutaraldehyde into the suspension prepared in the S2, uniformly mixing, reacting for 4-6 hours at 40-60 ℃, obtaining black microspheres from the suspension through magnetic separation after the reaction is finished, washing the black microspheres with absolute ethyl alcohol and deionized water for multiple times, and freeze-drying to obtain the magnetic carboxymethyl chitosan microsphere adsorbent.
2. The method for preparing the carboxymethyl chitosan adsorbent for adsorbing the cationic dye according to claim 1, wherein in the S1, the carboxymethyl chitosan is dispersed in water at a concentration of 0.045-0.09 g/mL.
3. The method for preparing carboxymethyl chitosan adsorbent adsorbing cationic dye according to claim 1, wherein in S1, carboxymethyl chitosan is mixed with Fe3O4Dispersing in water according to the mass ratio of 2-3: 1.
4. The method for preparing the carboxymethyl chitosan adsorbent for adsorbing the cationic dye according to claim 1, wherein in the step S2, the mass ratio of the carboxymethyl chitosan to the cyclohexane to span 80 is 1-1.5: 115-135 parts by weight: 1.
5. the method for preparing the carboxymethyl chitosan adsorbent for adsorbing the cationic dye according to claim 1, wherein in the step S3, the mass ratio of the carboxymethyl chitosan to the glutaraldehyde is 0.5-1: 1.
6. The application of a magnetic carboxymethyl chitosan adsorbent in cationic dye adsorption is to use the material to remove cationic dyes in water, including but not limited to crystal violet.
7. The application of the magnetic carboxymethyl chitosan adsorbent according to claim 6, wherein the magnetic carboxymethyl chitosan adsorbent is added into a solution containing crystal violet, and the solution is subjected to oscillation reaction for 5-24 hours in a constant-temperature oscillator at the temperature of 25-45 ℃ to adsorb and remove the crystal violet in the solution; the mass ratio of the magnetic carboxymethyl chitosan adsorbent to the crystal violet is 1: 0.02-2.
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| CN111774039A (en) * | 2020-06-12 | 2020-10-16 | 中国热带农业科学院农产品加工研究所 | Preparation and use of recyclable carboxymethyl chitosan/shell powder composite material capable of adsorbing Cd/Pb |
| CN113042006A (en) * | 2021-03-17 | 2021-06-29 | 重庆大学 | Preparation method and application of chitosan magnetic adsorbent wrapped by biomimetic polymer |
| CN113058563A (en) * | 2021-03-08 | 2021-07-02 | 上海应用技术大学 | Magnetic microsphere and preparation method and application thereof |
| CN114316141A (en) * | 2020-10-10 | 2022-04-12 | 中科院广州化学有限公司 | Magnetic carboxymethyl chitosan/acrylic acid/itaconic acid copolymerized hydrogel adsorbent and preparation method and application thereof |
| CN115845814A (en) * | 2022-11-21 | 2023-03-28 | 湖北第二师范学院 | Cyclodextrin modified chitosan microsphere and preparation method and application thereof |
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| CN115845814A (en) * | 2022-11-21 | 2023-03-28 | 湖北第二师范学院 | Cyclodextrin modified chitosan microsphere and preparation method and application thereof |
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