CN102258981A - Method for preparing magnetic chitosan nano particles and processing heavy metal wastewater - Google Patents

Method for preparing magnetic chitosan nano particles and processing heavy metal wastewater Download PDF

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Publication number
CN102258981A
CN102258981A CN 201110141164 CN201110141164A CN102258981A CN 102258981 A CN102258981 A CN 102258981A CN 201110141164 CN201110141164 CN 201110141164 CN 201110141164 A CN201110141164 A CN 201110141164A CN 102258981 A CN102258981 A CN 102258981A
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chitosan
magnetic nanoparticle
chitosan magnetic
ethyl acetate
solution
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CN102258981B (en
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王建龙
陈玉伟
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Tsinghua University
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Tsinghua University
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Abstract

The invention discloses a method for preparing magnetic chitosan nano particles and processing heavy metal wastewater, belonging to the technical field of material preparation. The method disclosed by the invention comprises the following steps: firstly, weighing ferrous salt and ferric salt as raw materials for preparing a magnetic material, wherein the raw materials are dispersed in a chitosan acetic acid solution after being dissolved; and dropping the mixed liquor into alkali liquor through an injector to obtain the magnetic chitosan particles, wherein the prepared magnetic chitosan particles are provided with a chitosan-nano ferroferric oxide core shell structure and a nano biological absorption material with excellent absorption performance. The method disclosed by the invention is simple and easy to operate. The nano biological absorption material prepared by the method disclosed by the invention is used for processing the heavy metal wastewater.

Description

The method of the preparation of chitosan magnetic nanoparticle and processing heavy metal wastewater thereby thereof
Technical field
The invention belongs to technical field of material, be specifically related to a kind of preparation of chitosan magnetic nanoparticle and the method for processing heavy metal wastewater thereby thereof.
Background technology
Shitosan is one of natural macromolecular material of excellent performance, and shitosan precursor chitin extensively is present in shellfish such as shrimp crab, is to be only second to cellulosic second largest class natural polymer in the world.Shitosan is a chitin deacetylase base product, contains active group-NH in the strand 2With-OH, has good complexing, the heavy metal ion in can the complexing water body.
But shitosan also exists weak point in actual applications, at first Ruo chemoresistance and strong mechanical constraints the application of chitosan gel rubber nanoparticle, secondly pollutant is difficult to separate from water body effectively apace behind adsorbing and removing.In recent years, magnetic separation technique has been applied in the water treatment field, and it is the effect by magnetic field force, to a kind of technology that different magnetisable materials separate, has that treating capacity is big, liquid-solid separation efficiency is high and advantage such as floor space is little.
Shitosan itself does not have magnetic, with shitosan and magnetisable material Fe 3O 4Organically combine, forming with the magnetisable material is nuclear, and shitosan is the so-called nucleocapsid structure of shell, thereby realize magnetization, and then adopt magnetic separation technique to reach the purpose of quick separation, simultaneously material, the mechanical stability of chitosan nanoparticles has also been strengthened in the adding of magnetic material.In addition, the also renewable under certain condition and recycling of chitosan magnetic nanoparticle makes it have more application prospect in water treatment field.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of chitosan magnetic nanoparticle.
The present invention also aims to provide a kind of chitosan magnetic nanoparticle to handle the method for heavy metal wastewater thereby.
A kind of preparation method of chitosan magnetic nanoparticle, carry out according to following steps:
(1) shitosan is dissolved in the 100mL acetic acid solution, makes the shitosan acetic acid solution, then trivalent iron salt and divalent iron salt are dissolved in the shitosan acetic acid solution, stir 1-4h it is mixed, and placed 0.3-2 hour;
(2) ethyl acetate being joined mass fraction is in 30% the NaOH solution, to mix, and makes the NaOH solution that contains ethyl acetate;
(3) slowly splash into step (1) gained solution in the NaOH solution that contains ethyl acetate with syringe, slowly stir 1-5h, the chitosan gel rubber nanoparticle is solidified, the NaOH solution that residue is contained ethyl acetate is outwelled, the particulate deionized water repeated washing that forms, until washing lotion becomes till the neutrality, obtain the chitosan magnetic nanoparticle, it is standby to place deionized water to preserve the chitosan magnetic nanoparticle.
It is that the volume ratio of 30% NaOH solution is (1-10) that step (2) adds ethyl acetate and mass fraction: 50.
The mol ratio that step (1) adds trivalent iron salt and divalent iron salt is (1-4): 1.
A kind of chitosan magnetic nanoparticle is handled the method for heavy metal wastewater thereby, will contain Cu 2+Waste water solution is put into container, adds the chitosan magnetic nanoparticle, stirs or vibration 4-24h.
Beneficial effect of the present invention: chitosan magnetic method for preparing Nano fine grains of the present invention is simple, and entire reaction course can be finished under temperate condition, and raw materials used cheap and easy to get, environmental condition does not have specific (special) requirements to external world, and it is little to take up room; With respect to shitosan, chitosan magnetic nanoparticle mechanical strength height, and magnetic separation technique can reach the purpose of quick separation; With respect to the existing treatment technology of heavy metal, the prepared material cost of the present invention is lower, and does not have secondary pollution.
Description of drawings
The Fe that Fig. 1 is pure 3O 4XRD figure with the chitosan magnetic nanoparticle;
Among the figure, 1-Fe 3O 4, 2-chitosan magnetic nanoparticle.
Fig. 2 chitosan magnetic nanoparticle Adsorption of Cu 2+Performance.
The variation diagram of the different initial pH value magnetic of Fig. 3 chitosan nanoparticles adsorption capacity.
The specific embodiment
The present invention will be further described below in conjunction with the drawings and specific embodiments.
Embodiment 1
The preparation method of chitosan magnetic nanoparticle, carry out according to following steps:
(1) the 2g shitosan is dissolved in the 100mL acetic acid solution, makes the shitosan acetic acid solution, then with 2.7g Fecl 36H 2O and 2.8g FeSO 4.7H 2O (mol ratio 1: 1) is dissolved in the shitosan acetic acid solution, stirs 1h it is mixed, and placed 0.3 hour;
(2) 6mL ethyl acetate being joined the 300mL mass fraction is in 30% the NaOH solution, to mix, and makes the NaOH solution that contains ethyl acetate;
(3) slowly splash into step (1) gained solution in the NaOH solution that contains ethyl acetate with syringe, slowly stir 1h, the chitosan gel rubber nanoparticle is solidified, the NaOH solution that residue is contained ethyl acetate is outwelled, the particulate deionized water repeated washing that forms, until washing lotion becomes till the neutrality, obtain the chitosan magnetic nanoparticle, it is standby to place deionized water to preserve the chitosan magnetic nanoparticle.
Embodiment 2
The preparation method of chitosan magnetic nanoparticle, carry out according to following steps:
(1) the 4g shitosan is dissolved in the 100mL acetic acid solution, makes the shitosan acetic acid solution, then with 5.4g Fecl 36H 2O and 2.8g FeSO 4.7H 2O (mol ratio 2: 1) is dissolved in the shitosan acetic acid solution, stirs 2h it is mixed, and placed 0.5 hour;
(2) 7.5mL ethyl acetate being joined the 300mL mass fraction is in 30% the NaOH solution, to mix, and makes the NaOH solution that contains ethyl acetate;
(3) slowly splash into step (1) gained solution in the NaOH solution that contains ethyl acetate with syringe, slowly stir 3h, the chitosan gel rubber nanoparticle is solidified, the NaOH solution that residue is contained ethyl acetate is outwelled, the particulate deionized water repeated washing that forms, until washing lotion becomes till the neutrality, obtain the chitosan magnetic nanoparticle, it is standby to place deionized water to preserve the chitosan magnetic nanoparticle.
Sample is dry under 60 ℃ of conditions in vacuum drying chamber, and dry sample carries out XRD analysis, and with pure Fe 3O 4XRD figure compare, the result is as shown in Figure 1.
Embodiment 3
The preparation method of chitosan magnetic nanoparticle, carry out according to following steps:
(1) the 6g shitosan is dissolved in the 100mL acetic acid solution, makes the shitosan acetic acid solution, then with 10.8gFecl 36H 2O and 2.8gFeSO 4.7H 2O (mol ratio 4: 1) is dissolved in the shitosan acetic acid solution, stirs 4h it is mixed, and placed 2 hours;
(2) 30mL ethyl acetate being joined the 300mL mass fraction is in 30% the NaOH solution, to mix, and makes the NaOH solution that contains ethyl acetate;
(3) slowly splash into step (1) gained solution in the NaOH solution that contains ethyl acetate with syringe, slowly stir 5h, the chitosan gel rubber nanoparticle is solidified, the NaOH solution that residue is contained ethyl acetate is outwelled, the particulate deionized water repeated washing that forms, until washing lotion becomes till the neutrality, obtain the chitosan magnetic nanoparticle, it is standby to place deionized water to preserve the chitosan magnetic nanoparticle.
Embodiment 4 chitosan magnetic nanoparticles are used for Cu 2+Absorption remove research
Embodiment 2 prepared chitosan magnetic nanoparticles are used for Cu 2+Absorption remove research, its experimental procedure is as follows:
(1) preparing initial concentration respectively is 50 and the Cu of 100mg/L 2+Solution is reactor with the 20mL reagent bottle, adds 15mL Cu in each reaction bulb 2+(weight is weight in wet base to the chitosan magnetic nanoparticle of the aqueous solution and 0.4g preparation, at first the chitosan magnetic nanoparticle places the 3min that absorbs water on six filter paper, filter paper sops up the surface moisture of nanoparticle, and place on the electronic balance immediately weigh), reaction bulb sealing is placed in the desk-top constant-temperature shaking culture case reacts.Vibration oven temperature, degree is made as 25 ℃, and rotating speed is made as 150rpm.
(2), behind the filtering with microporous membrane of sample, adopt atomic absorption method analysis residue Cu with 0.22 μ m in the different time sampling 2+Concentration.
(3) the preparation initial concentration is the Cu of 100mg/L 2+Solution is regulated its initial pH value and is respectively 3,4,5,5.6, is reactor with the 20mL reagent bottle, adds 15mL Cu in each reaction bulb 2+(weight is weight in wet base to the chitosan magnetic nanoparticle of the aqueous solution and 0.4g preparation, at first the chitosan magnetic nanoparticle places the 3min that absorbs water on six filter paper, filter paper sops up the surface moisture of nanoparticle, and place on the electronic balance immediately weigh), reaction bulb sealing is placed in the desk-top constant-temperature shaking culture case reacts.Vibration oven temperature, degree is made as 25 ℃, and rotating speed is made as 150rpm, reaction 12h, and reaction reaches balance, measures in the solution and remains Cu 2+Concentration.
Accompanying drawing 2 has provided under the different initial concentrations, and chitosan magnetic nanoparticle adsorption capacity is curve over time.As can be seen from the figure, adsorption capacity increased and increases along with the time; In preceding 2h, chitosan magnetic nanoparticle adsorption rate is very fast, the adsorption capacity adsorption capacity about 50% that reaches capacity; When adsorption time was 12h, adsorption process reached balance substantially.By adsorpting data is carried out the dynamics match, available plan second-order kinetics equation is described this adsorption process.
Accompanying drawing 3 has provided the variation diagram of different initial pH value magnetic chitosan nanoparticles adsorption capacities.As can be seen, when the pH value was 3-5.6, the adsorption capacity of chitosan magnetic nanoparticle increased along with the increase of system pH.
Embodiment 5
The chitosan magnetic nanoparticle is handled the method for heavy metal wastewater thereby, will contain Cu 2+Waste water solution is put into container, adds the chitosan magnetic nanoparticle, stirs or vibration 4-24h.

Claims (4)

1. the preparation method of a chitosan magnetic nanoparticle is characterized in that, carries out according to following steps:
(1) shitosan is dissolved in the acetic acid solution, makes the shitosan acetic acid solution, then trivalent iron salt and divalent iron salt are dissolved in the shitosan acetic acid solution, stir 1-4h it is mixed, and placed 0.3-2 hour;
(2) ethyl acetate being joined mass fraction is in 30% the NaOH solution, to mix, and makes the NaOH solution that contains ethyl acetate;
(3) slowly splash into step (1) gained solution in the NaOH solution that contains ethyl acetate with syringe, slowly stir 1-5h, the chitosan gel rubber nanoparticle is solidified, the NaOH solution that residue is contained ethyl acetate is outwelled, the particulate deionized water repeated washing that forms, until washing lotion becomes till the neutrality, obtain the chitosan magnetic nanoparticle, it is standby to place deionized water to preserve the chitosan magnetic nanoparticle.
2. according to the preparation method of the described a kind of chitosan magnetic nanoparticle of claim 1, it is characterized in that it is that the volume ratio of 30% NaOH solution is (1-10) that step (2) adds ethyl acetate and mass fraction: 50.
3. according to the preparation method of the described a kind of chitosan magnetic nanoparticle of claim 1, it is characterized in that the mol ratio that step (1) adds trivalent iron salt and divalent iron salt is (1-4): 1.
4. the method for a chitosan magnetic nanoparticle processing heavy metal wastewater thereby is characterized in that, will contain Cu 2+Waste water solution is put into container, adds the chitosan magnetic nanoparticle, stirs or vibration 4-24h.
CN 201110141164 2011-05-27 2011-05-27 Method for preparing magnetic chitosan nano particles and processing heavy metal wastewater Expired - Fee Related CN102258981B (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103044720A (en) * 2013-01-19 2013-04-17 桂林理工大学 Preparation method of magnetic peach gum
CN103480341A (en) * 2013-10-14 2014-01-01 中国科学院城市环境研究所 Hydrogel material capable of removing arsenic
CN103937779A (en) * 2014-05-13 2014-07-23 清华大学 Preparation and application method of magnetic chitosan biological immobilized particles
CN103949226A (en) * 2014-05-13 2014-07-30 清华大学 Preparation and application methods of magnetic polyvinyl alcohol-chitosan particles
CN105489330A (en) * 2015-11-27 2016-04-13 中北大学 Supergravity preparation method for chitosan-based magnetic nanomaterial
CN105854812A (en) * 2016-04-20 2016-08-17 中建中环工程有限公司 Liquid-phase mercury adsorbent and preparation method and application thereof
CN106732435A (en) * 2017-02-06 2017-05-31 武汉理工大学 A kind of Fe3O4The method that the co-precipitation of/shitosan prepares chitosan magnetic adsorbent
CN106914219A (en) * 2017-04-07 2017-07-04 安徽工业大学 A kind of application of magnetic carbosphere Cr VI in waste water is removed
CN108714415A (en) * 2018-06-22 2018-10-30 四川建筑职业技术学院 A kind of amination chitosan magnetic adsorbent and preparation method thereof
CN109126729A (en) * 2018-09-07 2019-01-04 北京工业大学 The application of Diclofenac in the method and removal waste water of a kind of ethylenediamine modified magnetic chitosan
CN114195208A (en) * 2021-12-09 2022-03-18 陕西关天易景科技有限公司 Composite sewage treatment agent and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101172096A (en) * 2007-11-30 2008-05-07 重庆医科大学附属儿童医院 Target controlling and releasing system for magnetic microsphere carrier in bipolar precipitous magnetic field impulse hunting magnetic field
CN101279776A (en) * 2008-05-21 2008-10-08 东华大学 Novel method for fast removing cupric ion with magnetic sorbent
CN101637709A (en) * 2009-07-10 2010-02-03 广东海洋大学 Methods for preparing carboxymethyl chitosan magnetic microspheres and adsorbing cadmium in oyster meat by using carboxymethyl chitosan magnetic microspheres
EP2251050A1 (en) * 2008-03-12 2010-11-17 AnGes MG, Inc. Drug elution-type catheter and method for manufacturing the drug elution-type catheter

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101172096A (en) * 2007-11-30 2008-05-07 重庆医科大学附属儿童医院 Target controlling and releasing system for magnetic microsphere carrier in bipolar precipitous magnetic field impulse hunting magnetic field
EP2251050A1 (en) * 2008-03-12 2010-11-17 AnGes MG, Inc. Drug elution-type catheter and method for manufacturing the drug elution-type catheter
CN101279776A (en) * 2008-05-21 2008-10-08 东华大学 Novel method for fast removing cupric ion with magnetic sorbent
CN101637709A (en) * 2009-07-10 2010-02-03 广东海洋大学 Methods for preparing carboxymethyl chitosan magnetic microspheres and adsorbing cadmium in oyster meat by using carboxymethyl chitosan magnetic microspheres

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103044720A (en) * 2013-01-19 2013-04-17 桂林理工大学 Preparation method of magnetic peach gum
CN103480341A (en) * 2013-10-14 2014-01-01 中国科学院城市环境研究所 Hydrogel material capable of removing arsenic
CN103937779A (en) * 2014-05-13 2014-07-23 清华大学 Preparation and application method of magnetic chitosan biological immobilized particles
CN103949226A (en) * 2014-05-13 2014-07-30 清华大学 Preparation and application methods of magnetic polyvinyl alcohol-chitosan particles
CN105489330B (en) * 2015-11-27 2017-10-31 中北大学 A kind of hypergravity preparation method of chitosan-based magnetic Nano material
CN105489330A (en) * 2015-11-27 2016-04-13 中北大学 Supergravity preparation method for chitosan-based magnetic nanomaterial
CN105854812A (en) * 2016-04-20 2016-08-17 中建中环工程有限公司 Liquid-phase mercury adsorbent and preparation method and application thereof
CN106732435A (en) * 2017-02-06 2017-05-31 武汉理工大学 A kind of Fe3O4The method that the co-precipitation of/shitosan prepares chitosan magnetic adsorbent
CN106732435B (en) * 2017-02-06 2019-08-23 武汉理工大学 A kind of Fe3O4The method that the co-precipitation of/chitosan prepares chitosan magnetic adsorbent
CN106914219A (en) * 2017-04-07 2017-07-04 安徽工业大学 A kind of application of magnetic carbosphere Cr VI in waste water is removed
CN108714415A (en) * 2018-06-22 2018-10-30 四川建筑职业技术学院 A kind of amination chitosan magnetic adsorbent and preparation method thereof
CN108714415B (en) * 2018-06-22 2021-12-10 四川建筑职业技术学院 Aminated magnetic chitosan adsorbent and preparation method thereof
CN109126729A (en) * 2018-09-07 2019-01-04 北京工业大学 The application of Diclofenac in the method and removal waste water of a kind of ethylenediamine modified magnetic chitosan
CN109126729B (en) * 2018-09-07 2021-11-12 北京工业大学 Method for modifying magnetic chitosan by using ethylenediamine and application of method for removing diclofenac in wastewater
CN114195208A (en) * 2021-12-09 2022-03-18 陕西关天易景科技有限公司 Composite sewage treatment agent and preparation method thereof

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