CN105709698B - A kind of N- carboxyetbyl chitosans nanometer magnetic bead and its preparation method and application - Google Patents
A kind of N- carboxyetbyl chitosans nanometer magnetic bead and its preparation method and application Download PDFInfo
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- CN105709698B CN105709698B CN201610212609.4A CN201610212609A CN105709698B CN 105709698 B CN105709698 B CN 105709698B CN 201610212609 A CN201610212609 A CN 201610212609A CN 105709698 B CN105709698 B CN 105709698B
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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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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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
- B01J20/28—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
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—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 form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
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- 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
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- 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
Abstract
The invention discloses a kind of N carboxyetbyl chitosans nanometer magnetic beads and its preparation method and application, belong to technical field of chemistry.The preparation method of the N carboxyetbyl chitosans nanometer magnetic bead includes：By N carboxyetbyl chitosans, Fe3O4Nano-particle and crosslinking agent, which are dissolved in acetic acid solution, to be reacted, and after the completion of reaction, adjusts pH value to neutrality, collects sediment, washing, it is dry to get.N carboxyetbyl chitosans are coated on nanometer magnetic bead surface by the present invention, improve the adsorption capacity to metal ion, it is especially significantly better than the similar adsorbent of existing major part in terms of the heavy metals such as Adsorption of Cu (II) and Pb (II), can be applied to the heavy metal in removal sewage；The N carboxyetbyl chitosans nanometer magnetic bead of the present invention can be recycled by magnet, widen its scope of application and condition.
Description
Technical field
The present invention relates to technical field of chemistry, and in particular to a kind of N- carboxyetbyl chitosans nanometer magnetic bead and preparation method thereof
And application.
Background technology
Chitosan (chitosan) is the second largest natural polymer in addition to cellulose, β-(Isosorbide-5-Nitrae) -2- amino -2- deoxidations -
D- glucans (glucose) and β-(Isosorbide-5-Nitrae) -2- acetylaminohydroxyphenylarsonic acid 2- deoxidation-D- glucans (N-Acetyl-D-glucosamine) composition, by first
The deacetylated acquisition under alkaline condition of shell element.It is chitosan abundance, cheap, nontoxic, in addition its excellent inoxidizability,
The good characteristics such as biocidal property, biocompatibility, biological degradability become the hot spot of research, in food, cosmetics, biology
It is widely applied in the fields such as medicine and pharmacy.And chitosan itself is water-soluble poor, seriously limits its processing and application.
In order to improve chitosan applications in various fields, chitosan need to be chemically modified.Contain in chitosan structure
Active-OH ,-NH2, other active groups can be introduced on N or O, for example that currently studies extensively have carboxylic
It methylates, is quaternized, lauroyl sulfonation, hydroxypropylation and PEG- grafting.In addition pertinent literature is reported, with raw materials of chitosan phase
Than a series of properties such as dissolubility, inoxidizability, biocompatibility, antibiotic property of chitosan derivatives have different degrees of
It improves.
Carboxyetbyl chitosan successfully overcomes chitosan disadvantage not soluble in water, and dissolubility greatly improves at basic ph.
Currently, the report carboxyetbyl chitosan such as Huang has preferable free radical scavenging ability, reducing power and external cholic acid binding ability,
There is preferable application in terms of medicine and health care, carboxyetbyl chitosan is as a kind of good biological adsorption agent, carboxyl in addition
As functional group, there is good heavy metal adsorption effect, to administering sewage, environmental protection drives economical with important meaning
Justice.
Currently, problem of environmental pollution caused by toxic heavy metal has attracted more and more attention from people in industrial wastewater, water is dirty
Dye control is increasingly subject to the close attention of environmental protection administration and industrial department.It has developed at present and the adsorbent used is mainly active
Charcoal, synthetic resin, biomass, clay, mud coal, activated sludge etc., but majority, there are of high cost, complicated for operation, adsorption capacity is not
The problems such as height, desorption is difficult.Therefore, it is more and more important to find low cost and high performance environment-friendly type sorbing material.
To be related to a kind of modified magnetic chitosan microball heavy metal ion adsorbed for the invention that notification number is 103263895 B of CN
The preparation method of agent, including chitosan magnetic micro-sphere is prepared by raw material of Chitosan powder, and further by chitosan magnetic
Microballoon is prepared into hydroxypropyl chlorine chitosan magnetic micro-sphere, and using the chitosan microball as parent, thiazolamine is ligand, to magnetic
Property chitosan microball carry out the grafting of hydroxypropyl chlorine magnetic chemical, obtained modified magnetic chitosan microball is heavy metal ion adsorbed
Agent.The modified magnetic chitosan microball adsorbent for heavy metal being prepared using the inventive method is to Hg2+Ion has choosing
Selecting property is adsorbed.Modified magnetic chitosan microball adsorbent for heavy metal chemical stability made from the invention is good, is easy elution,
It only needs a small amount of hydrochloric acid that can elute completely, reduces secondary pollution, and can be in outer quick separating under adding magnetic field condition.
Invention content
The present invention provides a kind of N- carboxyetbyl chitosans nanometer magnetic beads, utilize carboxyl and Fe3O4Nano-particle magnetic absorption
Heavy metal is of great significance to waste water control, environmental protection.
The present invention provides a kind of preparation methods of N- carboxyetbyl chitosans nanometer magnetic bead, include the following steps：By N- carboxylics
Ethyl chitosan, Fe3O4Nano-particle and crosslinking agent, which are dissolved in acetic acid solution, to be reacted, and after the completion of reaction, adjusts pH value into
Property, collect sediment, washing, dry, the obtained N- carboxyetbyl chitosans nanometer magnetic bead.
The Fe3O4Nano-particle and N- carboxyetbyl chitosans are combined together in a manner of co-precipitation.
The degree of substitution of the N- carboxyetbyl chitosans is 0.9~1.1.
The Fe3O4The grain size of nano-particle is 50~100nm.
Preferably, the N- carboxyetbyl chitosans and Fe3O4Nano-particle weight ratio is 1:5~6.More preferably, N-
Carboxyetbyl chitosan and Fe3O4Nano-particle ratio 1:5.4.
Preferably, the crosslinking agent is sodium tripolyphosphate (TPP).Generationization between the online shell glycan of sodium tripolyphosphate
Key is learned, linear molecule is made to be connected with each other, forms reticular structure.Compared to other crosslinking agents have DCP, BPO, DTBP, DBHP,
Double 25 etc., TPP cross-linking effect are best, therefore select TPP as crosslinking agent.
The dosage of crosslinking agent influences the formation of N- carboxyetbyl chitosan reticular structures, on the one hand avoids not filling because of crosslinking
Point, cause when being washed to neutrality, N- carboxyetbyl chitosans are dissolved and lost, and on the other hand avoid crosslinking excessive, reticular structure
It is uneven in magnetic bead surfaces precipitation, influence heavy metal adsorption effect.Preferably, the N- carboxyetbyl chitosans and tripolyphosphate
The weight ratio of sodium is 110~125:1.More preferably, the ratio of the N- carboxyetbyl chitosans and sodium tripolyphosphate is
119:1。
The present invention provides the N- carboxyetbyl chitosans nanometer magnetic beads made from the preparation method.
Purposes the present invention also provides the N- carboxyetbyl chitosans nanometer magnetic bead as adsorbent for heavy metal.
N- carboxyetbyl chitosans nanometer magnetic bead prepared by the present invention can be used to remove heavy metal ions in sewage, adsorption capacity
Better than similar adsorbent.The N- carboxyetbyl chitosans nanometer magnetic bead of the present invention is in the HAc-NaAc buffer solutions that pH is 4.6, to Cu
(II) adsorption capacity reaches 352.6mg/g, in the HAc-NaAc buffer solutions that pH is 5.4, is reached to the adsorption capacity of Pb (II)
To 533.9mg/g (0.002g adsorbents, in terms of the N- carboxyetbyl chitosans of 14.4% content).
By the recyclable heavy metal of magnet adsorption nanometer magnetic bead, and N- carboxyetbyl chitosans nanometer magnetic bead can repeat to make
With.
The advantageous effect that the present invention has：(1) N- carboxyetbyl chitosans are coated on nanometer magnetic bead surface by the present invention, are improved
To the adsorption capacity of metal ion, especially existing major part is significantly better than in terms of the heavy metals such as Adsorption of Cu (II) and Pb (II)
Similar adsorbent；(2) N- carboxyetbyl chitosans nanometer magnetic bead of the invention can be recycled by magnet, widen its scope of application
And condition.
Description of the drawings
Fig. 1 is that N- carboxyetbyl chitosans nanometer magnetic bead of the present invention prepares schematic diagram.
Fig. 2 is N- carboxyetbyl chitosans nanometer magnetic bead infrared spectrum testing result of the present invention.
Fig. 3 is N- carboxyetbyl chitosans nanometer magnetic bead thermal gravimetric analysis results of the present invention.
Specific implementation mode
It further illustrates the present invention with reference to embodiments.But following embodiments are only the preferred implementation of the present invention
Example, and it is not all.Based on the implementation example in the implementation mode, those skilled in the art are without making creative work
Obtained other embodiments, belong to protection scope of the present invention.
Embodiment 1
1, the preparation of nanometer magnetic bead
Take 5.4g FeCl3·6H2O and 1.99g FeCl2·4H2O is dissolved in 50mL deionized waters.Quickly to mixture
Middle addition 12mL concentrated ammonia liquors are simultaneously stirred continuously, at 80 DEG C, N2Reaction 2 hours is vigorously stirred under protection.After reaction, it spends
The pH that ion water washing is precipitated to cleaning solution is in neutrality, filtered on buchner funnel.Obtained solid forced air drying under the conditions of 60 DEG C
Case is dried 12 hours, up to Fe after grinding3O4Magnetic bead.
2, the preparation of N- carboxyetbyl chitosans
2g chitosans press 1 with 3- chloropropionic acids：5 molar ratio is dissolved in 140mL ddH2In O, magnetic agitation 1 hour, until shell
Glycan fully dissolves.By the NaHCO with 3- chloropropionic acid equimolar amounts3It is slowly added into chitosan solution in batches, stirs 30 points
More than clock, to remove excessive CO2(pH about 6.5).Later, magnetic agitation at 60 DEG C of reaction system starts to react timing.6 is small
6g sodium bicarbonates are added to reaction system in Shi Hou, and after 2 hours, the pH of mixture is adjusted to by the NaOH for adding 10wt%
8.5.When after reaction, orange solution is filtered to remove to the insoluble solid generated in reaction, and is poured into solution pure
Ethyl alcohol to concentration of alcohol is 75%, and sand core funnel filters out liquid, ddH2O dissolving precipitations, then use the (retention of cellulose dialysis bag
Molecular weight 3500) dialysis 2-3 days is carried out to product, and be freeze-dried, the N-CECS purified, -20 DEG C of refrigerator long-term preservations.
3, the preparation of N- carboxyetbyl chitosans nanometer magnetic bead
0.149g N-CECS are dissolved with the acetic acid solution of 10mL 1%, 1.25mL 1mg/mL TPP solution is then added and makees
For crosslinking agent, and it is incubated at room temperature 10 minutes.0.8g suspended magnetic nanometer Fes are added3O4, suspension is vigorously stirred 30 points
Clock, to ensure that N-CECS is coated on nano grain surface.It is then slowly added into 1M 0.8mL sodium hydroxides to suspension and precipitates
The nanoparticle of cladding.Resulting N- carboxyetbyl chitosans nanometer magnetic bead is recycled from suspension by magnet, is used
Deionized water washing reaches 7.0 to pH for several times, then is dried in vacuo for 24 hours at 60 DEG C, and is stored in -20 DEG C of refrigerators and preserves, at this time
The theoretical value content of N-CECS is 15.7% in N- carboxyetbyl chitosan nanometer magnetic beads, and detailed process is as shown in Figure 1.
4, characterization measures
4.1 infrared analysis methods：Fourier infrared linear light spectrometer power switch is opened, waits for instrument stabilizer, is opened on computer
7.0 softwares of opus, arrange parameter.Prepare sample sheet with pressed disc method, first with ethyl alcohol wash tabletting used in utensil, be evaporated naturally
After take 1.5mg samples, by 1:100 ratio is added potassium bromide, and the mixture of ground sample and potassium bromide waits being tested at powdered
It takes after substance and the mixture of potassium bromide are adherent three times and pours into mold in right amount, swager is integrally put on press, oil is locked
It compresses switch, pushes rocking bar, pressure is depressed under 10MPa and keeps 30s, open oil pressure shut-off switch later, take out swager, it is careful to take out
Sample (homogeneous transparent does not rupture), magnetic sample frame is put by the diaphragm after pressure.Background measurement is first carried out, then carries out sample
Product measure, and appropriateness is smooth and preserves data.The results are shown in Figure 2.
The characteristic peak of N-CECS is in 1562cm-1And 1416cm-1, in respectively-COONa the antisymmetry of C=O it is flexible and-
C=O's is symmetrical flexible in COONa, in 3439cm-1And 1074cm-1Absorption peak be O-H stretching vibrations and C-O stretching vibrations.
Fe3O4In the characteristic peaks of Fe-O keys appear in 589cm-1Place.By cross-linked composite compared with N-CECS, maximum difference is former
First in 3439cm-1Corresponding to O-H stretching vibrations, it is transferred to lower wave number 3418cm-1, originally in 1562cm-1Corresponding to-
The antisymmetry of C=O is flexible in COONa, goes to higher wave number 1584cm-1, originally in 1074cm-1It shakes corresponding to C-O is flexible
It is dynamic, go to lower wave number 1064cm-1, with Fe3O4It compares, originally in 589cm-1It is transferred to more corresponding to the characteristic peak of Fe-O keys
Low wave number 585cm-1, these the result shows that N- carboxyetbyl chitosan nanometer magnetic beads synthesis.
4.2 gravitational thermal analysis method：Thermogravimetric analyzer power switch, preheating 30min or so are opened, N is set2Flow 20mL/
Min, 20 DEG C/min of heating rate.It is put into the crucible for filling sample 10mg, empty crucible compares, and waits for 3 minutes, waits for above instrument
Quality show amplitude of variation very little when, run instrument, after there is hot weight curve, the results are shown in Figure 3.
The thermogravimetric curve of N- carboxyetbyl chitosan nanometer magnetic beads shows that N-CECS starts to be dehydrated at 49 DEG C or so, at 226 DEG C
N-CECS main chains start to decompose, until 626 DEG C of whens decompose completely substantially, 885 DEG C of residual weights are 13.4%.And Fe3O4In N2Under gas shielded
Almost without decomposition, the residual weight of compound is 85.6% at 885 DEG C, illustrates Fe in compound3O4Content is about 85.6%, N-CECS
Content is about 14.4%, this coincide substantially with theoretical value.Further, since thermogravimetric test used sample is grab sample, by Fe3O4
Fe can be calculated with the initial dosage of N-CECS3O4Content about 84.3%, this shows that N- carboxyetbyl chitosan nanometer magnetic beads are distributed
Uniformly, property is relatively stable.
5, heavy metal adsorption is tested：The CuSO of 40mM is configured with the pH HAc-NaAc buffer solutions for being 4.64Solution is with pH
The lead nitrate solution of 5.4 HAc-NaAc buffer solutions configuration 3.02mM, 0.22 μm of filtering with microporous membrane.Take respectively 0.5mL,
The above-mentioned solution of 1.0mL, 1.5mL adds to 5mL centrifuge tubes, weighs 0.002g N- carboxyetbyl chitosan nanometer magnetic beads, adds HAc-
NaAc buffer solutions are to 4mL.Above-mentioned absorption system is placed on shaking table and is shaken, condition 200rpm, 25 DEG C, 3h.After absorption
It takes out, centrifugal condition 8000rpm, 20 DEG C, 10min.Three groups of parallel laboratory test, blank group is not added with adsorbent, in Atomic absorption point
Heavy metal concentration is measured on light photometer (AA-6300C).
The adsorption experiment of N- carboxyetbyl chitosan nanometer magnetic beads shows that N- carboxyetbyl chitosans nanometer magnetic bead is to Cu's (II)
Adsorption capacity is 352.6mg/g (0.002g adsorbents, in terms of the N- carboxyetbyl chitosans of 14.4% content), with document
(Carbohydrate Polymers,2016,138:301-308) it compares, is 1.70 times of carboxyetbyl chitosan adsorbance,
It is 2.38 times of chitosan nano magnetic bead adsorbance, is 2.64 times of thiocarbamide modified magnetic chitosan microball.
N- carboxyetbyl chitosans nanometer magnetic bead to the adsorption capacity of Pb (II) be 533.9mg/g (0.002g adsorbents, with
The N- carboxyetbyl chitosans meter of 14.4% content), with document (Chemical Research and Application, 2013,
4:554-557) it compares, is Fe3O45.06 times of/chitosan composite nanoparticle adsorbance.
It is most of that the above results show that the N- carboxyetbyl chitosans nanometer magnetic bead of the present invention is better than in terms of adsorbing heavy metal
Similar adsorbent.
Claims (2)
1. a kind of purposes of N- carboxyetbyl chitosans nanometer magnetic bead as heavy metal ion Cu (II) or Pb (II) adsorbent, special
Sign is that the preparation method of the N- carboxyetbyl chitosans nanometer magnetic bead includes the following steps：By N- carboxyetbyl chitosans,
Fe3O4Nano-particle and crosslinking agent, which are dissolved in acetic acid solution, to be reacted, and after the completion of reaction, is adjusted pH value to neutrality, is collected precipitation
Object, washing, dry, the obtained N- carboxyetbyl chitosans nanometer magnetic bead；
The degree of substitution of the N- carboxyetbyl chitosans is 0.9~1.1；
The N- carboxyetbyl chitosans and Fe3O4Nano-particle weight ratio is 1:5~6；
The crosslinking agent is sodium tripolyphosphate；The weight ratio of the N- carboxyetbyl chitosans and sodium tripolyphosphate be 110~
125:1。
2. purposes as described in claim 1, which is characterized in that the Fe3O4The grain size of nano-particle is 50~100nm.
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| CN106512962B (en) * | 2017-01-18 | 2019-05-21 | 上海海洋大学 | A kind of loading Fe3O4Polyeletrolyte nano material preparation method and its usage |
| CN110801814A (en) * | 2019-11-01 | 2020-02-18 | 华东交通大学 | Preparation method of magnetic amino walnut shell biochar novel adsorbent |
| CN114768600B (en) * | 2020-12-21 | 2023-11-14 | 绍兴越信环保科技有限公司 | Stirring device for preparing fly ash magnetic bead-activated carbon composite adsorbent |
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Address after: 311100 floor 2, building 4, No. 2959, yuhangtang Road, Cangqian street, Yuhang District, Hangzhou City, Zhejiang Province Patentee after: HANGZHOU DANWEI BIOTECHNOLOGY Co.,Ltd. Address before: 311121 2 storeys, 4 blocks, No. 2959 Yuhangtang Road, Cangqian Street, Xihu District, Hangzhou City, Zhejiang Province Patentee before: HANGZHOU DANWEI BIOTECHNOLOGY Co.,Ltd. |
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