CN110327896A - A kind of magnetism poly-dopamine/carboxymethyl chitosan adsorbent and the preparation method and application thereof - Google Patents
A kind of magnetism poly-dopamine/carboxymethyl chitosan adsorbent and the preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of magnetic poly-dopamine/carboxymethyl chitosan adsorbents and the preparation method and application thereof.Method includes the following steps: carboxymethyl chitosan, dopamine and magnetic ferroferric oxide nanometer particle reaction are first added crosslinking agent reaction；Or dopamine and magnetic ferroferric oxide nanometer particle reaction are first added into carboxymethyl chitosan and crosslinking agent reaction；Magnetism poly-dopamine/carboxymethyl chitosan adsorbent is made, wherein magnetic ferroferric oxide nanometer particle is prepared by coprecipitation.Magnetic adsorbent prepared by method of the invention has very big adsorbance to cationic dyes aqueous solution absorption property with higher, and to dye of positive ion type aqueous solution, while having efficient renewable ability.
Description
Technical field
The invention belongs to polymeric material fields, and in particular to a kind of magnetism poly-dopamine/carboxymethyl chitosan adsorbent
And the preparation method and application thereof.
Background technique
With the fast development of industrialzation and urbanization, water pollution has become the focus of people's extensive concern, water pollution master
It to include heavy metal ion, dye discoloration etc., wherein dye discoloration is mainly derived from weaving, leather, plastics, papermaking, cosmetics
Deng other manufacturing industry.Since most of dyestuffs have complicated aromatic structure, these dye structures are stablized, and not degradable, because
This most of dyestuff can long-term existence be in natural environment and accumulation is to higher concentration, thus to ecological environment and human health structure
At grave danger.Some researches show that dyestuffs to cause directly to damage to the liver of human body, digestive system and central nervous system
Evil.Therefore, dyestuff is removed from contaminant water before contaminant water discharge, to protect environment, it is necessary to explore effective method.?
In past decades, various technologies, such as chemical oxidation, flocculation-condensation, precipitating, photocatalytic degradation and film have been developed
Traditional methods such as filtering, although these methods have been achieved for some achievements in terms of dyestuff removal, these feasible sides
The limitation that method also has its intrinsic, such as high energy demand, high operating cost and secondary pollution etc..Therefore, existing technology is also
To be modified and development.
Summary of the invention
To solve the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is that providing a kind of poly- DOPA of magnetism
Amine/carboxymethyl chitosan adsorbent preparation method.
Another object of the present invention is to provide a kind of magnetism poly-dopamine/carboxymethyl chitosans made from the above method to inhale
Attached dose.
A further object of the present invention is to provide a kind of above-mentioned magnetic poly-dopamine/carboxymethyl chitosan adsorbents in dyestuff
Application in absorption.
The object of the invention is achieved through the following technical solutions:
It is a kind of magnetism poly-dopamine/carboxymethyl chitosan adsorbent preparation method, specifically: by carboxymethyl chitosan,
Dopamine and magnetic ferroferric oxide nanometer particle are scattered in buffer solution, after being reacted 5~24 hours at 10~50 DEG C, then
Crosslinking agent is added to react 5~24 hours, collects product, it is dry, obtain magnetic poly-dopamine/carboxymethyl chitosan adsorbent.
The carboxymethyl chitosan, dopamine, crosslinking agent and magnetic ferroferric oxide nanometer particle mass ratio be preferably
(1~4): (1~4): (1~20): (1~4).
Concentration of the dopamine in buffer solution is preferably 1~10mg/mL；More preferably 2~10mg/mL；It is optimal
It is selected as 2mg/mL.
The magnetic ferroferric oxide nanometer particle is preferably made by following methods: under nitrogen or atmosphere of inert gases,
Fe will be contained3+And Fe2+Compound according to Fe3+With Fe2+Molar ratio be (1~5): 1 ratio is soluble in water, be warming up to 60~
85 DEG C, alkaline solution is added, reacts 2~3h, cooling, washing collects and dry, obtains magnetic ferroferric oxide nanometer particle.
It is described to contain Fe3+Compound concentration in water be preferably 1.0~3.5mol/L, more preferably 1.85mol/L；Institute
It states the alkaline matter in alkaline solution and contains Fe3+Compound molar ratio be preferably (3.5~4.5): 1, more preferably 4.18:
1。
It is described to contain Fe3+Compound be preferably FeCl3·6H2O and/or Fe (NO3)3·9H2O；It is described to contain Fe2+Chemical combination
Object is preferably FeSO4·7H2O、FeCl2·4H2O and FeSO4·4H2One or more of O.
The alkaline solution is preferably NaOH solution, NH3·H2One or more of O solution and KOH solution；More
Preferably NH3·H2O solution；The solvent of the alkaline solution is water.
The NH3·H2The volumetric concentration of O solution is preferably 15~40%；The quality of the NaOH solution and KOH solution is dense
Degree preferably 15~40%.
Washing in the magnetic ferroferric oxide nanometer particle-making step preferably with ethyl alcohol and is washed to respectively
Property；Described collect is carried out using permanent magnet；The drying preferably carries out under vacuum conditions, and dry temperature is 25~70
DEG C, it is dry to constant weight.
The dispersion is preferably ultrasonic disperse, and the time of dispersion is preferably 3~30min.
The buffer solution is preferably Tris-HCl buffer solution；The concentration of the Tris-HCl buffer solution is preferably 1
~50mmol；More preferably 10~50mmol；Most preferably 10mmol.
The pH of the Tris-HCl buffer solution is preferably 8.0~9.5；More preferably 8.5.
The speed of agitator of the reaction is preferably 300~700rpm；More preferably 500rpm.
The crosslinking agent is preferably glutaraldehyde, N, and N'- methylene-bisacrylamide (MBA), formaldehyde, ethylene glycol two shrink sweet
One or more of oily ether and epoxychloropropane.
The crosslinking agent is added preferably in the form of cross-linking agent aqueous solution, and the volumetric concentration of the cross-linking agent aqueous solution is preferred
It is 2~50%, more 25%.
The collection product is collected using permanent magnet, and the product of collection is washed with water；The drying is preferred
For vacuum drying, dry temperature is preferably 25~60 DEG C, dry to constant weight.
A kind of preparation method of magnetism poly-dopamine/carboxymethyl chitosan adsorbent, specifically: by dopamine and magnetism four
Fe 3 O nano particle is scattered in buffer solution, after reacting 5~24 hours at 10~50 DEG C, is collected product, is cleaned, does
It is dry, obtain magnetic poly-dopamine nano particle；It is molten that buffering is dispersed by magnetic poly-dopamine nano particle and carboxymethyl chitosan
In liquid, after being reacted 5~12 hours at 10~50 DEG C, adds crosslinking agent and react 5~12 hours, collect product, it is dry, it obtains
Magnetic poly-dopamine/carboxymethyl chitosan adsorbent.
The mass ratio of the dopamine and magnetic ferroferric oxide nanometer particle is preferably (1~4): (1~4), more preferably
For 1:1；The mass ratio of the magnetism poly-dopamine nano particle, carboxymethyl chitosan and crosslinking agent is preferably (1~4): (1~
6): (2~8), more preferably 1:2:4.
Concentration of the dopamine in buffer solution is preferably 1~10mg/mL；More preferably 2~10mg/mL；It is optimal
It is selected as 2mg/mL.
The magnetic ferroferric oxide nanometer particle is preferably made by following methods: under nitrogen or atmosphere of inert gases,
Fe will be contained3+And Fe2+Compound according to Fe3+With Fe2+Molar ratio be (1~5): 1 ratio is soluble in water, be warming up to 60~
85 DEG C, alkaline solution is added, reacts 2~3h, cooling, washing collects and dry, obtains magnetic ferroferric oxide nanometer particle.
It is described to contain Fe3+Compound concentration in water be preferably 1.0~3.5mol/L, more preferably 1.85mol/L；Institute
It states the alkaline matter in alkaline solution and contains Fe3+Compound molar ratio be preferably (3.5~4.5): 1, more preferably 4.18:
1。
It is described to contain Fe3+Compound be preferably FeCl3·6H2O and/or Fe (NO3)3·9H2O；It is described to contain Fe2+Chemical combination
Object is preferably FeSO4·7H2O、FeCl2·4H2O and FeSO4·4H2One or more of O.
The alkaline solution is preferably NaOH solution, NH3·H2One or more of O solution and KOH solution；More
Preferably NH3·H2O solution；The solvent of the alkaline solution is water.
The NH3·H2The volumetric concentration of O solution is preferably 15~40%；The quality of the NaOH solution and KOH solution is dense
Degree preferably 15~40%.
Washing in the magnetic ferroferric oxide nanometer particle-making step preferably with ethyl alcohol and is washed to respectively
Property；Described collect is carried out using permanent magnet；The drying preferably carries out under vacuum conditions, and dry temperature is 25~70
DEG C, it is dry to constant weight.
The dispersion is preferably ultrasonic disperse, and the time of dispersion is preferably 3~30min.
The buffer solution is preferably Tris-HCl buffer solution；The concentration of the Tris-HCl buffer solution is preferably 1
~50mmol；More preferably 10~50mmol；Most preferably 10mmol.
The pH of the Tris-HCl buffer solution is preferably 8.0~9.5；More preferably 8.5.
The speed of agitator of the reaction is preferably 300~700rpm；More preferably 500rpm.
Concentration of the magnetism poly-dopamine nano particle in buffer solution is preferably 1~10mg/mL；More preferably 2
~10mg/mL；Most preferably 2mg/mL.
The crosslinking agent is preferably glutaraldehyde, N, and N'- methylene-bisacrylamide (MBA), formaldehyde, ethylene glycol two shrink sweet
One or more of oily ether and epoxychloropropane.
The crosslinking agent is added preferably in the form of cross-linking agent aqueous solution, and the volumetric concentration of the cross-linking agent aqueous solution is preferred
It is 2~50%, more 25%.
The cleaning preferably washes with water 1~3 time.
The collection product is collected using permanent magnet, and the product of collection is washed with water；The drying is preferred
For vacuum drying, dry temperature is preferably 25~60 DEG C, dry to constant weight.
A kind of magnetism poly-dopamine/carboxymethyl chitosan adsorbent made from the above method.
A kind of application of the above-mentioned magnetic poly-dopamine/carboxymethyl chitosan adsorbent in organic dyestuff absorption.
The organic dyestuff is preferably cation and/or anionic organic dyes；The Cationic organic dyes are preferably
One or more of methylene blue, crystal violet and malachite green；The anionic organic dyes be preferably methyl orange, just
One or more of arnotto and Eosin B.
The method of the application are as follows: magnetic poly-dopamine/carboxymethyl chitosan adsorbent is added to containing the water-soluble of dyestuff
In liquid, 5~360min is adsorbed at 20~60 DEG C, the initial concentration of dyestuff is 50~500mg/L in the aqueous solution.
The pH value of the aqueous solution is preferably 2~11.
Magnetism poly-dopamine/the concentration of carboxymethyl chitosan adsorbent in aqueous solution is preferably 0.2~50mg/
ML, more preferably 0.2~1.4mg/mL.
The hunting speed of the absorption is preferably 100~300rpm, more preferably 180rpm.
Compared with prior art, the present invention has the following advantages and beneficial effects:
(1) raw material that the present invention prepares magnetic poly-dopamine/carboxymethyl chitosan adsorbent is easy to get, is from a wealth of sources.
(2) easily separated after magnetic poly-dopamine produced by the present invention/carboxymethyl chitosan adsorbent absorption, it is repeatable to make
With.
(3) preparation method of the present invention is simple, the reaction condition of no harshness, environmental-friendly, without toxic organic molten
Agent is also generated without toxic by-product.
Detailed description of the invention
Fig. 1 is the synthetic line figure of the magnetic poly-dopamine/carboxymethyl chitosan adsorbent of the present invention.
Fig. 2 is magnetism poly-dopamine/carboxymethyl chitosan adsorbent infrared spectroscopy (IR) figure made from embodiment 1.
Fig. 3 is magnetism poly-dopamine/carboxymethyl chitosan adsorbent transmission electron microscope made from embodiment 1
(TEM) figure, amplification factor are 12000 times.
Fig. 4 is the adsorption effect figure under NaCl concentration different in embodiment 6 to aqueous solution of methylene blue.
Fig. 5 is magnetic adsorbent in embodiment 11 to the sorption cycle number effect picture of aqueous solution of methylene blue.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Tris-HCl buffer solution described in the embodiment of the present application is prepared by following methods: 2.42gTris is added 2L's
1.9L distilled water is added in beaker, is completely dissolved within ultrasound 5 minutes to Tris, adjusts pH=8.5 with 1mol HCl to get arriving
The Tris-HCl buffer solution of 10mmol/L.
Embodiment 1
(1) synthesis of ferroso-ferric oxide: by the ferrous sulfate tetrahydrate of 25.0g ferric chloride hexahydrate and 15.0g
It being added in four-hole boiling flask, adds 50mL deionized water, then ultrasound is passed through nitrogen protection under condensing unit until dissolution,
After being heated to 80 DEG C, 50mL ammonium hydroxide is added and reacts 3 hours, is cooled to room temperature, is washed till neutrality with deionized water, dehydrated alcohol, uses
Permanent magnet is collected, and arrives magnetic ferroferric oxide nanometer particle to constant weight in 60 DEG C of vacuum drying ovens dryings.
(2) synthesis of magnetic poly-dopamine nano particle: the magnetic ferroferric oxide nanometer of 0.4g step (1) synthesis is weighed
Particle is added in Tris-HCl buffer solution of the 200mL containing dopamine, and wherein dopamine is in Tris-HCl buffer solution
Concentration is 2.0mg/mL, and ultrasound 15 minutes after reacting 24 hours at room temperature with 500rmp mixing speed, is received using permanent magnet
Collection, and cleaned three times with deionized water, magnetic adsorbent is collected with permanent magnet again, is dried extremely in 60 DEG C of vacuum drying oven
Constant weight is to get to magnetic poly-dopamine nano particle.
(3) it the synthesis of magnetic poly-dopamine/carboxymethyl chitosan adsorbent: weighs 0.80g carboxymethyl chitosan and is dissolved in
In 200mL Tris-HCl buffer solution, the magnetic poly-dopamine nano particle of the 0.40g prepared in step (2) is added, is surpassed
Sound 15 minutes, after reacting 6 hours at room temperature with 500rmp mixing speed, the volumetric concentration for adding 12.8mL was 25% penta 2
Aldehyde aqueous solution (i.e. addition 3.2g glutaraldehyde), the reaction was continued 6 hours, is collected using permanent magnet, and clean three with deionized water
It is secondary, magnetic adsorbent is collected with permanent magnet again, is dried in 60 DEG C of vacuum drying oven to constant weight to get magnetic poly- DOPA is arrived
Amine/carboxymethyl chitosan adsorbent.
Magnetic poly-dopamine/carboxymethyl chitosan adsorbent infrared test result such as Fig. 2 institute prepared by the present embodiment
Show, magnetic adsorbent is in wave number 578cm-1For the absorption peak of ferroso-ferric oxide, 1636cm-1、1558cm-1、1415cm-1For phenyl ring
Characteristic absorption peak, 3434cm-1Broad peak is attributed to the absorption peak of hydroxyl or amino, shows that magnetic adsorbent successfully synthesizes.Institute
The magnetic adsorbent of preparation proves its favorable dispersibility by the TEM of Fig. 3.
Comparative example 1
(1) synthesis of ferroso-ferric oxide: by the ferrous sulfate tetrahydrate of 25.0g ferric chloride hexahydrate and 15.0g
It being added in four-hole boiling flask, adds 50mL deionized water, then ultrasound is passed through nitrogen protection under condensing unit until dissolution,
After being heated to 80 DEG C, 50mL ammonium hydroxide is added and reacts 3 hours, is cooled to room temperature, is washed till neutrality with deionized water, dehydrated alcohol, uses
Permanent magnet is collected, and arrives magnetic ferroferric oxide nanometer particle to constant weight in 60 DEG C of vacuum drying ovens dryings.
(2) it the synthesis of magnetic carboxymethyl chitosan adsorbent: weighs 0.80g carboxymethyl chitosan and is dissolved in 200mL Tris-
In HCl buffer solution, the magnetic ferroferric oxide nanometer particle of the 0.40g prepared in step (1) is added, it is 15 minutes ultrasonic,
After reacting 6 hours at room temperature with 500rmp mixing speed, the glutaraldehyde water solution that 12.8mL volumetric concentration is 25% is added
(i.e. addition 3.2g glutaraldehyde), the reaction was continued 6 hours, is collected using permanent magnet, and cleaned three times with deionized water, is used again
Permanent magnet collects magnetic adsorbent, is dried in 60 DEG C of vacuum drying oven to constant weight and is inhaled to get to magnetic carboxymethyl chitosan
Attached dose.
Embodiment 2
(1) synthesis of ferroso-ferric oxide: by the ferrous sulfate tetrahydrate of 25.0g ferric chloride hexahydrate and 15.0g
It being added in four-hole boiling flask, adds 50mL deionized water, then ultrasound is passed through nitrogen protection under condensing unit until dissolution,
After being heated to 80 DEG C, 50mL ammonium hydroxide is added and reacts 3 hours, is cooled to room temperature, is washed till neutrality with deionized water, dehydrated alcohol, uses
Permanent magnet is collected, and arrives magnetic ferroferric oxide nanometer particle to constant weight in 60 DEG C of vacuum drying ovens dryings.
(2) it is more that 0.80g carboxymethyl chitosan, 0.4g the synthesis of magnetic poly-dopamine/carboxymethyl chitosan adsorbent: are weighed
Bar amine is dissolved in 200mL Tris-HCl buffer solution, and the magnetic ferroferric oxide for adding the 0.40g prepared in step (1) is received
Rice grain, ultrasound 15 minutes, after reacting 12 hours at room temperature with 500rmp mixing speed, adding 12.8mL volumetric concentration is
25% glutaraldehyde water solution (i.e. addition 3.2g glutaraldehyde), the reaction was continued 6 hours, is collected using permanent magnet, and spend from
Sub- water cleaning three times, collects magnetic adsorbent with permanent magnet again, is dried in 60 DEG C of vacuum drying oven to constant weight to get arriving
Magnetic poly-dopamine/carboxymethyl chitosan adsorbent.
Embodiment 3
20mg embodiment 1, magnetic poly-dopamine/carboxymethyl chitosan adsorbent in embodiment 2 and comparison are weighed respectively
Magnetic carboxymethyl chitosan adsorbent in example 1 is added in 25mL aqueous solution of methylene blue, in identical hunting speed
(180rpm), adsorption time (60 minutes), identical adsorption temp (25 DEG C), identical initial concentration (250mg/L) methylene blue water
Aqueous solution of methylene blue is adsorbed under solution and different pH (respectively 6,7,8,9,10 and 11), methylene after measurement absorption
The absorbance of base indigo plant aqueous solution calculates maximal absorptive capacity, the results showed that, in the pH=10 of aqueous solution of methylene blue, comparative example 1
With embodiment 1, embodiment 2 magnetic adsorbent to the maximal absorptive capacity of aqueous solution of methylene blue be respectively 135.6mg/g,
205.3mg/g、193.4mg/g。
Embodiment 4
20mg embodiment 1, magnetic poly-dopamine/carboxymethyl chitosan adsorbent in embodiment 2 and comparison are weighed respectively
Magnetic carboxymethyl chitosan adsorbent in example 1 is added in 25mL methyl orange aqueous solution, in identical hunting speed
(180rpm), adsorption time (60 minutes), identical adsorption temp (25 DEG C), identical initial concentration (250mg/L) methylene blue water
Solution, different pH adsorb methyl orange aqueous solution under (respectively 2,3,4,5,6 and 7), methyl orange water after measurement absorption
The absorbance of solution calculates maximal absorptive capacity, the results showed that, in the pH=4 of methyl orange aqueous solution, comparative example 1 and embodiment
1, the magnetic adsorbent of embodiment 2 to the maximal absorptive capacity of methyl orange aqueous solution be respectively 96.2mg/g, 107.3mg/g,
98.7mg/g。
Embodiment 5
20mg embodiment 1, magnetic poly-dopamine/carboxymethyl chitosan adsorbent in embodiment 2 and comparison are weighed respectively
25mL difference initial concentration (respectively 50mg/L, 100mg/L, 150mg/ is added in magnetic carboxymethyl chitosan adsorbent in example 1
L, 200mg/L and 250mg/L) aqueous solution of methylene blue in, in identical hunting speed (180rpm), identical adsorption time
Aqueous solution of methylene blue is adsorbed under (60 minutes), identical adsorption temp (25 DEG C), pH=10, methylene blue after measurement absorption
The absorbance of aqueous solution calculates maximal absorptive capacity, the results showed that, when the initial concentration of aqueous solution of methylene blue is 200mg/L,
The magnetic adsorbent of comparative example 1 and embodiment 1, embodiment 2 is respectively to the maximal absorptive capacity of aqueous solution of methylene blue
147.2mg/g、236.5mg/g、203.4mg/g。
Embodiment 6
20mg embodiment 1, magnetic poly-dopamine/carboxymethyl chitosan adsorbent in embodiment 2 and comparison are weighed respectively
Magnetic carboxymethyl chitosan adsorbent in example 1, is added in the aqueous solution of methylene blue of 25mL, in identical hunting speed
(180rpm), identical adsorption time (60 minutes), identical adsorption temp (25 DEG C), identical initial concentration (200mg/L), pH=
10 and different NaCl concentrations (concentration of the NaCl in aqueous solution of methylene blue be respectively 0mol/L, 0.02mol/L,
0.04mol/L, 0.06mol/L, 0.08mol/L and 0.1mol/L) under aqueous solution of methylene blue is adsorbed, measurement absorption after
The absorbance of aqueous solution of methylene blue calculates adsorption efficiency, as shown in Figure 4, the results showed that, with the increase of NaCl concentration, magnetic
Property adsorbent adsorption efficiency reduce.
Embodiment 7
25mg embodiment 1, magnetic poly-dopamine/carboxymethyl chitosan adsorbent in embodiment 2 and comparison are weighed respectively
Magnetic carboxymethyl chitosan adsorbent in example 1 is added to the aqueous solution of methylene blue that concentration is 200mg/L, volume is 25mL
In, identical hunting speed (180rpm), pH=10, identical adsorption temp (25 DEG C) and different adsorption time (respectively
To be carried out under 5min, 30min, 60min, 120min, 180min, 240min, 300min and 360min) to aqueous solution of methylene blue
Absorption, the absorbance of aqueous solution of methylene blue, calculates maximal absorptive capacity after measurement absorption, the results showed that, it is 90 in adsorption time
When minute, the magnetic adsorbent of comparative example 1 and embodiment 1, embodiment 2 is respectively to the maximal absorptive capacity of aqueous solution of methylene blue
152.6mg/g、248.8mg/g、184.5mg/g。
Embodiment 8
Weigh respectively various dose (three kinds of magnetic adsorbents be respectively 5mg, 10mg, 15mg, 20mg, 25mg, 30mg and
Magnetic adsorbent in embodiment 1 35mg), embodiment 2 and comparative example 1 is added to that concentration is 200mg/L, volume is 25mL's
In aqueous solution of methylene blue, in identical hunting speed (180rpm), identical adsorption temp (25 DEG C), identical adsorption time (60
Minute), aqueous solution of methylene blue is adsorbed under pH=10, the absorbance of aqueous solution of methylene blue, calculates after measurement absorption
Maximal absorptive capacity, the results showed that, when the additional amount of magnetic adsorbent is 25mg, the magnetic of comparative example 1 and embodiment 1, embodiment 2
Property adsorbent is respectively 138.5mg/g, 237mg/g, 192.8mg/g to the maximal absorptive capacity of aqueous solution of methylene blue.
Embodiment 9
The concentration that is added to for weighing the magnetic adsorbent of 25mg embodiment 1, embodiment 2 and comparative example 1 respectively is 200mg/
L, volume is to be adsorbed in the aqueous solution of methylene blue of 25mL in identical hunting speed (180rpm), identical adsorption time
To methylene blue water under (60 minutes), pH=10 and different adsorption temp (respectively 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C and 60 DEG C)
Solution is adsorbed, and the absorbance of aqueous solution of methylene blue, calculates maximal absorptive capacity after measurement absorption, the results showed that, it is adsorbing
When temperature is 45 DEG C, comparative example 1 and embodiment 1, embodiment 2 magnetic adsorbent to the maximal absorptive capacity of aqueous solution of methylene blue
Respectively 142mg/g, 249.7mg/g, 211.3mg/g.
Embodiment 10
It is the cationic dyes aqueous solution of methylene blue and anionic dyes methyl orange of 200mg/L by initial concentration
Aqueous solution mixes in equal volume, takes liquid 25mL after mixing, and the magnetic adsorbent for weighing 20mg embodiment 1 and comparative example 1 respectively adds
Enter into above-mentioned 25mL mixed liquor, pH=10, temperature are 25 DEG C, mixing speed is 180rpm and adsorption time be 60 minutes into
Row absorption after absorption reaches balance (adsorption time 60min), measures the absorbance of mixed dye aqueous solution, the results showed that, it is magnetic
Adsorbent has selective absorption effect to cationic dyes aqueous solution of methylene blue.
Embodiment 11
20mg embodiment 1, magnetic poly-dopamine/carboxymethyl chitosan adsorbent in embodiment 2 and comparison are weighed respectively
Magnetic carboxymethyl chitosan adsorbent in example 1 is added in 25mL aqueous solution of methylene blue, in identical hunting speed
(180rpm), adsorption time (60 minutes), identical adsorption temp (25 DEG C), identical initial concentration (250mg/L) methylene blue water
Aqueous solution of methylene blue is adsorbed under solution and pH=10, the absorbance of aqueous solution of methylene blue, calculates after measurement absorption
Removal rate.It uses 0.1mol/L hydrochloric acid, 0.1mol/L sodium hydroxide solution as eluent respectively, has been carried out at absorption to aforementioned
The adsorbent of reason goes to elute, dry, repeats above-mentioned adsorption treatment operation, such circulating repetition 4 times.Test result such as Fig. 5
Shown, experiment shows that magnetic poly-dopamine/carboxymethyl chitosan adsorbent removal efficiency in embodiment 1 is best, measures 5
The removal rate of secondary absorption is respectively 97%, 94%, 90%, 87% and 85%, i.e., the magnetic adsorbent is after five times recycle
Adsorption efficiency still 85% or more.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of magnetism poly-dopamine/carboxymethyl chitosan adsorbent, which is characterized in that specifically: by carboxylic first
Base enclosure glycan, dopamine and magnetic ferroferric oxide nanometer particle are scattered in buffer solution, and 5~24 are reacted at 10~50 DEG C
It after hour, adds crosslinking agent and reacts 5~24 hours, collect product, it is dry, obtain magnetic poly-dopamine/carboxymethyl chitosan
Adsorbent.
2. a kind of preparation method of magnetism poly-dopamine/carboxymethyl chitosan adsorbent, which is characterized in that specifically: by DOPA
Amine and magnetic ferroferric oxide nanometer particle are scattered in buffer solution, after reacting 5~24 hours at 10~50 DEG C, are collected and are produced
Object cleans, dry, obtains magnetic poly-dopamine nano particle；By magnetic poly-dopamine nano particle and carboxymethyl chitosan sugar
It dissipates in buffer solution, after being reacted 5~12 hours at 10~50 DEG C, adds crosslinking agent and react 5~12 hours, collect and produce
Object, it is dry, obtain magnetic poly-dopamine/carboxymethyl chitosan adsorbent.
3. a kind of preparation method of magnetic poly-dopamine/carboxymethyl chitosan adsorbent, feature exist according to claim 1
In the mass ratio of, the carboxymethyl chitosan, dopamine, crosslinking agent and magnetic ferroferric oxide nanometer particle be (1~4): (1
~4): (1~20): (1~4).
4. a kind of preparation method of magnetic poly-dopamine/carboxymethyl chitosan adsorbent, feature exist according to claim 2
In the mass ratio of the dopamine and magnetic ferroferric oxide nanometer particle is (1~4): (1~4)；The magnetism poly-dopamine
The mass ratio of nano particle, carboxymethyl chitosan and crosslinking agent is (1~4): (1~6): (2~8)；The magnetism poly-dopamine
Concentration of the nano particle in buffer solution is 1~10mg/mL.
5. special according to a kind of preparation method of magnetic poly-dopamine/carboxymethyl chitosan adsorbent of claim 3 or 4
Sign is that concentration of the dopamine in buffer solution is 1~10mg/mL；
The crosslinking agent is glutaraldehyde, N, N'- methylene-bisacrylamide, formaldehyde, ethylene glycol diglycidylether and epoxy chlorine
One or more of propane；The buffer solution is Tris-HCl buffer solution；
The magnetic ferroferric oxide nanometer particle is made by following methods: under nitrogen or atmosphere of inert gases, will contain Fe3+With
Fe2+Compound according to Fe3+With Fe2+Molar ratio be (1~5): 1 ratio is soluble in water, is warming up to 60~85 DEG C, is added
Alkaline solution reacts 2~3h, and cooling, washing collects and dry, obtains magnetic ferroferric oxide nanometer particle.
6. a kind of preparation method of magnetic poly-dopamine/carboxymethyl chitosan adsorbent, feature exist according to claim 5
In described to contain Fe3+Compound concentration in water be 1.0~3.5mol/L；Alkaline matter in the alkaline solution with contain
Fe3+Compound molar ratio be (3.5~4.5): 1；
It is described to contain Fe3+Compound be FeCl3·6H2O and/or Fe (NO3)3·9H2O；It is described to contain Fe2+Compound be
FeSO4·7H2O、FeCl2·4H2O and FeSO4·4H2One or more of O；
The alkaline solution is NaOH solution, NH3·H2One or more of O solution and KOH solution；The NH3·H2O
The volumetric concentration of solution is 15~40%；The mass concentration of the NaOH solution and KOH solution is 15~40%.
7. a kind of preparation method of magnetic poly-dopamine/carboxymethyl chitosan adsorbent, feature exist according to claim 5
In the concentration of the Tris-HCl buffer solution is 1~50mmol, and pH is 8.0~9.5；
The crosslinking agent is added in the form of cross-linking agent aqueous solution, and the volumetric concentration of the cross-linking agent aqueous solution is 2~50%.
8. a kind of magnetic poly-dopamine/carboxymethyl chitosan adsorbent made from any one of claim 1~7 the method.
9. described in claim 8 it is a kind of magnetism poly-dopamine/carboxymethyl chitosan adsorbent organic dyestuff absorption in application.
10. a kind of magnetic poly-dopamine/carboxymethyl chitosan adsorbent is in organic dyestuff absorption according to claim 9
Using, which is characterized in that the organic dyestuff is cation and/or anionic organic dyes；The Cationic organic dyes are
One or more of methylene blue, crystal violet and malachite green；The anionic organic dyes are methyl orange, Congo red
One or more of with Eosin B；
The method of the application are as follows: magnetic poly-dopamine/carboxymethyl chitosan adsorbent is added in the aqueous solution containing dyestuff,
5~360min is adsorbed at 20~60 DEG C, the initial concentration of dyestuff is 50~500mg/L in the aqueous solution；
The pH value of the aqueous solution is 2~11；Magnetism poly-dopamine/carboxymethyl chitosan the adsorbent is dense aqueous solution kind
Degree is 0.2~50mg/mL.
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