CN105903448A - Method for preparing nanocrystalline cellulose magnetic particle adsorbent - Google Patents
Method for preparing nanocrystalline cellulose magnetic particle adsorbent Download PDFInfo
- Publication number
- CN105903448A CN105903448A CN201610302212.4A CN201610302212A CN105903448A CN 105903448 A CN105903448 A CN 105903448A CN 201610302212 A CN201610302212 A CN 201610302212A CN 105903448 A CN105903448 A CN 105903448A
- Authority
- CN
- China
- Prior art keywords
- nano
- crystal
- magnetic particle
- preparation
- absorption agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- 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
-
- 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
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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 relates to a method for preparing a nanocrystalline cellulose magnetic particle adsorbent. The method comprises the steps of preparing nanocrystalline cellulose from microcrystalline cellulose, then, preparing nanocrystalline cellulose magnetic particles through grafting modification, and finally, encapsulating the nanocrystalline cellulose magnetic particles by microcapsules, thereby obtaining the nanocrystalline cellulose magnetic particle adsorbent. According to the method, the nanocrystalline cellulose magnetic particle adsorbent is prepared through preparing the nanocrystalline cellulose from the microcrystalline cellulose, then, preparing the nanocrystalline cellulose magnetic particles through grafting modification, and finally, encapsulating the nanocrystalline cellulose magnetic particles by the microcapsules. The method has the characteristics of extensive raw materials and low cost, and the prepared adsorbent is environment-friendly and pollution-free, can be used for adsorbing a variety of heavy metals such as lead, chromium and copper in sewage, is high in adsorption capacity and good in effect and has regeneration capacity.
Description
Technical field
The present invention relates to nano-crystal cellulose family field of compound material, particularly relate to a kind of absorption of heavy metal in absorption effluent
The preparation method of the nano-crystal fibrin magnetic particle absorption agent of heavy metal ion.
Background technology
Along with modern Economy Development and the development and utilization of marine resources of field, coastal waters, a large amount of waste water containing heavy metal ion and life
Sewage of living is discharged into sea, and heavy metal pollution sharp deterioration in ocean water body, ecological environment has also suffered from huge destruction.With much money
Belonging to ion to be built up by food chain enrichment, existing substantial amounts of research shows, the content of beary metal of sea water Mesichthyes the most seriously surpasses
Mark.
Heavy metal has certain toxicity.Such as cadmium, after environment is contaminated, it is rich that cadmium can enter human body by food chain etc.
Collection, destroy internal sulfydryl enzyme system, affect tissue metabolism, to local histiocyte cause damage, cause various inflammation with
Edema.Once be absorbed into blood, cadmium albumen can be formed in human body, the most optionally be accumulated in the histoorgan such as liver, kidney,
Thus damage the function of the organ such as liver, kidney.Copper is a kind of required trace element, if but take in too much, then can cause digestion
System disorders, long-term excess also can result in liver cirrhosis, and too much copper can produce copper poisoning, copper and protein etc. after entering human body
The fat-soluble height of complex formed, easily has an effect with enzyme, nucleic acid etc., and malignant differentiation can be promoted after reacting with DNA raw
Long, the mortality rate of hepatocarcinoma also exists positively related relation with the copper content in environment to have research to think.
In traditional aqueous solution, heavy metal removing method mainly has: chemical precipitation method, ion-exchange-resin process, absorption method etc..
Chemical precipitation method is to process one of the most widely used method in heavy metal pollution in wastewater, and the method technique is simple, but needs
Chemical precipitation agent to be used.Ion-exchange-resin process has the process advantages such as capacity is the most convenient and swift, but its operating cost is high, from
Sub-exchanger regenerative operation is complicated, and the porogen easy contaminating protein enzymolysis solution of residual in resin.Therefore from the angle of food safety
From the point of view of Du, above two method is not suitable for the removing of heavy metal ion in protein enzymatic hydrolyzate.Absorption method technique is relatively simple, absorption
Capacity is big, and adsorbent species is many, conventional activated carbon, attapulgite, kieselguhr etc..Natural adsorbing material is (such as chitosan, wood
Matter cellulose etc.) heavy metal ion report in adsorbent solution is a lot.From the point of view of the microstructure of natural wooden fiber's element, its molecule
Arrangement there is directionality, possess the feature (referred to as cellulose crystallite district) of crystal, lignocellulose in plant tissue with other high score
Son combines with covalent bond often and forms lignin-carbohydrate complexes, and absorption may be held by these microstructures both ways
Amount produces impact with adsorptive selectivity: the existence of (1) crystal region limits metal ion in solution to lignocellulose absorbent particles
Internal diffusion, crystal region also can masked segment activated adoption group, and then cause adsorption capacity on the low side；(2) due to lignin-
The existence of carbohydrate complex, the surface area of lignocellulose absorbent particles, pore volume, average pore radius and aperture
Distribution, not in applicable scope, affects adsorptive selectivity and adsorption capacity.Above-mentioned reason causes only higher at concentration of metal ions
In solution system, natural wooden fiber's element just shows efficient absorption property.Solution ion strength to metal ion at wood fibre
Adsorption Effect in element is relatively big, when there is the electrolyte such as NaCl of high concentration in solution, can reduce system adsorption capacity.
Summary of the invention
The invention aims to solve the deficiency of existing technique and a kind of absorption of heavy metal in absorption effluent is provided
The preparation method of the nano-crystal fibrin magnetic particle absorption agent of heavy metal ion.
To achieve these goals, the present invention is by the following technical solutions:
A kind of preparation method of nano-crystal fibrin magnetic particle absorption agent, described preparation method is that microcrystalline Cellulose is prepared nano-crystal cellulose,
Then prepared in nano-crystal fibrin magnetic particle is finally wrapped in microcapsule by nano-crystal fibrin magnetic particle by graft modification and obtain
Nano-crystal fibrin magnetic particle absorption agent.
As preferably, microcrystalline Cellulose is prepared the preparation method of nano-crystal cellulose and is: microcrystalline Cellulose adds ammonium persulfate solution
In, high speed centrifugation after ultrasonic reaction, washs to neutrality addition citric acid solution and obtains continuing ultrasonic reaction, then high speed centrifugation is washed
Wash to neutrality dialysis and obtain carboxylated nano-crystal cellulose.In the technical program, owing to existing preparation nano-crystal fibrination is with strong
Aqueous acid hydrolysis and make, but owing to strong acid solution reclaims difficulty, and can be to environment, therefore the present invention selects micro-
Crystalline cellulose and citric acid solution prepare nano-crystal cellulose.
As preferably, the preparation method of nano-crystal fibrin magnetic particle absorption agent be configuration concentration be that the nano-crystal of 0.2-0.5wt% is fine
Dimension element dispersion liquid, standby after ultrasonic disperse 1-2h；The amount of material is added than for 2:1 in the acetone that liquid-solid ratio is 1mL:4-6mg
FeCl3·6H2O and FeCl2·4H2O, logical N2After use NH3·H2O regulates pH to about 10, reacts 3-5h under room temperature, then
Add the ethylenediamine of acetone volume 1-2%, the magnetic field of additional 1.0-1.5T, continue reaction 2-3h, remove organic solvent and be placed on
30-50min at 0-4 DEG C, then with Magnet by product and solution separating, washes 3 times with water and ethanol after product washing to neutrality repeatedly,
Vacuum drying is pulverized, and obtains nano-crystal fibrin magnetic particle.
As preferably, modified starch and cyclodextrin are dissolved in 85-90 DEG C of deionized water, are configured to saturated solution, under stirring
Nano-crystal fibrin magnetic particle is slowly added in saturated solution, the ultrasonic and magnetic field of 1.0-1.5T, after stirring 5-10h
Drying makes granule, and particle diameter is 100-500 μm, obtains nano-crystal fibrin magnetic particle absorption agent.In the technical program,
Nano-crystal fibrin magnetic particle is wrapped up into microcapsule, so that the effective ingredient of adsorbent keeps stable chemical nature so that
Its number of dropouts in preserving transportation reduces, and can make the adsorbent environmental protection prepared simultaneously, pollution-free, can be used to adsorb
The various heavy such as lead, chromium, copper in sewage, adsorption capacity is big, effective, and has regeneration capacity.
As preferably, the saturated solution that mass ratio is 1:3-5, modified starch and cyclodextrin of modified starch and cyclodextrin and nano-crystal
The solid-liquid ratio of fibrin magnetic particle is 1mL:2-4g.
As preferably, the concentration of ammonium persulfate solution is 2mol/L, and the concentration of citric acid solution is 1mol/L.
As preferably, supersonic frequency is 70-90KHz.
The invention has the beneficial effects as follows: the present invention utilizes microcrystalline Cellulose to prepare nano-crystal cellulose, then is prepared by graft modification
Nano-crystal fibrin magnetic particle, obtains nano-crystal fibrin magnetic particle in finally nano-crystal fibrin magnetic particle being wrapped in microcapsule
Adsorbent, have raw material extensively, the feature of low cost, prepared adsorbent environmental protection, pollution-free, can be used to absorption effluent
The various heavy such as middle lead, chromium, copper, adsorption capacity is big, effective, and has regeneration capacity.
Accompanying drawing explanation
Fig. 1 is the scanning electricity of ferroferric oxide magnetic nanoparticle (a) and carboxylated nano-crystal cellulose coated ferriferrous oxide (b)
Mirror figure.
Fig. 2 is that carboxylated nano-crystal cellulose (a), ferroferric oxide magnetic nanoparticle (b) and carboxylated nano-crystal cellulose are coated with four
The Fourier transform infrared spectroscopy figure of Fe 3 O (c).
Detailed description of the invention
Technical scheme in the embodiment of the present invention will be carried out clear, complete description below, it is clear that described embodiment
It is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, the common skill in this area
All other embodiments that art personnel are obtained under not making creative work premise, broadly fall into the scope of protection of the invention.
Table 1, reagent source
Table 2, instrument
Ferroferric oxide magnetic nano-particles (Fe3O4) preparation
Take 70mL water and join in 250mL there-necked flask, logical N at 65 DEG C230min.0.374g is weighed than for 2:1 according to the amount of material
FeCl3·6H2O and 0.138g FeCl24H2O is dissolved in 10mL water, logical N for a moment2After join in flask, use NH3·H2O
Regulation pH to about 10, terminates after reaction 10min.With Magnet by product and solution separating, incline supernatant, wash with water to
After weakly acidic pH, repeatedly washing 3 times with water, ethanol, vacuum lyophilization obtains product.
Embodiment 1
A kind of preparation method of nano-crystal fibrin magnetic particle absorption agent, described preparation method is that microcrystalline Cellulose is prepared nano-crystal cellulose,
Then prepared in nano-crystal fibrin magnetic particle is finally wrapped in microcapsule by nano-crystal fibrin magnetic particle by graft modification and obtain
Nano-crystal fibrin magnetic particle absorption agent.
Microcrystalline Cellulose prepares the preparation method of nano-crystal cellulose: 6gMCC adds 2mol/L ammonium persulfate solution 200mL,
Mix homogeneously, time of infusion, it is placed in ultrasound wave 70KHz reactor, stirring reaction at 60 DEG C, reaction obtains after terminating
To suspension, suspension is placed in 9000r/rnin in high speed centrifuge and is centrifuged repeatedly washing weakly acidic pH, use 200mL1mol/L lemon
The colloidal substance prepared is dissolved by lemon acid solution, continues 60 DEG C of stirring reaction response 2h in ultrasonic reactor.Reaction terminates
After, suspension is placed in 9000r/rnin in high speed centrifuge and is centrifuged repeatedly washing weakly acidic pH, with deionized water dissolving, load thoroughly
Analysis bag dialysis 10h, makes the carboxylated nano-crystal cellulose (CCN) prepared in neutrality.
The preparation method of nano-crystal fibrin magnetic particle absorption agent be configuration concentration be the nano-crystal cellulose dispersion liquid of 0.2wt%, super
Sound is standby after disperseing 1h；The amount of material is added than the FeCl for 2:1 in the acetone that liquid-solid ratio is 1mL:4mg3·6H2O and
FeCl2·4H2O, logical N2After use NH3·H2O regulates pH to about 10, reacts 3-5h, add acetone volume 1% under room temperature
Ethylenediamine, the magnetic field of additional 1T, continue reaction 2h, remove organic solvent be placed on 0-4 DEG C at 30min, then use Magnet
By product and solution separating, repeatedly washing 3 times with water and ethanol after product washing to neutrality, vacuum drying is pulverized, and obtains nano-crystal fine
Dimension element magnetic particle.
Modified starch and cyclodextrin are dissolved in 85 DEG C of deionized waters, are configured to saturated solution, by nano-crystal fiber biscuit porcelain under stirring
Property particle be slowly added in saturated solution, the magnetic field of ultrasonic 70KHz and 1T, stirring 5h after through be dried makes granule,
Particle diameter is 100 μm, obtains nano-crystal fibrin magnetic particle absorption agent.
The saturated solution that mass ratio is 1:3, modified starch and cyclodextrin of modified starch and cyclodextrin and nano-crystal fibrin magnetic
The solid-liquid ratio of particle is 1mL:2g.
Embodiment 2
A kind of preparation method of nano-crystal fibrin magnetic particle absorption agent, described preparation method is that microcrystalline Cellulose is prepared nano-crystal cellulose,
Then prepared in nano-crystal fibrin magnetic particle is finally wrapped in microcapsule by nano-crystal fibrin magnetic particle by graft modification and obtain
Nano-crystal fibrin magnetic particle absorption agent.
Microcrystalline Cellulose prepares the preparation method of nano-crystal cellulose: 6gMCC adds 2mol/L ammonium persulfate solution 200mL,
Mix homogeneously, time of infusion, it is placed in ultrasound wave 80KHz reactor, stirring reaction at 60 DEG C, reaction obtains after terminating
To suspension, suspension is placed in 9000r/rnin in high speed centrifuge and is centrifuged repeatedly washing weakly acidic pH, use 200mL1mol/L lemon
The colloidal substance prepared is dissolved by lemon acid solution, continues 60 DEG C of stirring reaction response 2h in ultrasonic reactor.Reaction terminates
After, suspension is placed in 9000r/rnin in high speed centrifuge and is centrifuged repeatedly washing weakly acidic pH, with deionized water dissolving, load thoroughly
Analysis bag dialysis 10h, makes the carboxylated nano-crystal cellulose (CCN) prepared in neutrality.
The preparation method of nano-crystal fibrin magnetic particle absorption agent be configuration concentration be the nano-crystal cellulose dispersion liquid of 0.3wt%, super
Sound is standby after disperseing 1.5h；The amount of material is added than the FeCl for 2:1 in the acetone that liquid-solid ratio is 1mL:5mg3·6H2O and
FeCl2·4H2O, logical N2After use NH3·H2O regulates pH to about 10, reacts 4h, add acetone volume 1.5% under room temperature
Ethylenediamine, the magnetic field of additional 1.2T, continue reaction 2.5h, remove organic solvent be placed on 0-4 DEG C at 40min, then use
Magnet, by product and solution separating, is washed 3 times with water and ethanol after product washing to neutrality repeatedly, and vacuum drying is pulverized, and is received
Crystalline cellulose magnetic particle.
Modified starch and cyclodextrin are dissolved in 86 DEG C of deionized waters, are configured to saturated solution, by nano-crystal fiber biscuit porcelain under stirring
Property particle be slowly added in saturated solution, the magnetic field of ultrasonic 80KHz and 1.3T, stirring 7h after through be dried makes granule,
Particle diameter is 400 μm, obtains nano-crystal fibrin magnetic particle absorption agent.
Modified starch is 14 with the mass ratio of cyclodextrin, the saturated solution of modified starch and cyclodextrin and nano-crystal fibrin magnetic grain
The solid-liquid ratio of son is 1mL:3g.
Embodiment 3
A kind of preparation method of nano-crystal fibrin magnetic particle absorption agent, described preparation method is that microcrystalline Cellulose is prepared nano-crystal cellulose,
Then prepared in nano-crystal fibrin magnetic particle is finally wrapped in microcapsule by nano-crystal fibrin magnetic particle by graft modification and obtain
Nano-crystal fibrin magnetic particle absorption agent.
Microcrystalline Cellulose prepares the preparation method of nano-crystal cellulose: 6gMCC adds 2mol/L ammonium persulfate solution 200mL,
Mix homogeneously, time of infusion, it is placed in ultrasound wave 90KHz reactor, stirring reaction at 60 DEG C, reaction obtains after terminating
To suspension, suspension is placed in 9000r/rnin in high speed centrifuge and is centrifuged repeatedly washing weakly acidic pH, use 200mL1mol/L lemon
The colloidal substance prepared is dissolved by lemon acid solution, continues 60 DEG C of stirring reaction response 2h in ultrasonic reactor.Reaction terminates
After, suspension is placed in 9000r/rnin in high speed centrifuge and is centrifuged repeatedly washing weakly acidic pH, with deionized water dissolving, load thoroughly
Analysis bag dialysis 10h, makes the carboxylated nano-crystal cellulose (CCN) prepared in neutrality.
The preparation method of nano-crystal fibrin magnetic particle absorption agent be configuration concentration be the nano-crystal cellulose dispersion liquid of 0.5wt%, super
Sound is standby after disperseing 2h；The amount of material is added than the FeCl for 2:1 in the acetone that liquid-solid ratio is 1mL:6mg3·6H2O and
FeCl2·4H2O, logical N2After use NH3·H2O regulates pH to about 10, reacts 5h, add acetone volume 2% under room temperature
Ethylenediamine, the magnetic field of additional 1.5T, continue reaction 3h, remove organic solvent be placed on 0-4 DEG C at 50min, then use magnetic
Ferrum, by product and solution separating, is washed 3 times with water and ethanol after product washing to neutrality repeatedly, and vacuum drying is pulverized, and obtains nano-crystal
Fibrin magnetic particle.
Modified starch and cyclodextrin are dissolved in 90 DEG C of deionized waters, are configured to saturated solution, by nano-crystal fiber biscuit porcelain under stirring
Property particle be slowly added in saturated solution, the magnetic field of ultrasonic 90KHz and 1.5T, make through being dried after stirring 5-10h
Grain, particle diameter is 500 μm, obtains nano-crystal fibrin magnetic particle absorption agent.
The saturated solution that mass ratio is 1:5, modified starch and cyclodextrin of modified starch and cyclodextrin and nano-crystal fibrin magnetic
The solid-liquid ratio of particle is 1mL:4g.
See Fig. 1, by tem observation Fe3O4And CCN-Fe3O4Form visible, uncoated CCN prepares
Fe3O4(a), the high aggregation due to the strongest dipolar magnetic interaction.By contrast, prepare in CCN solution with
Fe3O4For core, the CCN-Fe of CCN in cladding3O4The most more disperse.This most more verifies CCN-Fe3O4Generation process be
With CCN as template with dispersant, by hydroxyl substantial amounts of on CCN surface and carboxyl and Fe3O4The hydroxyl on surface interacts,
These groups on CCN supply Fe as anchor point3O4Generate core, be dispersed in CCN structure.The most both Fe had been added3O4
Dispersion, make Fe3O4It is not easy to reunite, also allows, with several functions group, heavy metal ion, there is fine adsorption
CCN and Fe3O4In conjunction with, obtaining easily separated and heavy metal lead has the CCN-Fe of efficient absorption effect3O4Magnetic nano-particle
Adsorbent.
See Fig. 2, use Fourier infrared spectrograph to CCN (a), Fe3O4(b) and CCN-Fe3O4C () carries out table
Levy.Three kinds of materials are at 3360cm-1And 1620cm-1Near occur absworption peak, the two peak is belonging respectively to the flexible of-OH and shakes
The dynamic characteristic absorption peak with-COOH.After carboxylated nano-crystal cellulose is coated on ferroso-ferric oxide ,-OH's and-COOH
Absworption peak the most substantially weakens, this great amount of hydroxy group being likely due to CCN surface and carboxyl and Fe3O4Interact.CCN(a)
And CCN-Fe3O4C () is at 2900cm-1The peak at place belongs to the-C-H vibration of nano-crystal cellulose, is coated on four at nano-crystal cellulose
After on Fe 3 O magnetic nanoparticle, (c) material-C-H vibration has weakened.Additionally, CCN-Fe3O4Magnetic particle is at 571cm-1
A new absworption peak occur, this peak belongs to the vibration peak of Fe-O.As can be seen here, CCN and Fe3O4Success is reacted and is prepared carboxylic
The magnetic nano-particle of base nano-crystal cellulose coated ferriferrous oxide.
It should be appreciated that to those skilled in the art, can be improved according to the above description or be converted,
And all these modifications and variations all should belong to the protection domain of claims of the present invention.
Claims (7)
1. the preparation method of a nano-crystal fibrin magnetic particle absorption agent, it is characterised in that described preparation method is by microcrystalline Cellulose
Preparation nano-crystal cellulose, then prepares nano-crystal fibrin magnetic particle finally by nano-crystal fibrin magnetic particle bag by graft modification
Nano-crystal fibrin magnetic particle absorption agent is obtained in being rolled in microcapsule.
The preparation method of a kind of nano-crystal fibrin magnetic particle absorption agent the most according to claim 1, it is characterised in that crystallite is fine
The preparation method of dimension element preparation nano-crystal cellulose is: microcrystalline Cellulose adds in ammonium persulfate solution, high speed centrifugation after ultrasonic reaction,
Wash to neutrality addition citric acid solution and obtain continuing ultrasonic reaction, then high speed centrifugation washs to neutrality dialysis and obtains carboxylated
Nano-crystal cellulose.
The preparation method of a kind of nano-crystal fibrin magnetic particle absorption agent the most according to claim 2, it is characterised in that nano-crystal is fine
Dimension biscuit porcelain particle absorption agent preparation method be configuration concentration be the nano-crystal cellulose dispersion liquid of 0.2-0.5wt%, ultrasonic disperse
After 1-2h standby；The amount of material is added than the FeCl for 2:1 in the acetone that liquid-solid ratio is 1mL:4-6mg3·6H2O and FeCl2
·4H2O, logical N2After use NH3·H2O regulates pH to about 10, reacts 3-5h, add acetone volume 1-2%'s under room temperature
Ethylenediamine, the magnetic field of additional 1.0-1.5T, continue reaction 2-3h, remove 30-50min at organic solvent is placed on 0-4 DEG C, so
Afterwards with Magnet by product and solution separating, repeatedly washing 3 times with water and ethanol after product washing to neutrality, vacuum drying is pulverized,
To nano-crystal fibrin magnetic particle.
The preparation method of a kind of nano-crystal fibrin magnetic particle absorption agent the most according to claim 3, it is characterised in that by degeneration
Starch and cyclodextrin are dissolved in 85-90 DEG C of deionized water, are configured to saturated solution, by slow for nano-crystal fibrin magnetic particle under stirring
Join in saturated solution, the ultrasonic and magnetic field of 1.0-1.5T, make granule through dry after stirring 5-10h, particle diameter is
100-500 μm, obtains nano-crystal fibrin magnetic particle absorption agent.
The preparation method of a kind of nano-crystal fibrin magnetic particle absorption agent the most according to claim 4, it is characterised in that degeneration is formed sediment
The saturated solution that mass ratio is 1:3-5, modified starch and cyclodextrin of powder and cyclodextrin and the solid-liquid ratio of nano-crystal fibrin magnetic particle
For 1mL:2-4g.
The preparation method of a kind of nano-crystal fibrin magnetic particle absorption agent the most according to claim 2, it is characterised in that persulfuric acid
The concentration of ammonium salt solution is 2mol/L, and the concentration of citric acid solution is 1mol/L.
7. according to the preparation method of a kind of nano-crystal fibrin magnetic particle absorption agent described in claim 2-6, it is characterised in that ultrasonic
Frequency is 70-90KHz.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610302212.4A CN105903448B (en) | 2016-05-09 | 2016-05-09 | A kind of preparation method of nano-crystal fibrin magnetic particle absorption agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610302212.4A CN105903448B (en) | 2016-05-09 | 2016-05-09 | A kind of preparation method of nano-crystal fibrin magnetic particle absorption agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105903448A true CN105903448A (en) | 2016-08-31 |
| CN105903448B CN105903448B (en) | 2018-11-06 |
Family
ID=56747898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610302212.4A Active CN105903448B (en) | 2016-05-09 | 2016-05-09 | A kind of preparation method of nano-crystal fibrin magnetic particle absorption agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105903448B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107721057A (en) * | 2017-10-25 | 2018-02-23 | 镇江市丹徒区华发五金有限公司 | A kind of method for treating copper-containing waste water based on magnetic adsorbent |
| CN109012638A (en) * | 2018-07-20 | 2018-12-18 | 浙江理工大学 | A kind of preparation method of carboxylated multi-stage porous cellulose adsorbing sphere |
| CN109550480A (en) * | 2018-11-23 | 2019-04-02 | 浙江海洋大学 | A kind of preparation method of amination magnetic carbon nano-tube |
| CN112442377A (en) * | 2020-11-30 | 2021-03-05 | 胡海波 | Soil conditioner based on cadmium pollution remediation and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109517181B (en) * | 2018-11-23 | 2022-03-18 | 浙江海洋大学 | Preparation method of aminated magnetic nanocrystalline cellulose |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63274452A (en) * | 1987-05-01 | 1988-11-11 | Sumiyoshi Jukogyo Kk | Magnetic adsorbent for manufacturing nitrogen |
| CN103535376A (en) * | 2013-09-15 | 2014-01-29 | 浙江理工大学 | Preparation method of nanometer zinc oxide-bamboo charcoal composite particle with antibacterial and adsorption functions |
| CN103709422A (en) * | 2013-12-20 | 2014-04-09 | 华南理工大学 | Preparation method of magnetic cellulose nanocrystal |
| CN105195112A (en) * | 2015-10-26 | 2015-12-30 | 福建农林大学 | Preparation method of melamine-modified chitosan-coated magnetic nanocellulose adsorbent and product thereof |
| CN105195111A (en) * | 2015-10-26 | 2015-12-30 | 福建农林大学 | Preparation method of polyethylenimine modified chitosan-coated magnetic nanocellulose adsorbent and product thereof |
-
2016
- 2016-05-09 CN CN201610302212.4A patent/CN105903448B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63274452A (en) * | 1987-05-01 | 1988-11-11 | Sumiyoshi Jukogyo Kk | Magnetic adsorbent for manufacturing nitrogen |
| CN103535376A (en) * | 2013-09-15 | 2014-01-29 | 浙江理工大学 | Preparation method of nanometer zinc oxide-bamboo charcoal composite particle with antibacterial and adsorption functions |
| CN103709422A (en) * | 2013-12-20 | 2014-04-09 | 华南理工大学 | Preparation method of magnetic cellulose nanocrystal |
| CN105195112A (en) * | 2015-10-26 | 2015-12-30 | 福建农林大学 | Preparation method of melamine-modified chitosan-coated magnetic nanocellulose adsorbent and product thereof |
| CN105195111A (en) * | 2015-10-26 | 2015-12-30 | 福建农林大学 | Preparation method of polyethylenimine modified chitosan-coated magnetic nanocellulose adsorbent and product thereof |
Non-Patent Citations (2)
| Title |
|---|
| XIAOLIN YU ET AL: ""Adsorption of heavy metal ions from aqueous solution by carboxylated cellulose nanocrystals"", 《JOURNAL OF ENVIRONMENTAL SCIENCES》 * |
| 李现艳: ""一锅法制备羧基化纳米纤维素晶体"", 《北京林业大学学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107721057A (en) * | 2017-10-25 | 2018-02-23 | 镇江市丹徒区华发五金有限公司 | A kind of method for treating copper-containing waste water based on magnetic adsorbent |
| CN109012638A (en) * | 2018-07-20 | 2018-12-18 | 浙江理工大学 | A kind of preparation method of carboxylated multi-stage porous cellulose adsorbing sphere |
| CN109012638B (en) * | 2018-07-20 | 2021-01-12 | 浙江理工大学 | Preparation method of carboxylated hierarchical porous cellulose adsorption balls |
| CN109550480A (en) * | 2018-11-23 | 2019-04-02 | 浙江海洋大学 | A kind of preparation method of amination magnetic carbon nano-tube |
| CN109550480B (en) * | 2018-11-23 | 2022-01-11 | 浙江海洋大学 | Preparation method of aminated magnetic carbon nanotube |
| CN112442377A (en) * | 2020-11-30 | 2021-03-05 | 胡海波 | Soil conditioner based on cadmium pollution remediation and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105903448B (en) | 2018-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105903449B (en) | A kind of method of heavy metal in carboxylated nano-crystal fibrin magnetic particle absorption solution | |
| CN105903448A (en) | Method for preparing nanocrystalline cellulose magnetic particle adsorbent | |
| CN105903441B (en) | A kind of preparation method of nano-crystal fibrin magnetic particle | |
| CN100386141C (en) | Composite absorption material for removing arsenic from water and its prepn. method | |
| CN106268679B (en) | A kind of preparation method of chitosan nano fiber element base composite spherical adsorbent material | |
| CN101314123B (en) | Magnetic biological adsorption agent and preparation method thereof | |
| CN107362777B (en) | A kind of preparation method of magnetism stalk cellulose adsorbent for heavy metal | |
| CN102814163B (en) | Preparation method of magnetic charcoal for efficiently removing tetracycline | |
| CN107999033A (en) | A kind of poly-dopamine/aminated carbon nano tube/sodium alginate micro ball of arsenic-adsorbing | |
| CN101091906B (en) | Cationoid adsorbent for quarternary ammonium salt of agricultural waste, and preparation technique | |
| CN111450806B (en) | Preparation method of porous adsorption antibacterial composite material based on waste corncobs | |
| CN109569725B (en) | Method for preparing magnetic Cu (I) microsphere catalyst by one-step method | |
| CN112521617B (en) | Polyacid-based metal organic framework material for adsorbing antibiotics and preparation method and application thereof | |
| CN106046256B (en) | The preparation method of geniposide molecular engram polymer magnetic microballoon | |
| CN106040185A (en) | Method for preparing magnetic adsorbent for methylene blue wastewater treatment | |
| Shi et al. | Multifunctional cellulose and cellulose-based (nano) composite adsorbents | |
| Tripathi et al. | Overview on synthesis of magnetic bio char from discarded agricultural biomass | |
| CN108620044B (en) | Magnetic response graphene oxide/plant fiber adsorption material and preparation method and application thereof | |
| CN105195116B (en) | A kind of beta cyclodextrin modifies the preparation method of porous dextrangel adsorbent | |
| Wang et al. | Enhanced heterogeneous fenton degradation of organic pollutants by CRC/Fe3O4 catalyst at neutral pH | |
| CN107638872A (en) | A kind of flyash/magnetic stalk compound material and preparation method and application | |
| CN109621920A (en) | A kind of pipe/polyhenylethylene nano zero-valent iron composite material and its preparation method and application | |
| CN106311187B (en) | A kind of preparation of cyanurotriamide modified magnetic coconut skin adsorbent | |
| CN107774227A (en) | A kind of preparation method of ferro manganese composite oxides/ferroso-ferric oxide core-shell nano material | |
| CN102504283A (en) | Method for preparing lignosulfonate micro gel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |