CN105413661B - Polyethyleneimine-chitosan absorbent one-step synthesis - Google Patents
Polyethyleneimine-chitosan absorbent one-step synthesis Download PDFInfo
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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
- B01J20/22—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
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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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
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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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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Abstract
The present invention relates to polyethyleneimine chitosan absorbent one-step synthesis, and this approach includes the following steps：(i) chitosan, polyethyleneimine glacial acetic acid are configured to interior phase solution, atoleine and petroleum ether is configured to external solution；(ii) the interior phase solution and external solution that are obtained in step (i) injection focused flow are declined fluidic chip respectively, a series of chitosan drops is made；(iii) it after the chitosan droplets stable in step (ii) generates, is conducted into crosslinking curing liquid, chitosan microball is made；(iv) chitosan microball obtained in step (iii) is cleaned multiple times using ethanol solution, acetone soln and deionized water successively；And (v) chitosan microball obtained in step (iv) is lyophilized, obtain polyethyleneimine chitosan absorbent.
Description
Technical field
The invention belongs to water-treatment technology fields, are related to a kind of polyethyleneimine-chitosan absorbent one-step synthesis.
Background technology
Derived energy chemical industrial wastewater usually contains heavy metal ion (such as copper, cobalt, manganese), azo dyes (such as methyl orange), strong
The complex components such as sour strong basicity, existing wastewater treatment method, such as neutralisation, reduction method, vulcanization, are faced with single treatment
Measure that small, long processing period, treatment effect be not good enough, processing cost is high, there are the problems such as secondary pollution.
Therefore, simple and effective to processing method at present, process cycle is short, processing cost is low, to environment non-secondary pollution
The cry of efficient wastewater treatment method is higher and higher.
Invention content
For derived energy chemical industrial wastewater complicated component, single treatment amount is small, long processing period, treatment effect is not good enough, place
Manage it is with high costs, there are problems such as secondary pollutions, the present invention provides a kind of novel polyethyleneimine-chitosan absorbents one
Synthetic method is walked, this method has preparation method is simple and reliable, absorption property stabilization is effective, can handle Various Complex component simultaneously to give up
The features such as aqueous systems, to solve problems of the prior art.
The present invention provides a kind of polyethyleneimine-chitosan absorbent one-step synthesis, and this approach includes the following steps：
(i) chitosan, polyethyleneimine glacial acetic acid are configured to interior phase solution, atoleine and petroleum ether are configured to outer
Phase solution；
(ii) the interior phase solution and external solution that are obtained in step (i) injection focused flow are declined fluidic chip respectively, system
Obtain a series of chitosan drops；
(iii) it after the chitosan droplets stable in step (ii) generates, is conducted into crosslinking curing liquid, shell is made
Glycan microballoon；
(iv) it is poly- that the shell obtained in step (iii) is cleaned multiple times using ethanol solution, acetone soln and deionized water successively
Sugared microballoon；And
(v) chitosan microball obtained in step (iv) is lyophilized, obtains polyethyleneimine-chitosan absorbent.
In one preferred embodiment, in step (i), the interior phase solution includes being added with 1-3 parts by weight
Chitosan, the aqueous solution of 30% polyethyleneimine of 1-3 parts by weight and the glacial acetic acid of 1-2 parts by weight, and in 45-50 DEG C of water-bath
Under the conditions of be slowly stirred 5-6 hours；The external solution includes atoleine and petroleum ether according to volume ratio 7:5-2:1 mixing
Solution, and the Span 80 added with 1-2 parts by weight.
In another preferred embodiment, in step (ii), by by the interior phase solution and external solution
Velocity ratio control is 1:5 to 1:20 are made a series of chitosan drops.
In another preferred embodiment, in step (ii), using External infusion pumping system respectively by step (i)
In obtained interior phase solution and external solution injection focused flow decline fluidic chip.
In another preferred embodiment, in step (iii), the crosslinking curing liquid includes containing 0.5-1 weights
Measure the normal octane solution of the glutaraldehyde of part and the Span 80 of 1-2 parts by weight.
In another preferred embodiment, in step (iii), chitosan drop is passed through in crosslinking curing liquid simultaneously
It is slowly stirred, control mixing speed is 450-650r/min, reaction time 30-60min.
In another preferred embodiment, in step (iv), a concentration of 30-40% of ethanol solution, acetone is molten
A concentration of 25-35% of liquid, cleans chitosan microball 3-4 times successively.
In another preferred embodiment, in step (v), the freeze temperature is -40 to -60 DEG C, when freeze-drying
Between control at 10-12 hours.
In another preferred embodiment, the volume ratio of the atoleine and petroleum ether is 7:5.
In another preferred embodiment, the velocity ratio control of the interior phase solution and external solution is 1:7.
Description of the drawings
Fig. 1 is the stream of polyethyleneimine-chitosan absorbent one-step synthesis according to embodiment of the present invention
Cheng Tu.
Fig. 2 is polyethyleneimine-chitosan absorbent pictorial diagram according to embodiment of the present invention.
Fig. 3 is to adsorb various concentration methyl orange dye according to the polyethyleneimine-chitosan absorbent of the embodiment of the present application 1
Color contrast.
Fig. 4 is to adsorb different pH value acidity and alkalinity according to polyethyleneimine-chitosan absorbent of the embodiment of the present application 2
The color contrast of solution.
Specific implementation mode
Term
Term chitosan (Chitosan) used herein, refers to the product of chitin deacetylation.It is nature
The unique natural alkaline glycosaminoglycan in boundary is nontoxic with product after good biocompatibility, biological degradability and degradation
Property.Contain a large amount of hydroxyl and amino on its macromolecular chain, wherein amino can be reacted with metal ion, form metal-chelating
Object to adsorbing metal ions, while can also modify chitosan itself using hydroxyl and amino, and then it is right to enhance its
The absorption property of metal ion.
Term focused flow used herein declines flow control, refers to preparing dispersion by the shear action between immiscible fluid
Drop, and prepare as template the microflow control technique of the products such as particle, gel.Drop microflow control technique can be applied to multiple friendships
Fork field.In terms of chemical analysis, each drop is an independent enclosure space, enhances the anti-interference of sample in drop
Property, cross contamination between sample is not easily caused, improves analysis efficiency and repeatability；In terms of reaction, micro- reaction is substantially improved
The size uniformity degree of device and structure complexity, expansion microreactor preparation method；Can be particle, gel, micro- in Material Field
The preparation of capsule provides excellent template, assigns its good physical and chemical performance.
Present inventor has found afterwards after extensive and in-depth study, in derived energy chemical industry, existing industry
Wastewater treatment method complex process, operating cost are high, cannot meet while handle heavy metal ion, acid-base property and organic dyestuff etc.
The requirement of complex component is used as matrix after mixing polyethyleneimine and chitosan, ethylene glycol diglycidylether is as crosslinking
Agent, the adsorbent that one-step synthesis monodispersity is good in micro-fluidic chip, high mechanical strength, absorption property are strong, can be efficiently
Multicomponent industrial wastewater is handled, and eliminates the cumbersome technique that traditional chitosan absorbent needs later stage surface to be modified, is prepared
Process is simple and reliable, has broad application prospects.Based on above-mentioned discovery, the present invention is accomplished.
The present invention provides a kind of polyethyleneimine-chitosan absorbent one-step synthesis, include the following steps：
Step 1：Chitosan, polyethyleneimine and glacial acetic acid are configured to interior phase solution according to a certain percentage, by liquid stone
Wax and petroleum ether are configured to external solution according to certain volume ratio；
Step 2：By External infusion pumping system according to certain flow velocity respectively by the interior phase obtained in step 1 and foreign minister
It each leads into micro-fluidic chip, chitosan drop is made；
Step 3：The chitosan drop obtained in step 2 is passed through in certain density crosslinking curing liquid, control stirring
Chitosan microball is made in speed and mixing time；
Step 4：The chitosan obtained in certain density ethyl alcohol, acetone and deionized water cleaning step three is utilized successively
Microballoon is for several times；And
Step 5：After the chitosan microball obtained in step 4 is freeze-dried, polyethyleneimine-chitosan absorption is obtained
Agent.
In the present invention, interior phase described in step 1 is the chitosan of about 1-3 parts by weight, and the 30% of about 1-3 parts by weight is poly-
The mixed solution of aziridine and the glacial acetic acid of about 1-2 parts by weight, and under about 45-50 DEG C, preferably from about 50 DEG C of water bath condition
It is slowly stirred about 5-6 hours；The foreign minister is atoleine and petroleum ether with volume ratio about 7:5-2:1, preferably from about 7:5 mixing
Solution, and the Span 80 added with about 1-2 parts by weight.
In the present invention, interior foreign minister's velocity ratio described in step 2 is controlled about 1:5-1:20, preferably from about 1:7.
In the present invention, the crosslinking curing liquid described in step 3 is the glutaraldehyde containing about 0.5-1 parts by weight and about 1-2
The normal octane solution of the Span 80 of parts by weight；Chitosan drop is passed through in the crosslinking curing liquid, and is slowly stirred, mixing speed
About 450-650r/min, preferably about 600r/min, mixing time about 30-60min, preferably about 1 hour.
In the present invention, the about 30-40% of ethanol solution concentration used in step 4, preferably about 40%, acetone soln
Concentration about 25-35%, preferably about 30%, chitosan microball is cleaned successively 3-4 times.
In the present invention, about -40 to -60 DEG C of the freeze-drying operation temperature described in step 5, preferably about -45 DEG C,
Freeze-drying time about 10-12 hours.
Below referring to attached drawing.
Fig. 1 is the stream of polyethyleneimine-chitosan absorbent one-step synthesis according to embodiment of the present invention
Cheng Tu.As shown in Figure 1, continuous phase obtained and dispersed phase injection focused flow are declined stream respectively using External infusion pumping system 5
Chip 1 is controlled, a series of chitosan drops are made；The chitosan drop of gained is imported into crosslinking curing liquid 2, stirring in water bath,
Chitosan microball is made；The chitosan microball of gained is cleaned, polyethyleneimine-chitosan microball 3 is obtained；By gained
Polyethyleneimine-chitosan microball freeze-drying, obtains polyethyleneimine-chitosan absorbent 4.
Fig. 2 is polyethyleneimine-chitosan absorbent pictorial diagram according to embodiment of the present invention.
Fig. 3 is to adsorb various concentration methyl orange dye according to the polyethyleneimine-chitosan absorbent of the embodiment of the present application 1
Color contrast.As shown in figure 3, orange red from before adsorbing of left 1 methyl orange solution (0.1%) becomes light yellow after absorption
(left side 2), in orange-yellow from before adsorbing of 1 methyl orange solution (0.01%) become colourless (in 2) after absorption, right 1 methyl orange is molten
Yellow of the liquid (0.001%) from before adsorbing becomes colourless (right side 2) after absorption.
Fig. 4 is to adsorb different pH value acidity and alkalinity according to polyethyleneimine-chitosan absorbent of the embodiment of the present application 2
The color contrast of solution.As shown in figure 4, a row above is to be added with acid indicator (0.1% methyl orange) respectively before adsorbing
Dilute hydrochloric acid solution and added with basic indicator (0.5% phenolphthalein) sodium hydroxide solution；It is prepared using the method for the present invention
After polyethyleneimine-chitosan absorbent processing, color just obviously shoals in the short time, it was demonstrated that is prepared using the method for the present invention
Polyethyleneimine-chitosan absorbent can fast and effeciently adsorb the acidity and alkaline solution of different pH value, such as a following row
It is shown.
Main advantages of the present invention are：
The present invention provides a kind of polyethyleneimine-chitosan absorbent one-step synthesis, using polyethyleneimine and shell
Glycan complex matrix eliminates the cumbersome technique that traditional chitosan absorbent needs later stage surface to be modified, and uses ethylene glycol two
Glycidol ether has preparation side as crosslinking agent by microflow control technique one-step synthesis polyethyleneimine-chitosan absorbent
Method is simple and reliable, absorption property stabilization is effective, can handle the features such as Various Complex component waste water system simultaneously.Obtained poly- second
Good, high mechanical strength, absorption property are strong with monodispersity for alkene imines-chitosan absorbent, can efficiently handle multicomponent
The characteristics of industrial wastewater, has broad application prospects.
Embodiment
With reference to specific embodiment, the present invention is further explained.It should be appreciated, however, that these embodiments are only used for
It is bright the present invention and be not meant to limit the scope of the invention.The test method of actual conditions is not specified in the following example, usually
According to normal condition, or according to the normal condition proposed by manufacturer.Unless otherwise indicated, all percentage and number be by weight
Meter.
Embodiment 1：The methyl orange dye of different initial concentrations is adsorbed using polyethyleneimine-chitosan absorbent
The preparation of polyethyleneimine-chitosan absorbent：
Step 1：By the chitosan of 2 parts by weight, the glacial acetic acid of 30% polyethyleneimine and 2 parts by weight of 3 parts by weight,
It is slowly stirred 6 hours under 50 DEG C of water bath condition to being uniformly mixed, obtains interior phase；In addition, atoleine and petroleum ether are pressed body
Product ratio 7:5 are mixed, and add the Span 80 (being purchased from Sinopharm Chemical Reagent Co., Ltd.) of 2 parts by weight thereto, are filled
Foreign minister is obtained after dividing mixing；
Step 2：Using External infusion pumping system according to 1:The interior phase and foreign minister are passed into poly- by 7 velocity ratio respectively
In burnt streaming micro-fluidic chip, chitosan drop is made；
Step 3：After the chitosan droplets stable obtained in step 2, it is passed into the glutaraldehyde and 2 weights by 1 parts by weight
It in the crosslinking curing liquid that is formed of normal octane for measuring the Span 80 of part, and is slowly stirred, mixing speed 600r/min, when stirring
Between be 40 minutes；
Step 4：A concentration of 40% ethanol solution, 30% acetone soln and deionized water rinsing step are used successively
The chitosan microball obtained in three 3 times；
Step 5：By the chitosan microball obtained in step 4 under the conditions of -45 DEG C, it is freeze-dried 10 hours, is gathered
Aziridine-chitosan absorbent.
The absorption of the methyl orange dye of different initial concentrations：
Weigh polyethyleneimine-chitosan absorbent made from 0.01g be respectively added to 5mL contain 0.1%, 0.01%
In the straight rib collar vial of 0.001% methyl orange solution, and with vibration frequency 800min in test tube mixer-1And vibration
After amplitude 6mm vibrates 5 hours, variation of the comparison polyethyleneimine-chitosan absorbent to different initial concentration methyl orange colors,
As shown in Figure 3.
Experimental result：
It is demonstrated experimentally that polyethyleneimine-chitosan absorbent of the present invention has very the methyl orange dye of various concentration
Good absorption property.
Embodiment 2：Different pH value acidity and alkaline solution are adsorbed using polyethyleneimine-chitosan absorbent
The preparation of polyethyleneimine-chitosan absorbent：
Polyethyleneimine-chitosan absorbent is made by 1 the method for embodiment.
The absorption of different pH value acidity and alkaline solution：
Secure ph is respectively 3,4,5 dilute hydrochloric acid solution, is transferred in the straight rib collar vial of 30mL, and thereto
Add the acid indicator (0.1% methyl orange solution) of 0.1mL.
Secure ph is respectively 8,9,10 sodium hydroxide solution, is transferred in the straight rib collar vial of 30mL, and to
Wherein add the basic indicator (0.5% phenolphthalein solution) of 0.1mL.
It weighs 0.01g polyethyleneimines-chitosan absorbent and is added separately to the straight of different pH value acidity and alkaline solution
In shape rib collar vial, and with vibration frequency 800min in test tube mixer-1It is vibrated 5 hours with vibration amplitude 8mm.
The supernatant liquid 3mL for extracting above-mentioned solution respectively is transferred to straight rib collar vial.Compare polyethyleneimine-shell
Glycan adsorbent is acid to different pH value and the color contrast of alkaline solution, as shown in Figure 4.
Acidity and alkaline solution after absorption are measured using pH test paper, pH value is all close to neutrality.
The acidity and alkaline solution of the corresponding pH value of addition again into the solution after above-mentioned absorption, occur indicator colour developing
Reaction.
Experimental result：
It is demonstrated experimentally that polyethyleneimine-chitosan absorbent of the present invention is acid to different pH value and alkaline solution has
Good absorption property.
Embodiment 3：Utilize the copper ion in polyethyleneimine-chitosan absorbent absorption copper-bath
The preparation of polyethyleneimine-chitosan absorbent：
Polyethyleneimine-chitosan absorbent is made by 1 the method for embodiment.
The absorption of copper ion in copper-bath：
It weighs 0.1g polyethyleneimines-chitosan absorbent and is added to that 50mL initial pH values are 5, copper ion concentration is
In the copper-bath of 100ppm.And with vibration frequency 800min in test tube mixer-1With vibration amplitude 8mm continuous shakings.
Every 10 minutes, the copper-bath of 2mL is taken, it is measured using full spectrum direct-reading plasma emission spectrometer.Finally
It measuring polyethyleneimine-chitosan absorbent and reaches adsorption equilibrium after 80 minutes, copper ion concentration at this time is 11.08ppm,
Adsorption efficiency is 88.92%.
Experimental result：
It is demonstrated experimentally that the chitosan absorbent of the present invention has good absorption property to copper ion.
Above-mentioned listed embodiment is only presently preferred embodiments of the present invention, implementation model not for the purpose of limiting the invention
It encloses.Equivalence changes and modification made by the content of i.e. all claims according to the present invention all should be the technology model of the present invention
Farmland.
All references mentioned in the present invention is incorporated herein by reference, independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can
To be made various changes or modifications to the present invention, such equivalent forms equally fall within model defined by the application the appended claims
It encloses.
Claims (8)
1. a kind of method of one-step synthesis polyethyleneimine-chitosan absorbent, this approach includes the following steps：
(i) chitosan, polyethyleneimine glacial acetic acid are configured to interior phase solution, atoleine and petroleum ether is configured to outer mix
Liquid；
(ii) the interior phase solution and external solution that are obtained in step (i) injection focused flow are declined fluidic chip respectively, is made one
Serial chitosan drop；
(iii) it after the chitosan droplets stable in step (ii) generates, is conducted into crosslinking curing liquid, chitosan is made
Microballoon；
(iv) it is micro- that the chitosan obtained in step (iii) is cleaned multiple times using ethanol solution, acetone soln and deionized water successively
Ball；And
(v) chitosan microball obtained in step (iv) is lyophilized, obtains polyethyleneimine-chitosan absorbent,
Wherein, in step (i), the interior phase solution includes the chitosan added with 1-3 parts by weight, and the 30% of 1-3 parts by weight
The aqueous solution of polyethyleneimine and the glacial acetic acid of 1-2 parts by weight, and be slowly stirred under 45-50 DEG C of water bath condition 5-6 hours；
The external solution includes atoleine and petroleum ether according to volume ratio 7:5-2:1 mixed solution, and it is added with 1-2 parts by weight
Span 80；
In step (iii), the crosslinking curing liquid includes the Span of the glutaraldehyde containing 0.5-1 parts by weight and 1-2 parts by weight
80 normal octane solution.
2. the method as described in claim 1, which is characterized in that in step (ii), by by the interior phase solution and foreign minister
The velocity ratio control of solution is 1:5 to 1:20 are made a series of chitosan drops.
3. the method as described in claim 1, which is characterized in that in step (ii), respectively will using External infusion pumping system
Interior phase solution and external solution the injection focused flow obtained in step (i) declines fluidic chip.
4. the method as described in claim 1, which is characterized in that in step (iii), chitosan drop is passed through crosslinking curing
It in liquid and is slowly stirred, control mixing speed is 450-650r/min, reaction time 30-60min.
5. the method as described in claim 1, which is characterized in that in step (iv), a concentration of 30-40% of ethanol solution,
A concentration of 25-35% of acetone soln, cleans chitosan microball 3-4 times successively.
6. the method as described in claim 1, which is characterized in that in step (v), the freeze temperature is -40 to -60 DEG C,
Freeze-drying time was controlled at 10-12 hours.
7. the method as described in claim 1, which is characterized in that the volume ratio of the atoleine and petroleum ether is 7:5.
8. method as claimed in claim 2, which is characterized in that the control of the velocity ratio of the interior phase solution and external solution is 1:
7。
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| CN109174040B (en) * | 2018-10-12 | 2021-08-06 | 浙江理工大学 | Preparation method of polyfunctional group metal adsorbent |
| CN110665482B (en) * | 2019-10-29 | 2022-08-05 | 中冶武汉冶金建筑研究院有限公司 | Preparation method of chitosan composite microspheres for removing chromium and copper heavy metal ions |
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| CN104258830B (en) * | 2014-10-14 | 2016-05-25 | 河北工业大学 | A kind of chitosan microball medium and methods for making and using same thereof of polyethylene imine beautify |
| CN104437395A (en) * | 2014-11-03 | 2015-03-25 | 中国科学院过程工程研究所 | Acid-resistant magnetic chitosan microspheres as well as preparation method and application thereof |
| CN104741089A (en) * | 2015-02-15 | 2015-07-01 | 华东理工大学 | Method for preparing crosslinked-chitosan-system azo dye wastewater adsorbent |
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