CN102716720A - 1,6-hexamethylenediamine modified chitosan-based magnetic adsorbent and preparation method thereof - Google Patents
1,6-hexamethylenediamine modified chitosan-based magnetic adsorbent and preparation method thereof Download PDFInfo
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- CN102716720A CN102716720A CN2012102358021A CN201210235802A CN102716720A CN 102716720 A CN102716720 A CN 102716720A CN 2012102358021 A CN2012102358021 A CN 2012102358021A CN 201210235802 A CN201210235802 A CN 201210235802A CN 102716720 A CN102716720 A CN 102716720A
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Abstract
The invention discloses a 1,6-hexamethylenediamine modified chitosan-based magnetic adsorbent and further discloses a preparation method of the adsorbent. The preparation method comprises three steps as follows: preparing a chitosan-based magnetic adsorbent, preparing an activated chitosan-based magnetic adsorbent, and preparing the 1,6-hexamethylenediamine modified chitosan-based magnetic adsorbent. The 1,6-hexamethylenediamine modified chitosan-based magnetic adsorbent provided by the invention has the advantages of high amino content, good magnetic separation property and good effect in removing organic pollutants. The preparation method is simple; the preparation process is easy to control; and the quality of the prepared 1,6-hexamethylenediamine modified chitosan-based magnetic adsorbent is stable.
Description
Technical field
The present invention relates to a kind ofly 1,6-hexamethylene diamine chitosan modified base magnetic adsorbent also relates to its preparation method.
Background technology
Water pollutes situation sternness day by day, the particularly organic pollution of trace in the water source now, and owing to its complicated component, difficult degradation, easy accumulation, toxic, the improvement and the drink water purifying of boiler contamination bring huge challenge.Usually polluting for water and adopt the method for absorption to administer, promptly in polluted source, add the adsorbents adsorb pollutant, because the method for absorption belongs to physical method, avoided secondary pollution, is a kind of method for treating water of green.Traditional adsorbent has active carbon, synthetic resin etc.Yet active carbon has non-selective absorption, utilizes shortcomings such as heat and chemical method regeneration cost height, and synthetic resin also has shortcomings such as resource-constrained, preparation cost height, complex process and hydrophilicity are low, has therefore limited its application in water treatment field.
In recent years, international advanced water treatment agent just is being tending towards pollution-free industry direction high-effect, nuisanceless, multi-functional, compoundization and is developing.Shitosan is a kind of adsorbent that can effectively adsorb targeted contaminants, have the higher rate of adsorption and adsorption capacity.Simultaneously, as a kind of natural biological macromolecular material, shitosan can be directly by biodegradation, and the catabolite avirulence, and shitosan is prone to regeneration, and is cheap, the applicable object wide ranges.Its exploitation meets the development trend of international advanced water treatment agent.Yet, pulverous shitosan and solution separating difficulty, and because its good hydrophilicity is easy to swelling caking generation clogging in solution; In addition, shitosan is prone to run off in weakly acidic solution.
Therefore, to above defective, often shitosan is carried out certain physical and chemical modification.Yet; Existing method of modifying has reduced the content of the activated adoption functional group of shitosan after the modification because the amino effect in crosslinking agent and the chitosan molecule can consume the amino that a large amount of shitosans contain itself; Have a strong impact on the absorption property of shitosan after the modification, reduced adsorption capacity.Therefore, press for a kind of new method of modifying of research and development, to promote its application in water treatment to shitosan.
Summary of the invention
Goal of the invention: first purpose of the present invention provide a kind of adsorption capacity high 1,6-hexamethylene diamine chitosan modified base magnetic adsorbent.
Second purpose of the present invention provides 1, the preparation method of 6-hexamethylene diamine chitosan modified base magnetic adsorbent.
Technical scheme: provided by the invention 1,6-hexamethylene diamine chitosan modified base magnetic adsorbent, its structural formula is:
The present invention also provide this 1, the preparation method of 6-hexamethylene diamine chitosan modified base magnetic adsorbent may further comprise the steps:
(1) preparation of chitosan-based magnetic adsorbent (MCP): shitosan and Fe
3O
4Ultrasonic dispersion in acetic acid aqueous solution adds atoleine, class of department 80, ethyl acetate, glutaraldehyde water solution successively under the constant temperature, transfer pH to 7-9, and insulation reaction promptly gets chitosan-based magnetic adsorbent behind the purifying;
(2) preparation of the chitosan-based magnetic adsorbent of activation (MCP of activation): chitosan-based magnetic adsorbent in the mixed solution of the NaOH aqueous solution and methyl-sulfoxide with the epoxychloropropane priming reaction, promptly get the chitosan-based magnetic adsorbent of activation behind the purifying;
The preparation of (3) 1,6-hexamethylene diamine chitosan modified base magnetic adsorbents (A-MCP): the chitosan-based magnetic adsorbent and 1 of activation, the reaction of 6-hexamethylene diamine promptly gets 1 behind the purifying, 6-hexamethylene diamine chitosan modified base magnetic adsorbent.
This preparation method is directly with the Fe of powdered
3O
4Particle and shitosan have been obtained good dispersion effect through ultrasonic dispersion in acetic acid aqueous solution, need not Fe
3O
4Particle carries out surface modification, makes the preparation process simple and easy quick, has made full use of Fe simultaneously
3O
4Hydrophilic and the shitosan good hydrophilicity ability of particle surface makes the nucleocapsid structure of MCP be easy to form.
The absorbent particles amino content for preparing is high, the magnetic stalling characteristic is good, the size even in order to make, dispersive property is good, and the present invention has optimized preparation condition:
In the step (1), the volume fraction of acetate is 1-3% in the said acetic acid aqueous solution;
The mass ratio of shitosan and acetic acid aqueous solution is (1-4): 100, and preferred 2.5:100, shitosan and Fe
3O
4Mass ratio be (0.5-3): 1, preferred 2:1;
Ultrasonic time is 20-40min, preferred 30min; Obtained good dispersion effect through ultrasonic dispersion, made the uniform particles for preparing;
The volume ratio of atoleine and acetic acid aqueous solution is (1-1.5): 1, and preferred 1.25:1; The mass ratio of sorbester p17 and shitosan is (0.5-1): 1, and preferred 0.6:1; The volume ratio of ethyl acetate and acetic acid aqueous solution is (0.2-0.5): 1, and preferred 0.25:1; The concentration of glutaraldehyde water solution is 20-30%, preferred 25%; The amount ratio of glutaraldehyde solution and shitosan is 2-6mL:1g, preferred 4mL:1g;
Reaction temperature is 40-60 ℃, preferred 50 ℃; Reaction time is 2-8h, preferred 5h;
MCP prepares also to be needed in the whole process to stir, and mixing speed is 300-700r/min, preferred 500r/min; Whole process using is unified rotating speed, has reduced the adverse effect of rotation speed change to the diameter of particle distributing homogeneity, makes that reaction condition is more stable, and the diameter of particle for preparing distributes more concentrated;
In the step (2), the concentration of the said NaOH aqueous solution is 0.5-2.0mol/L, and the volume ratio of the said NaOH aqueous solution and methyl-sulfoxide is (0.5-2): 1, and preferred 1:1; The amount ratio of epoxychloropropane and MCP is (0.2-0.4) mL:1g, preferred 0.3mL:1g;
Reaction temperature is 30-50 ℃, preferred 40 ℃; Reaction time is 3-5h, preferred 4h;
The MCP of activation prepares also to be needed in the whole process to stir, and mixing speed is 200-400r/min, preferred 250r/min;
In the step (3), 1, the amount ratio of the MCP of 6-hexamethylene diamine and activation is (3-6) mL:1g, preferred 5mL:1g;
Reaction temperature is 50-70 ℃, preferred 60 ℃; Reaction time is 4-5h, preferred 4.5h;
Also need in the preparation whole process of MCP-A to stir, mixing speed is 200-400r/min, preferred 250r/min.
Beneficial effect: provided by the invention 1,6-hexamethylene diamine chitosan modified base magnetic adsorbent amino content is high, the magnetic stalling characteristic is good, and is effective to organic pollutant removal.This adsorbent has significantly improved the amino content of adsorbent through the chitosan-based magnetic adsorbent of amination modifying; Avoided the traditional shell glycan problem that absorption property descends after modification; Overcome the defective of traditional adsorbent on preparation, regeneration and absorption property, for a kind of new way is sought in the removal of micro quantity organic pollutant.Infrared spectrogram (Fig. 3) by MCP, activation MCP, MCP-A can be known; Activation mainly occurs on the alcoholic extract hydroxyl group of shitosan; X-ray energy spectrum figure (Fig. 4) by MCP, activation MCP, MCP-A can know, the success of MCP chemical modification that nitrogen element content has changed simultaneous verification.Optical microscopic image and scanning electron microscope image (Fig. 5) by MCP-A can know that it is transparent spherical that MCP-A is rufous, and particle diameter is about 120 μ m, and microballoon shows uneven, has bigger contact area.Hysteresis curve figure (Fig. 6) by MCP-A can know that the remanent magnetism of MCP-A is very little, near zero; Can think to belong to superparamagnetic material, its specific saturation magnetization is higher, explains that MCP-A is prone to magnetized by external magnetic field; Can reach the purpose of quick separation; After removing external magnetic, agglomeration can not take place in MCP-A yet, good dispersion property in solution.
This preparation of adsorbent method provided by the invention is with Fe
3O
4Magnetic particle and shitosan are raw material, through the inverse suspension polymerization method, have synthesized with Fe
3O
4Magnetic particle is nuclear; Shitosan is magnetic chitosan particle (the Magnetic Chitosan Particulate of shell; MCP); Simultaneously MCP is carried out activation and amination modifying successively, prepare the high amination magnetic chitosan particle of amino content (Magnetic Chitosan Particulate-Amine, MCP-A).This preparation method is directly with the Fe of powdered
3O
4Particle joins in the chitosan solution, has only just obtained good dispersion effect through ultrasonic dispersion, need not Fe
3O
4Particle carries out surface modification, makes the preparation process simple and easy quick, has made full use of Fe simultaneously
3O
4Hydrophilic and the shitosan good hydrophilicity ability of particle surface makes the nucleocapsid structure of MCP be easy to form.This preparation method is in the MCP building-up process; Whole process using is unified rotating speed, has reduced the adverse effect of rotation speed change to the diameter of particle distributing homogeneity, makes that reaction condition is more stable; Can know that by optical microscopic image and scanning electron microscope image the diameter of particle for preparing distributes more concentrated.
This preparation method is simple, and the preparation process is prone to control, 1 of preparation, 6-hexamethylene diamine chitosan modified base magnetic adsorbent steady quality.
Description of drawings
Fig. 1 a is Fe
3O
4The infrared spectrogram of particle.
Fig. 1 b is the infrared spectrogram of shitosan.
Fig. 1 c is the infrared spectrogram of MCP.
Fig. 2 a is the optical microscopic image of MCP
Fig. 2 b is the scanning electron microscope image of MCP.
Fig. 3 a is the infrared spectrogram of MCP.
Fig. 3 b is the infrared spectrogram of activation MCP.
Fig. 3 c is the infrared spectrogram of MCP-A.
Fig. 4 a is the X-ray energy spectrum of MCP.
Fig. 4 b is the X-ray energy spectrum of activation MCP.
Fig. 4 c is MCP-A three's a X-ray energy spectrum.
Fig. 5 a is the optical microscopic image of MCP-A.
Fig. 5 b is the scanning electron microscope image of MCP-A.
Fig. 6 is the hysteresis curve figure of MCP-A.
Fig. 7 is that MCP-A removes rate diagram to the absorption of micro-Atrazine.
The specific embodiment
According to following embodiment, can understand the present invention better.Yet, those skilled in the art will readily understand that the described concrete material proportion of embodiment, process conditions and result thereof only are used to explain the present invention, and the present invention that should also can not limit in claims to be described in detail.
(1) preparation of MCP:
Dissolving: get volume fraction and be 2% 100mL acetic acid aqueous solution, add the 2.5g shitosan, be mixed with mass fraction and be 2.5% shitosan acetic acid aqueous solution, leave standstill to treat that shitosan all dissolves and is yellow colloidal.
Mix: with the Fe of 1.25g powdered
3O
4Particle joins in the chitosan solution that has dissolved, stirs with glass bar earlier, and ultrasonic 30min in ultrasonic cleaner forms magnetic fluid shitosan mixed liquor then.
Disperse: the 125mL atoleine is poured in the there-necked flask, there-necked flask is placed water-bath, 25 ℃ of waters bath with thermostatic control; Start mechanical stirring device; Stir with 500r/min, in there-necked flask, pour the magnetic fluid shitosan mixed liquor that has made in the whipping process into, stir 20min with this understanding.
Emulsification: keep water-bath and stirring condition in the dispersion process, in mixed liquor, add 1.5g Span-80, add 25mL ethyl acetate again, stir 20min.
Crosslinked: in mixed liquor, add 10mL concentration and be 25% glutaraldehyde solution, the pH value of regulating mixed liquor with the NaOH solution of 2mol/L again is between the 7-9, and it is 50 ℃ of 500r/min stirring 3h that bath temperature is set.
Filter: reaction is poured reaction mixture in the beaker into after finishing, and adds the 350mL benzinum, stirs to make with glass bar to mix.By magnet, treat that MCP is deposited to beaker bottom after, topple over the upper strata milky white solution, in beaker, pour the 150mL benzinum again into, adopt the Buchner funnel vacuum filtration to remove benzinum and obtain MCP.
Washing: with 150mL washing with acetone MCP, add rotor, place and do not heat on the magnetic stirring apparatus standing sedimentation behind the stirring 5min, topple over the upper strata clear solution.Add the 150mL ethanol solution, stir standing sedimentation behind the 5min on the magnetic stirring apparatus, repeat this process once after toppling over the upper strata clear solution.At last MCP is immersed in the ultra-pure water, the last bubble of MCP is too much, places the ultrasonic 2min of ultrasonic cleaner; After treating that MCP is deposited to beaker bottom; Topple over upper solution and the MCP that is suspended in the surface, add ultra-pure water again and soak, this process repeats 3～6 times.Finish in the washing process of back MCP in cross-linking reaction; The use of magnetic stirring apparatus has increased detersive efficiency, has reduced the number of times of later stage with the ultra-pure water washing; Accurate cleaning solvent dosage optimization washing process; Reduce the consumption of acetone and absolute ethyl alcohol, practiced thrift cost, reduced environmental pollution.
Dry: as to isolate MCP with the Buchner funnel vacuum filtration, again MCP is placed vacuum drying chamber, behind 50 ℃ of following vacuum drying 2d, obtain the MCP of dry 3.5g.
(2) activation of MCP:
Swelling: take by weighing 3.0g MCP and place there-necked flask, adding 100mL volume ratio is the 1.0mol/L NaOH aqueous solution of 1:1 and the mixed solution that methyl-sulfoxide is formed, and MCP is in below the mixed liquor liquid level fully, leaves standstill swelling 30min.
Activation: there-necked flask is placed water-bath, and the control bath temperature is 25 ℃, stirs speed with 250r/min and fully stirs, and in there-necked flask, slowly drips the 0.9mL epoxychloropropane in the whipping process, reacts 4h between the warming-in-water to 40 ℃.
Wash dry: reaction finishes the back and obtains activation MCP with the separation of Buchner funnel vacuum filtration, and the activation MCP that separation is obtained pours in the beaker, adds 100mL acetone; Standing sedimentation behind the stirring 10min under the magnetic stirring apparatus; Topple over the upper strata clear solution, add the 100mL ultra-pure water again, till identical mode of washing washs and is neutrality to pH; Behind the suction filtration activation MCP is placed 50 ℃ of vacuum drying 2d of vacuum drying chamber, obtain the MCP of 3.0g activation.
(3) preparation of MCP-A:
Swelling: take by weighing 3.0g activation MCP and place there-necked flask, add 100mL ultra-pure water swelling 30min.
Amination: there-necked flask is placed water-bath, and the control bath temperature is 25 ℃, under the 250r/min stirring condition, in there-necked flask, adds 15mL1, and the 6-hexamethylene diamine reacts 4.5h between the warming-in-water to 60 ℃.
Washing is dry: reaction is left standstill cooling after finishing; Behind the vacuum filtration MCP-A that obtains is placed beaker; Add the 100mL ultra-pure water; The mode cyclic washing MCP-A that adopts magnetic agitation places 50 ℃ of vacuum drying 2d of vacuum drying chamber with MCP-A behind the suction filtration till pH is neutrality, obtain dry final products MCP-A.
By infrared spectrum, light microscope figure, X-ray energy spectrum, scanning electron microscope image and combine this preparation method, can confirm this compound structure.
(1) preparation of MCP:
Dissolving: get volume fraction and be 1% 100mL acetic acid aqueous solution, add the 3g shitosan, be mixed with mass fraction and be 3% shitosan acetic acid solution, leave standstill with treat shitosan all dissolving be yellow colloidal.
Mix: with the Fe of 1.0g powdered
3O
4Particle joins in the chitosan solution that has dissolved, stirs with glass bar earlier, and ultrasonic 30min in ultrasonic cleaner forms magnetic fluid shitosan mixed liquor then.
Disperse: the 150mL atoleine is poured in the there-necked flask, there-necked flask is placed water-bath, 25 ℃ of waters bath with thermostatic control; Start mechanical stirring device; Stir with 600r/min, in there-necked flask, pour the magnetic fluid shitosan mixed liquor that has made in the whipping process into, stir 20min with this understanding.
Emulsification: keep water-bath and stirring condition in the dispersion process, in mixed liquor, add 1.5g Span-80, add 50mL ethyl acetate again, stir 20min.
Crosslinked: in mixed liquor, add 18mL concentration and be 20% glutaraldehyde solution, the pH value of regulating mixed liquor with the NaOH solution of 2mol/L again is between 7～9, and it is 40 ℃ of 600r/min stirring 5h that bath temperature is set.
Filter: reaction is poured reaction mixture in the beaker into after finishing, and adds the 250mL benzinum, stirs to make with glass bar to mix.By magnet, treat that MCP is deposited to beaker bottom after, topple over the upper strata milky white solution, in beaker, pour the 100mL benzinum again into, adopt the Buchner funnel vacuum filtration to remove benzinum and obtain MCP.
Washing: with 100mL washing with acetone MCP, add rotor, place and do not heat on the magnetic stirring apparatus standing sedimentation behind the stirring 10min, topple over the upper strata clear solution.Add the 100mL ethanol solution, stir standing sedimentation behind the 10min on the magnetic stirring apparatus, repeat this process once after toppling over the upper strata clear solution.At last MCP is immersed in the ultra-pure water, treat that MCP is deposited to beaker bottom after, topple over upper solution and the MCP that is suspended in the surface, add ultra-pure water again and soak, this process repeats 3～6 times.
Dry: as to isolate MCP with the Buchner funnel vacuum filtration, again MCP is placed vacuum drying chamber, behind 50 ℃ of following vacuum drying 1d, obtain dry MCP.
(2) activation of MCP:
Swelling: take by weighing 1.0g MCP and place there-necked flask, adding 150mL volume ratio is the 1.0mol/L NaOH of 1:1 and the mixed solution that methyl-sulfoxide is formed, and leaves standstill swelling 30min.
Activation: there-necked flask is placed water-bath, and the control bath temperature is 25 ℃, stirs speed with 300r/min and fully stirs, and in there-necked flask, slowly drips the 0.4mL epoxychloropropane in the whipping process, reacts 3h between the warming-in-water to 50 ℃.
Wash dry: reaction finishes the back and obtains activation MCP with the separation of Buchner funnel vacuum filtration; The activation MCP that separation is obtained pours in the beaker, adds 200mL acetone, standing sedimentation behind the stirring 10min under the magnetic stirring apparatus; Topple over the upper strata clear solution; Add the 200mL ultra-pure water again, identical mode of washing places 50 ℃ of vacuum drying 1d of vacuum drying chamber with activation MCP behind the suction filtration till washing and being neutrality to pH.
(3) preparation of MCP-A:
Swelling: take by weighing 5.0g activation MCP and place there-necked flask, add 150mL ultra-pure water swelling 30min.
Amination: there-necked flask is placed water-bath, and the control bath temperature is 25 ℃, under the 300r/min stirring condition, in there-necked flask, adds 6mL1, and the 6-hexamethylene diamine reacts 4h between the warming-in-water to 70 ℃.
Washing is dry: reaction is left standstill cooling after finishing; Behind the vacuum filtration MCP-A that obtains is placed beaker; Add the 200mL ultra-pure water; The mode cyclic washing MCP-A that adopts magnetic agitation places 50 ℃ of vacuum drying 1d of vacuum drying chamber with MCP-A behind the suction filtration till pH is neutrality, obtain dry final products MCP-A.
(1) preparation of MCP:
Dissolving: get volume fraction and be 3% 100mL acetic acid aqueous solution, add the 1.0g shitosan, be mixed with mass fraction and be 1% shitosan acetic acid solution, leave standstill with treat shitosan all dissolving be yellow colloidal.
Mix: with the Fe of 2.0g powdered
3O
4Particle joins in the chitosan solution that has dissolved, stirs with glass bar earlier, and ultrasonic 20min in ultrasonic cleaner forms magnetic fluid shitosan mixed liquor then.
Disperse: the 100mL atoleine is poured in the there-necked flask, there-necked flask is placed water-bath, 25 ℃ of waters bath with thermostatic control; Start mechanical stirring device; Stir with 700r/min, in there-necked flask, pour the magnetic fluid shitosan mixed liquor that has made in the whipping process into, stir 20min with this understanding.
Emulsification: keep water-bath and stirring condition in the dispersion process, in mixed liquor, add 1.0g Span-80, add 20mL ethyl acetate again, stir 20min.
Crosslinked: in mixed liquor, add 5mL concentration and be 25% glutaraldehyde solution, the pH value of regulating mixed liquor with the NaOH solution of 2mol/L again is between 7～9, and it is 60 ℃ of 700r/min stirring 2h that bath temperature is set.
Filter: reaction is poured reaction mixture in the beaker into after finishing, and adds the 250mL benzinum, stirs to make with glass bar to mix.By magnet, treat that MCP is deposited to beaker bottom after, topple over the upper strata milky white solution, in beaker, pour the 100mL benzinum again into, adopt the Buchner funnel vacuum filtration to remove benzinum and obtain MCP.
Washing: with 100mL washing with acetone MCP, add rotor, place and do not heat on the magnetic stirring apparatus standing sedimentation behind the stirring 5min, topple over the upper strata clear solution.Add the 100mL ethanol solution, stir standing sedimentation behind the 5min on the magnetic stirring apparatus, repeat this process once after toppling over the upper strata clear solution.At last MCP is immersed in the ultra-pure water, the last bubble of MCP is too much, places the ultrasonic 5min of ultrasonic cleaner; After treating that MCP is deposited to beaker bottom; Topple over upper solution and the MCP that is suspended in the surface, add ultra-pure water again and soak, this process repeats 3～6 times.
Dry: as to isolate MCP with the Buchner funnel vacuum filtration, again MCP is placed vacuum drying chamber, behind 50 ℃ of following vacuum drying 2d, obtain dry MCP.
(2) activation of MCP:
Swelling: take by weighing 2.0g MCP and place there-necked flask, adding 200mL volume ratio is the 1.0mol/L NaOH of 0.5:1 and the mixed solution that methyl-sulfoxide is formed, and leaves standstill swelling 30min.
Activation: there-necked flask is placed water-bath, and the control bath temperature is 25 ℃, stirs speed with 200r/min and fully stirs, and in there-necked flask, slowly drips the 0.4mL epoxychloropropane in the whipping process, reacts 5h between the warming-in-water to 30 ℃.
Wash dry: reaction finishes the back and obtains activation MCP with the separation of Buchner funnel vacuum filtration; The activation MCP that separation is obtained pours in the beaker, adds 150mL acetone, standing sedimentation behind the stirring 5min under the magnetic stirring apparatus; Topple over the upper strata clear solution; Add the 150mL ultra-pure water again, identical mode of washing places 50 ℃ of vacuum drying 2d of vacuum drying chamber with activation MCP behind the suction filtration till washing and being neutrality to pH.
(3) preparation of MCP-A:
Swelling: take by weighing 2.0g activation MCP and place there-necked flask, add 200mL ultra-pure water swelling 30min.
Amination: there-necked flask is placed water-bath, and the control bath temperature is 25 ℃, under the 200r/min stirring condition, in there-necked flask, adds 6mL1, and the 6-hexamethylene diamine reacts 5h between the warming-in-water to 50 ℃.
Washing is dry: reaction is left standstill cooling after finishing; Behind the vacuum filtration MCP-A that obtains is placed beaker; Add the 100mL ultra-pure water; The mode cyclic washing MCP-A that adopts magnetic agitation places 50 ℃ of vacuum drying 2d of vacuum drying chamber with MCP-A behind the suction filtration till pH is neutrality, obtain dry final products MCP-A.
(1) preparation of MCP:
Dissolving: get volume fraction and be 2% 100mL acetic acid aqueous solution, add the 4.0g shitosan, be mixed with mass fraction and be 4.0% shitosan acetic acid solution, leave standstill to treat that shitosan all dissolves and is yellow colloidal.
Mix: with the Fe of 2g powdered
3O
4Particle joins in the chitosan solution that has dissolved, stirs with glass bar earlier, and ultrasonic 40min in ultrasonic cleaner forms magnetic fluid shitosan mixed liquor then.
Disperse: the 150mL atoleine is poured in the there-necked flask, there-necked flask is placed water-bath, 25 ℃ of waters bath with thermostatic control; Start mechanical stirring device; Stir with 300r/min, in there-necked flask, pour the magnetic fluid shitosan mixed liquor that has made in the whipping process into, stir 20min with this understanding.
Emulsification: keep water-bath and stirring condition in the dispersion process, in mixed liquor, add 3g Span-80, add 50mL ethyl acetate again, stir 20min.
Crosslinked: in mixed liquor, add 8mL concentration and be 30% glutaraldehyde solution, the pH value of regulating mixed liquor with the NaOH solution of 2mol/L again is between the 7-9, and it is 40 ℃ of 300r/min stirring 8h that bath temperature is set.
Filter: reaction is poured reaction mixture in the beaker into after finishing, and adds the 350mL benzinum, stirs to make with glass bar to mix.By magnet, treat that MCP is deposited to beaker bottom after, topple over the upper strata milky white solution, in beaker, pour the 150mL benzinum again into, adopt the Buchner funnel vacuum filtration to remove benzinum and obtain MCP.
Washing: with 150mL washing with acetone MCP, add rotor, place and do not heat on the magnetic stirring apparatus standing sedimentation behind the stirring 5min, topple over the upper strata clear solution.Add the 150mL ethanol solution, stir standing sedimentation behind the 5min on the magnetic stirring apparatus, repeat this process once after toppling over the upper strata clear solution.At last MCP is immersed in the ultra-pure water, the last bubble of MCP is too much, places the ultrasonic 2min of ultrasonic cleaner; After treating that MCP is deposited to beaker bottom; Topple over upper solution and the MCP that is suspended in the surface, add ultra-pure water again and soak, this process repeats 3～6 times.
Dry: as to isolate MCP with the Buchner funnel vacuum filtration, again MCP is placed vacuum drying chamber, behind 50 ℃ of following vacuum drying 2d, obtain the dry MCP of 12g.
(2) activation of MCP:
Swelling: take by weighing 3.0g MCP and place there-necked flask, adding 100mL volume ratio is the 0.5mol/L NaOH aqueous solution of 2:1 and the mixed solution that methyl-sulfoxide is formed, and makes MCP be positioned at the mixed liquor liquid level fully once, leaves standstill swelling 30min.
Activation: there-necked flask is placed water-bath, and the control bath temperature is 25 ℃, stirs speed with 400r/min and fully stirs, and in there-necked flask, slowly drips the 0.9mL epoxychloropropane in the whipping process, reacts 4h between the warming-in-water to 40 ℃.
Wash dry: reaction finishes the back and obtains activation MCP with the separation of Buchner funnel vacuum filtration, and the activation MCP that separation is obtained pours in the beaker, adds 100mL acetone; Standing sedimentation behind the stirring 10min under the magnetic stirring apparatus; Topple over the upper strata clear solution, add the 100mL ultra-pure water again, till identical mode of washing washs and is neutrality to pH; Behind the suction filtration activation MCP is placed 50 ℃ of vacuum drying 2d of vacuum drying chamber, obtain the MCP (amount) of 3g activation.
(3) preparation of MCP-A:
Swelling: take by weighing 3.0g activation MCP and place there-necked flask, add 100mL ultra-pure water swelling 30min.
Amination: there-necked flask is placed water-bath, and the control bath temperature is 25 ℃, under the 400r/min stirring condition, in there-necked flask, adds 15mL1, and the 6-hexamethylene diamine reacts 4.5h between the warming-in-water to 60 ℃.
Washing is dry: reaction is left standstill cooling after finishing; Behind the vacuum filtration MCP-A that obtains is placed beaker; Add the 100mL ultra-pure water; The mode cyclic washing MCP-A that adopts magnetic agitation places 50 ℃ of vacuum drying 2d of vacuum drying chamber with MCP-A behind the suction filtration till pH is neutrality, obtain dry final products MCP-A.
Embodiment 5
MCP among the embodiment 1, activation MCP, the contrast of MCP-A three's amino content
The amino content assay method is following:
The MCP, activation MCP, MCP-A that take by weighing 0.05g respectively add the standard HCl solution of 20mL, 0.1mol/L respectively in conical flask, place the constant temperature water bath oscillator; Normal temperature vibration 2h; After making it complete reaction, get the 15mL supernatant, add 2 phenolphthalein indicators (1%); With the remaining hydrochloric acid of standard NaOH solution titration of 0.1mol/L, titration end-point is that solution is by the colourless redness that becomes; Measure the result and see table 1, the amino content computing formula is:
In the formula, N
1The concentration of-standard HCl, i.e. 0.1mol/L
V
1The volume of-standard HCl, i.e. 20mL
N
2The concentration of-standard NaOH, i.e. 0.1mol/L
V
2The volume of the used standard NaOH of-titration (mL)
The quality of m-MCP, i.e. 0.05g
Table 1MCP, activation MCP, the contrast of MCP-A amino content
MCP-A removes the absorption of micro-Atrazine, proves beneficial effect of the present invention with the adsorption test of Atrazine.
Adopting the Atrazine initial concentration is 100 μ g/L, MCP-A throwing amount 1g/20mL, and pH value of solution value 4.0,25 ℃ of water temperatures, Atrazine concentration is measured through the LC-20A high performance liquid chromatograph.Accompanying drawing 7 is that MCP-A removes rate diagram to the absorption of micro-Atrazine.The Atrazine clearance reaches balance during 2h, and after this clearance maintains about 65%, and MCP-A has obtained removal effect preferably to micro-Atrazine.
Claims (9)
1. one kind 1,6-hexamethylene diamine chitosan modified base magnetic adsorbent, its structural formula is:
2. one kind 1, the preparation method of 6-hexamethylene diamine chitosan modified base magnetic adsorbent is characterized in that: may further comprise the steps:
(1) preparation of chitosan-based magnetic adsorbent: shitosan and Fe
3O
4Ultrasonic dispersion in acetic acid aqueous solution adds atoleine, class of department 80, ethyl acetate, glutaraldehyde water solution successively under the constant temperature, transfer pH to 7-9, and insulation reaction promptly gets chitosan-based magnetic adsorbent behind the purifying;
(2) preparation of the chitosan-based magnetic adsorbent of activation: chitosan-based magnetic adsorbent in the mixed solution of the NaOH aqueous solution and methyl-sulfoxide with the epoxychloropropane priming reaction, promptly get the chitosan-based magnetic adsorbent of activation behind the purifying;
The preparation of (3) 1,6-hexamethylene diamine chitosan modified base magnetic adsorbents: the chitosan-based magnetic adsorbent and 1 of activation, the reaction of 6-hexamethylene diamine promptly gets 1 behind the purifying, 6-hexamethylene diamine chitosan modified base magnetic adsorbent.
3. according to claim 2 a kind of 1; The preparation method of 6-hexamethylene diamine chitosan modified base magnetic adsorbent is characterized in that: in the step (1), the volume fraction of said acetic acid aqueous solution is 1-3%; The mass ratio of shitosan and acetic acid aqueous solution is (14): 100, and shitosan and Fe
3O
4Mass ratio be (0.5-3): 1, ultrasonic time is 20-40min.
4. according to claim 2 a kind of 1; The preparation method of 6-hexamethylene diamine chitosan modified base magnetic adsorbent; It is characterized in that: in the step (1), the volume ratio of atoleine and acetic acid aqueous solution is (1-1.5): 1, and the mass ratio of sorbester p17 and shitosan is (0.5-1): 1; The volume ratio of ethyl acetate and acetic acid aqueous solution is (0.2-0.5): 1; The concentration of glutaraldehyde water solution is 20-30%, and the amount ratio of glutaraldehyde water solution and shitosan is 2-6mL:1g.
5. according to claim 2 a kind of 1, the preparation method of 6-hexamethylene diamine chitosan modified base magnetic adsorbent is characterized in that: in the step (1), reaction temperature is 40-60 ℃; Reaction time is 2-8h; Also need to stir, mixing speed is 300-700r/min.
6. according to claim 2 a kind of 1; The preparation method of 6-hexamethylene diamine chitosan modified base magnetic adsorbent; It is characterized in that: in the step (2); The concentration of the said NaOH aqueous solution is 0.5-2.0mol/L, and the volume ratio of the said NaOH aqueous solution and methyl-sulfoxide is (0.5-2): 1, and the amount ratio of the chitosan-based magnetic adsorbent of epoxychloropropane and activation is (0.2-0.4) mL:1g.
7. according to claim 2 a kind of 1, the preparation method of 6-hexamethylene diamine chitosan modified base magnetic adsorbent is characterized in that: in the step (2), reaction temperature is 30-50 ℃; Reaction time is 3-5h; Also need to stir, mixing speed is 200-400r/min.
8. according to claim 2 a kind of 1, the preparation method of 6-hexamethylene diamine chitosan modified base magnetic adsorbent is characterized in that: in the step (3), and 1, the amount ratio of the chitosan-based magnetic adsorbent of 6-hexamethylene diamine and activation is (3-6) mL:1g.
9. according to claim 2 a kind of 1, the preparation method of 6-hexamethylene diamine chitosan modified base magnetic adsorbent is characterized in that: in the step (3), reaction temperature is 50-70 ℃; Reaction time is 4-5h; Also need to stir, mixing speed is 200-400r/min.
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| CN106107242A (en) * | 2016-07-29 | 2016-11-16 | 舟山市瑞丰生物技术有限公司 | A kind of nonreactive aquatic immune reinforcing agent |
| CN109317114A (en) * | 2018-12-24 | 2019-02-12 | 重庆大学 | A kind of preparation method and application of compound magnetic chitosan adsorbent material |
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| Title |
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| 丁明等: "Fe3O4/壳聚糖核壳磁性微球的制备及特性", 《磁性材料及器件》 * |
| 张梦霜等: "盐酸和硝酸介质中己二胺接枝壳聚糖微球吸附Hg(Ⅱ)的行为", 《环境工程学报》 * |
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|---|---|---|---|---|
| CN106107242A (en) * | 2016-07-29 | 2016-11-16 | 舟山市瑞丰生物技术有限公司 | A kind of nonreactive aquatic immune reinforcing agent |
| CN109317114A (en) * | 2018-12-24 | 2019-02-12 | 重庆大学 | A kind of preparation method and application of compound magnetic chitosan adsorbent material |
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