CN104056604B - The preparation method of the just arsenious scavenging material of a kind of water body - Google Patents

The preparation method of the just arsenious scavenging material of a kind of water body Download PDF

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CN104056604B
CN104056604B CN201410333404.2A CN201410333404A CN104056604B CN 104056604 B CN104056604 B CN 104056604B CN 201410333404 A CN201410333404 A CN 201410333404A CN 104056604 B CN104056604 B CN 104056604B
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preparation
rice
shitosan
nano grain
arsenic
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CN104056604A (en
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宋晓丽
张清清
郭荣
朱爱萍
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Yangzhou University
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Yangzhou University
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Abstract

A preparation method for the just arsenious scavenging material of water body, relates to field of environmental technology.The chitosan-based micro-nano grain of rice that the present invention for carrier material, adopts inverse suspension crosslinking polymerization parcel titanium dioxide with shitosan and quaternary ammonium salt derivative thereof, ferriferrous oxide nano-particle preparation has photocatalysis and Magneto separate function.Material therefor environmental protection of the present invention, preparation method is simple, gained micro-nano grain of rice uniform particle sizes, water body arsenic (III) adsorption rate is high, and being expected to becomes the novel green material for water treatment that one has high arsenic removal (III) efficiency and Magneto separate function.

Description

The preparation method of the just arsenious scavenging material of a kind of water body
Technical field
The present invention relates to the preparing technical field of material, relate to the preparation method of the scavenging material with photocatalysis and Magneto separate function, belong to field of environmental technology.
Background technology
Arsenic is a kind of metalloid element being prevalent in occurring in nature, and different according to form, arsenic can be divided into inorganic arsenic and organo-arsenic.Different according to chemical valence, arsenic can be divided into again positive pentavalent arsenic As(V) and positive trivalent arsenic As(III).All the time, arsenic is well-known with its high toxicity.Arsenic element official confirmation was human carcinogen in 1980 by international cancer research institution.In recent years, because mankind's activity is to the destruction of natural environment, the pollution of arsenic to environment is on the rise, especially to the pollution of global water resources.Therefore, extremely urgent to the purified treatment research of water body arsenic.
In water body, arsenic is mainly with arsenious acid (AsO 3 3-) and arsenic acid (AsO 4 3-) form exist, under natural environment pH condition, the general neutral of arsenious acid, and arsenic acid is electronegative, therefore in traditional water treatment procedure, first pass through pretreatment, arsenious acid oxidation conversion is become arsenic acid, then by electrostatic adsorption, the arsenic in water is all removed.But this process is loaded down with trivial details, subsequent treatment bothers.
Summary of the invention
The object of the invention is to propose a kind of efficient and arsenic adsorbent of environmental protection, especially can remove the preparation method of the environmental protection water purification material of water body arsenic (III) simply and effectively.
The present invention includes following steps:
1) by Fe 3o 4, TiO 2the quaternary ammonium salt derivative of nanoparticle and shitosan or shitosan is dissolved in acetum, forms mixed liquor;
2) mixed liquor and atoleine are added 0.6mL Tween 80 and 4mL ethyl acetate after stirring 20min, obtain W/O emulsion;
3) after W/O emulsion being warming up to 40 DEG C, being under the condition of 500r/min at rotating speed, adding formaldehyde, then add glutaraldehyde after being warming up to 50 DEG C, form mixed system;
4) with sodium hydrate aqueous solution regulating step 3) the mixed system pH to 7.5 that makes, through stirring reaction to terminating, more successively with the washing of benzinum, acetone, ethanol and intermediate water, drying, obtains the chitosan-based micro-nano grain of rice, i.e. scavenging material.
The present invention adopts a kind of biodegradable, eco-friendly shitosan or its quaternary ammonium salt derivative to be carrier material, employing inverse suspension crosslinking polymerization parcel titanium dioxide, ferriferrous oxide nano-particle prepare the chitosan-based micro-nano grain of rice, study it to the removal efficiency of water body arsenic (III) and service condition.The final obtained chitosan-based micro-nano grain of rice effectively can remove water body arsenic (III), and there is light sensitivity and Magneto separate function, especially substitution value is the quaternization chitosan-based micro-nano grain of rice natural environment pH(4-10 that may exist of 64.47%) scope in arsenic removal (III) can more than 90% be reached, and substantially not by the impact of sulfate radical, phosphate anion in water body.
The present invention overcomes existing arsenic removal material, and especially for the deficiency that water body arsenic (III) arsenic removal material exists, preparation method is reliably easy, and experimental period is shorter, is expected batch production to be applied to actual water treatment.
The shitosan micro-nano grain of rice (MTCNPs) obtained by the present invention, the Quaternary Ammonium Salt of Chitosan micro-nano grain of rice (MTHCNPs-1, MTHCNPs-2) arsenic removal (III) efficiency are high, and increase with quaternary ammonium salt substitution value, removal efficiency is higher; When pH value is neutral, arsenic removal (III) is most effective; In 0.5h, three kinds of composites all can reach comparatively high adsorption rate, reach absorption saturated in 2h; Under low ion concns, gained micro-nano grain of rice arsenic removal (III) efficiency is substantially unaffected, only at high PO 4 3-under concentration, its arsenic removal (III) efficiency reduces (under natural conditions, the phosphate concentration in underground water is general all very low); UV-irradiation, effectively can increase the adsorption capacity of the micro-nano grain of rice and have Magneto separate function, being convenient to subsequent treatment.Research shows that MTHCNPs-2 arsenic removal in the scope of pH5-10 (III) efficiency all can reach more than 90%, and the pH of natural water is generally 4-10, show that MTHCNPs-2 effectively can be applied to the adsorption treatment of arsenic (III) in various natural water.MTHCNPs-2 is expected to become the new green environment protection material that one has high arsenic removal (III) efficiency and Magneto separate function, and preparation technology is simple, is applicable to batch production.
In addition, described Fe 3o 4, TiO 2be 2 ︰ 2 ︰ 5 with the mixing quality ratio of shitosan or chitosan quaternary ammonium salt derivatives.Under this ratio, the obtained chitosan-based micro-nano grain of rice has Magneto separate function and photo-catalysis function and has higher arsenic (III) adsorption efficiency.
Acetum of the present invention is the aqueous acetic acid of 2wt%, fully to dissolve shitosan and chitosan quaternary ammonium salt; And adopt ultrasonic process, with accelerate dissolution speed when dissolving.
In described W/O emulsion, the percent by volume of Tween 80 is 1.5%, ethyl acetate percent by volume be 10%, to form stable water-in-oil emulsion.
In the mixed system that described step 3) is made, the percent by volume of formaldehyde is 8%, and the percent by volume of glutaraldehyde is 4%, to make cross-linking reaction complete, obtains the more uniform chitosan-based micro-nano grain of rice of particle diameter.
In order to make cross-linking reaction fully carry out, preferably in 30min, formaldehyde is added in W/O emulsion.
Accompanying drawing explanation
Fig. 1 is the FT-IR collection of illustrative plates of shitosan and chitosan quaternary ammonium salt.
Fig. 2 is the preparation flow figure of the chitosan-based micro-nano grain of rice.
Fig. 3 is the FT-IR figure of MTCNPs, MTHCNPs-1, MTHCNPs-2.
Fig. 4 is the SEM figure of shitosan micro-nano grain of rice MTCNPs.
Fig. 5 is the SEM figure of chitosan-based micro-nano grain of rice MTHCNPs-1.
Fig. 6 is the SEM figure of chitosan-based micro-nano grain of rice MTHCNPs-2.
Fig. 7 is the magnetization curve figure of MTCNPs, MTHCNPs-1, MTHCNPs-2.
Fig. 8 is dispersed in the photo in water without the micro-nano grain of rice under magnetic action.
Fig. 9 is the photo that the micro-nano grain of rice is precipitated out from water under magnetic field.
Figure 10 As 2o 3aFS canonical plotting.
Figure 11 is the effect diagram of pH value to chitosan-based micro-nano grain of rice arsenic-adsorbing (III) efficiency.
Figure 12 is the kinetic curve of chitosan-based micro-nano grain of rice arsenic-adsorbing (III).
Figure 13 is PO 4 3-and SO 4 2-the impact of ion pair shitosan micro-nano grain of rice MTCNPs arsenic-adsorbing (III) efficiency.
Figure 14 is PO 4 3-and SO 4 2-the impact of ion pair chitosan-based micro-nano grain of rice MTHCNPs-1 arsenic-adsorbing (III) efficiency.
Figure 15 is PO 4 3-and SO 4 2-the impact of ion pair chitosan-based micro-nano grain of rice MTHCNPs-2 arsenic-adsorbing (III) efficiency.
Figure 16 is the effect diagram of UV-irradiation to shitosan micro-nano grain of rice MTCNPs arsenic-adsorbing (III) efficiency.
Figure 17 is the effect diagram of UV-irradiation to chitosan-based micro-nano grain of rice MTHCNPs-1 arsenic-adsorbing (III) efficiency.
Figure 18 is the effect diagram of UV-irradiation to chitosan-based micro-nano grain of rice MTHCNPs-2 arsenic-adsorbing (III) efficiency.
Detailed description of the invention
one, preparation technology:
1, Fe is prepared 3 o 4 nanoparticle:
Will containing Fe 2+solution and containing Fe 3+solution with Fe 2+and Fe 3+mol ratio is that 1 ︰ 2 mixing is reacted, and take concentration as the ammoniacal liquor adjust pH to 13 of 1mol/L, after no longer including black precipitate and producing, then wash pH value to 7 ~ 8 of system to reaction with anaerobic water, freeze drying, obtains Fe 3o 4nanoparticle.
2, chitosan quaternary ammonium salt (HTCC) is synthesized:
Getting 0.5g shitosan (CS) is dissolved in the acetum of 2wt%, dropwise adds 1mol/L sodium hydroxide solution and CS is separated out, and system pH, 9 ~ 10, soaks 8h, suction filtration, gets solid matter washing to neutral, obtains white flock shitosan.
White flock shitosan is dispersed in 15mL isopropyl alcohol, shitosan system in the pasty state after being uniformly dispersed.
Respectively 2, the 3-epoxypropyltrimethylchloride chlorides (GTA) of 1.0g, 2.0g are dissolved in 5mL isopropyl alcohol, make the aqueous isopropanol of 2, the 3-epoxypropyltrimethylchloride chlorides (GTA) of variable concentrations respectively.
At 80 DEG C, slowly 2 of variable concentrations is dripped respectively in pasty state shitosan system, the aqueous isopropanol of 3-epoxypropyltrimethylchloride chloride (GTA), 2h drips off, react 6h respectively, make precipitating reagent with absolute ethyl alcohol again product is precipitated out, through suction filtration, drying, namely obtain chitosan quaternary ammonium salt HTCC respectively.
3, the IR Characterization of quaternization shitosan:
Determinand and KBr are mixed with the mass ratio of 1:100, measures on NiocetFT-IR type infrared spectrometer after compressing tablet.Sweep limits is 4000-400cm -1, resolution ratio 0.09cm -1.
The FT-IR collection of illustrative plates of shitosan as shown in Figure 1 and chitosan quaternary ammonium salt.
In figure, curve a represents: the FT-IR collection of illustrative plates of GTA; Curve b represents: the FT-IR collection of illustrative plates of shitosan; Curve c represents: the FT-IR collection of illustrative plates of chitosan quaternary ammonium salt HTCC-1; Curve d represents: the FT-IR collection of illustrative plates of chitosan quaternary ammonium salt HTCC-2.
As can be seen from Figure at 1486cm -1there is a new characteristic absorption peak, shown successfully to synthesize HTCC.Along with the increase of epoxy chloropropane, 1600cm -1the intensity of the characteristic absorption peak of N-H obviously reduces, and 1486cm thereupon -1the C-H flexural vibrations characteristic absorption peak occurred strengthens gradually.
the preparation (MTCNPs, MTHCNPs-1, MTHCNPs-2) of 4, scavenging material---the chitosan-based micro-nano grain of rice:
As shown in Figure 2, step is as follows:
(1) get 1g shitosan or chitosan quaternary ammonium salt HTCC joins in the solution of 20mL acetic acid (2%), then add 0.4gFe 3o 4and 0.4gTiO 2nanoparticle, with being uniformly mixed rear ultrasonic mixing 10min.
(2) above-mentioned solution is added in 20mL atoleine, stir 20min.Add 0.6mL Tween 80 (1.5%), 4mL ethyl acetate (10%) at room temperature stir the condition of 20min with rotating speed 300r/min under, obtain W/O emulsion.
(3) after the temperature of W/O emulsion being increased to 40 DEG C, be under the condition of 500r/min at rotating speed, in 30min, add 3.2mL crosslinking agent formaldehyde (8%).
(4), after again the temperature of mixed system being increased to 50 DEG C, 1.6mL crosslinking agent glutaraldehyde (4%) is added.
(5) with 2M NaOH, the pH value of system is adjusted to 7.5, then stir emulsion 3h with the rotating speed of 250r/min.
(6) benzinum, acetone, ethanol and intermediate water is adopted to wash the shitosan micro-nano grain of rice (MTCNPs), the chitosan quaternary ammonium salt micro-nano grain of rice of synthesis successively (mTHCNPs-1, MTHCNPs-2), then drying also at room temperature stores in 50 DEG C of vacuum drying chambers.
two, the sign of the chitosan-based micro-nano grain of rice:
Employing model is that the fourier infrared spectrometer (FTIR) of TENSOR27 characterizes respectively to the nanoparticle made, as shown in Figure 3.In Fig. 3, curve a represents: the FT-IR collection of illustrative plates of the shitosan micro-nano grain of rice (MTCNPs); Curve b represents: the FT-IR collection of illustrative plates of the chitosan quaternary ammonium salt micro-nano grain of rice (MTHCNPs-1); Curve c represents: the FT-IR collection of illustrative plates of the chitosan quaternary ammonium salt micro-nano grain of rice (MTHCNPs-2); Curve d represents: Fe 3o 4fT-IR collection of illustrative plates; Curve e represents: TiO 2fT-IR collection of illustrative plates.
583cm in FT-IR spectrogram can be found out by the FT-IR figure of MTCNPs, MTHCNPs-1, MTHCNPs-2 in Fig. 3 -1and 528cm -1there is corresponding characteristic peak at place, and Fe is described 3o 4and TiO 2nanoparticle is successfully coated in the composite micro-nano grain of rice.
Employing model is that the SEM (SEM) of XL-30E characterizes respectively to the nanoparticle made, shown in Fig. 4,5,6.The SEM figure of chitosan-based the micro-nano grain of rice MTCNPs, MTHCNPs-1, MTHCNPs-2 of representing respectively from Fig. 4,5,6 can find out: the micro-nano grain of rice rough surface of gained, size uniform.
Show the magnetization curve of MTCNPs, MTHCNPs in Fig. 7, employing model is that the oscillation sample magnetometer (VSM) of EV7 is tested it, and in figure, curve a represents: the magnetization curve of the shitosan micro-nano grain of rice (MTCNPs); Curve b represents: the magnetization curve of the chitosan quaternary ammonium salt micro-nano grain of rice (MTHCNPs-1); Curve c represents: the magnetization curve of the chitosan quaternary ammonium salt micro-nano grain of rice (MTHCNPs-2).
Fig. 7 shows: the micro-nano of gained has superparamagnetism, can be removed in water treatment by externally-applied magnetic field.
Fig. 8 is for be dispersed in water without micro-nano grain of rice each under magnetic action.When after the effect of employing externally-applied magnetic field, as shown in Figure 9, each micro-nano grain of rice is precipitated out from water, illustrates that the micro-nano of gained has Magneto separate function.
Figure 10 is As 2o 3aFS calibration curve.Accurately measure 0.0,0.1,0.2,0.3,0.4,0.5,0.6, the As of 0.7mL 2o 3standard solution (1 μ g/mL) is in the volumetric flask of 10mL, and add the hydrochloric acid 2mL of 6mol/L respectively, the thiourea and ascorbic acid 1mL of 50g/L, distilled water is settled to 10mL, wherein containing As 2o 3concentration is respectively 0,10,20,30,40,50,60,70ng/mL.After leaving standstill 10min, measure with atomic fluorescence spectrophotometer.Read the fluorescence intensity level of each standard serial solution, with As wherein 2o 3concentration is abscissa, and corresponding fluorescence intensity level is ordinate, drawing standard curve.Calibration curve is I=51.332C-44.522, and wherein I is fluorescence intensity, and C is arsenic concentration.Gained equation of linear regression R 2value is 0.9970, illustrates that this calibration curve linear relationship is good, can be used as standard working curve application.
three, the research of chitosan-based micro-nano grain of rice arsenic removal (III) efficiency:
(1) pH impact
Figure 11 is the effect diagram of pH value to chitosan-based micro-nano grain of rice arsenic-adsorbing (III) efficiency, and employing model is that the atomic fluorescence spectrophotometer of AFS-3100 measures fluorescence intensity, thus calculates adsorption rate.
As can be seen from Figure, when pH value is neutral, the adsorption efficiency of three kinds of materials is the highest, and MTHCNPs-2 has higher adsorption efficiency in the scope of pH5-10, illustrates and does not substantially affect by pH.
(2) time effects
Figure 12 is the kinetic curve figure of chitosan-based micro-nano grain of rice arsenic-adsorbing (III), and as can be seen from the figure in 0.5h, three kinds of composites all can reach comparatively high adsorption rate, reach absorption saturated, and the absorption of MTHCNPs-2 is the highest in 2h.
(3) ion impact
Figure 13,14,15 is respectively PO 4 3-and SO 4 2-the effect diagram of ion pair chitosan-based micro-nano grain of rice arsenic-adsorbing (III) efficiency.
As shown in the figure, gained chitosan-based micro-nano grain of rice arsenic removal (III) efficiency is not substantially by SO 4 2-ion affects, low PO 4 3under ion concentration, gained chitosan-based micro-nano grain of rice arsenic removal (III) efficiency is substantially unaffected, and only at high PO 4 3-under concentration, its arsenic removal (III) efficiency reduces (under natural conditions, the phosphate concentration in underground water is general all very low).
(4) influence of ultraviolet light
Figure 16,17,18 is the effect diagram of UV-irradiation to chitosan-based micro-nano grain of rice arsenic-adsorbing (III) efficiency respectively, as can be seen from Figure, when UV-irradiation, effectively can increase the adsorption efficiency of material 10% ~ 20%, illustrate that prepared material has light sensitive effect.
sum up:by the research to chitosan-based micro-nano grain of rice arsenic removal (III) efficiency, show MTHCNPs-2 substantially not by the impact of pH, applied range, adsorption time is shorter, and effect of removing arsenic is best, be expected to become a kind of new green environment protection material with high removal efficiency, light sensitive effect and Magneto separate function.

Claims (5)

1. a preparation method for the just arsenious scavenging material of water body, is characterized in that comprising the following steps:
1) by Fe 3o 4, TiO 2the quaternary ammonium salt derivative of nanoparticle and shitosan or shitosan is dissolved in acetum, forms mixed liquor; Described Fe 3o 4, TiO 2be 2 ︰ 2 ︰ 5 with the mixing quality ratio of the quaternary ammonium salt derivative of shitosan or shitosan;
2) be mixed into Tween 80 and ethyl acetate again after being mixed with atoleine by mixed liquor, obtain W/O emulsion;
3) after W/O emulsion being warming up to 40 DEG C, being under the condition of 500r/min at rotating speed, adding formaldehyde, then add glutaraldehyde after being warming up to 50 DEG C, form mixed system;
4) with sodium hydrate aqueous solution regulating step 3) pH value to 7.5 of mixed system made, stirring reaction is to terminating, more successively with the washing of benzinum, acetone, ethanol and intermediate water, drying, obtains the chitosan-based micro-nano grain of rice, i.e. scavenging material.
2. preparation method described in claim 1, is characterized in that described acetum is the aqueous acetic acid of 2wt%; Ultrasonic process is adopted during dissolving.
3. preparation method according to claim 1, it is characterized in that in described W/O emulsion, the percent by volume of Tween 80 is 1.5%, ethyl acetate percent by volume be 10%.
4. preparation method according to claim 1, it is characterized in that in the mixed system made in described step 3), the percent by volume of formaldehyde is 8%, and the percent by volume of glutaraldehyde is 4%.
5. preparation method according to claim 1 or 4, is characterized in that being added in W/O emulsion by formaldehyde in 30min.
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CN105056912A (en) * 2015-07-23 2015-11-18 江苏大学 Preparation method for immobilized metal ion affinity magnetic nanoparticles and application thereof
CN105347425A (en) * 2015-11-23 2016-02-24 扬州大学 Method used for removing trivalent arsenic in water body effectively in point processing scheme
CN105664894A (en) * 2016-01-25 2016-06-15 扬州大学 Preparation method of purifying material for selectively removing positive trivalent arsenic from water body
CN106076274A (en) * 2016-06-29 2016-11-09 扬州大学 A kind of preparation method of the sulfhydrylation chitosan magnetic composite of heavy-metal ion removal
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102875830A (en) * 2012-10-29 2013-01-16 江南大学 Preparation method and application of sulfhydryl chitosan/activated carbon composite functional membrane
CN103706335A (en) * 2013-11-05 2014-04-09 中国科学院城市环境研究所 Iron/chitosan/polyoxyethylene composite nanofiber membrane arsenic removal material and electrostatic spinning preparation method thereof
CN103752268A (en) * 2014-01-16 2014-04-30 广东工业大学 Preparation method of filter core for adsorbing heavy metal, arsenic and fluorine in drinking water and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2814068A1 (en) * 2009-10-14 2011-04-21 The Administrators Of The Tulane Educational Fund Novel multifunctional materials for in-situ environmental remediation of chlorinated hydrocarbons

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102875830A (en) * 2012-10-29 2013-01-16 江南大学 Preparation method and application of sulfhydryl chitosan/activated carbon composite functional membrane
CN103706335A (en) * 2013-11-05 2014-04-09 中国科学院城市环境研究所 Iron/chitosan/polyoxyethylene composite nanofiber membrane arsenic removal material and electrostatic spinning preparation method thereof
CN103752268A (en) * 2014-01-16 2014-04-30 广东工业大学 Preparation method of filter core for adsorbing heavy metal, arsenic and fluorine in drinking water and application thereof

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