CN101298039B - Preparation of chitosan molecular imprinting adsorbing agent - Google Patents
Preparation of chitosan molecular imprinting adsorbing agent Download PDFInfo
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- CN101298039B CN101298039B CN2008100563985A CN200810056398A CN101298039B CN 101298039 B CN101298039 B CN 101298039B CN 2008100563985 A CN2008100563985 A CN 2008100563985A CN 200810056398 A CN200810056398 A CN 200810056398A CN 101298039 B CN101298039 B CN 101298039B
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Abstract
The invention provides a preparation method for a print adsorbent of chitosan molecules, which relates to a preparation method for an adsorbent that can selectively remove perfluorooctane sulfonate (PFOS) in water. The preparation method adopts a molecular imprinting technique to construct a plurality of specific adsorption sites and the worthy adsorbent has remarkable selectivity adsorption to the PFOS in water. The method takes chitosan as raw material to prepare micro-cross linking chitosan beads; then the chitosan beads are printed with template molecules PFOS for 5 to 24 hours in an acid water solution, a mass ratio between the template molecules and the micro-cross linking chitosan beads is 0.005 to 0.06: 1, and reaction with a cross linker is carried out for 2 to12 hours after printing; the mass ratio between the volume of the cross linker and the micro-cross linking chitosan beads after being printed is 0.0125 to 0.119ml/g; finally, an organic solvent is used for eluting for 1 to 8 hours and the print adsorbent of chitosan molecules is obtained after freeze-drying. The adsorbent is suitable for adsorbing and removing PFOS in complicated water substances and is characterized by strong selectivity and being able to be reused.
Description
Technical field
The present invention relates to a kind of chitosan molecule trace preparation of adsorbent method, the prepared adsorbent of this method can optionally adsorb in the water body of complexity removes PFOS based compound (PFOS) in the water body, belongs to water treatment adsorption technology field.
Background technology
PFOS based compound (PFOS) is the important perfluorochemical of a class, all has a wide range of applications at numerous areas as surfactant, anti-fouling agent, fire foam and chemical intermediate etc.Simultaneously, PFOS also is the final catabolite of multiple perfluorochemical.In recent years, increasing researcher studies refractory organics, biological accumulation, endocrine interference, toxicity and the distribution on global situation of PFOS and reports.As a kind of candidate substances of new continuation organic pollution (POPs), maxima solubility is up to 570mg/L in water for PFOS, and this makes them have bigger potential hazard with respect to other POPs material to human body and environment.Therefore, work out the PFOS that suitable technology removes in the water body effectively and just seem particularly important.
At present, only there is the several method of minority to report removal to PFOS, comprise ultrasonotomography (EnvironmentalScience and Technology, 2005,39,3388-3392), the reduction of the Zero-valent Iron in the subcritical water (EnvironmentalScience and Technology, 2006,40,1049-1054), reverse osmosis membrane (Environmental Science and Technology, 2006,40,7343-7349) and charcoal absorption (Organohalogen Compounds, 2007,69,2820-2823) etc.Above several method, except existence costs an arm and a leg, the reaction condition requirement is high or shortcoming such as regeneration difficulty, they do not have the ability of selective removal PFOS yet.Yet, no matter be in the nature natural water body, still in industrial former water such as semiconductor, plating, be present in a lot of other polluters that also have in the water body simultaneously with PFOS, they can reduce the removal effect of conventional art for PFOS greatly.Therefore, selectivity is removed for the PFOS in the complicated water body crucial effects.
Molecular imprinting is meant by the steps such as wash-out of template and monomer interphase interaction, crosslinked, polymerization and template molecule, finally makes a kind of polymer that can discern object on space structure and adsorption site.The adsorbent that method by molecular engram makes, its maximum characteristics are that object is had very high adsorptive selectivity.Though conventional adsorbent also has certain adsorption effect to PFOS, but in the water body of complexity, because the interference of other polluter, its adsorption effect tends to reduce greatly, molecular imprinting adsorbing agent then just in time can remedy the deficiency of conventional adsorbent, can optionally remove the PFOS in the water body.
Shitosan is the product after chitin is sloughed the N-acetyl group, and in general, the chitin of sloughing 55% above N-acetyl group promptly can be described as shitosan.The shitosan raw material sources is extensive, has excellent biological compatibility, nonhazardous and biodegradability.In addition, shitosan contains multiple functional groups such as hydroxyl and amino simultaneously, can carry out modifications such as crosslinked, grafting easily, makes it become a kind of important environmental friendliness functional material.Utilize shitosan to be dissolved in diluted acid and be insoluble to the characteristics of alkali, shitosan can be dissolved in the solution such as acetic acid, hydrochloric acid of low concentration, again it is splashed into shitosan bead (the Industrial and Engineering Chemistry Research that just can obtain the water-setting glue in the alkaline solution, 1998,37,1454-1463).At present, this material has had certain application in fields such as the immobilization of pollutant removal, enzyme and catalyst carriers.(however, we also do not have to find have document utilization shitosan bead directly to carry out the preparation of molecular imprinting adsorbing agent as functive, the present invention then utilizes the shitosan bead as raw material, successfully utilizes the crosslinked method of substep to prepare the molecular imprinting adsorbing agent that a kind of energy selectivity is effectively removed PFOS in the water).
Summary of the invention
The purpose of this invention is to provide a kind of chitosan molecule trace preparation of adsorbent method of removing at PFOS in the complicated water body, by the interaction of template molecule and functional polymer, crosslinked and wash-out, on the shitosan bead, construct a large amount of specific adsorption sites, thereby make prepared adsorbent good adsorptive selectivity be arranged for PFOS.
Technical scheme of the present invention is as follows:
A kind of chitosan molecule trace preparation of adsorbent method is characterized in that this method carries out as follows:
1) shitosan is dissolved in makes chitosan solution in the diluted acid, splash into subsequently that granulation obtains gelatinous shitosan bead in the alkaline solution, at 40～60 ℃ of following and epichlorohydrin reaction 2～12h, add epoxychloropropane the ratio of volume and the quality of shitosan bead be 0.0125～0.0278ml/g, at last little crosslinked shitosan bead is cleaned and is left in the deionized water standby;
2) little crosslinked shitosan bead is joined trace 5～24h in the acid solution that contains template molecule PFOS, add template molecule PFOS and little cross-linked chitosan bead mass ratio be 0.005: 1～0.06: 1, the pH value of solution value remains at 2～4; Trace finishes the back and reacts 2～12h with crosslinking agent down at 40～60 ℃, add crosslinking agent volume and trace after the ratio of quality of little cross-linked chitosan bead be 0.0125～0.119ml/g;
3) with step 2) the shitosan bead that obtains removes template molecule with eluent wash-out 1～8h, washes repeatedly with deionized water again, and last freeze drying makes chitosan molecule trace adsorbent to constant weight.
The used crosslinking agent of the present invention is epoxychloropropane or glutaraldehyde; Template molecule PFOS based compound is PFOS, PFOS potassium or PFOS sodium; Eluent is that acetone/alkali mixed solution, methyl alcohol/alkali mixed solution and other have the organic solvent of good solubility and the mixed solution of alkali to PFOS.
The present invention compared with prior art has the following advantages and the high-lighting effect:
In traditional molecular imprinting, the interaction of template molecule and monomer, polymerisation and cross-linking reaction are normally carried out simultaneously, in most cases formed bulky polymer also needs just can obtain required molecular imprinting adsorbing agent through repeatedly grinding and screening, and the process of grinding, sieving then often wastes time and energy.The present invention has adopted a kind of natural polymers-shitosan as functive, the characteristic of utilizing it to be dissolved in acid and being insoluble to alkali makes the shitosan bead and is directly used in trace, successfully avoiding last grinding, is a kind of very simple and easy to do molecular imprinting adsorbing agent preparation method.
At present, several PFOS removal technology of crossing of bibliographical information all do not have selectivity to PFOS.In complicated water body, they can not effectively remove PFOS, and the prepared chitosan molecule trace of the present invention adsorbent then can provide good selectivity.In selective absorption experiment, the present invention utilizes this adsorbent all contaminations of molar concentration such as absorption respectively under identical adsorption conditions.The result shows, chitosan molecule trace adsorbent reaches 47.9% for the clearance of PFOS, and for common pollutant 2, the clearance of 4-dichlorphenoxyacetic acid, perfluoro caprylic acid, neopelex, penta sodium pentachlorophenate and phenol then is respectively 4.7%, 4.2%, 17.0%, 11.5% and 5.1%, and this has proved absolutely that the prepared adsorbent of the present invention has good adsorption selectivity and selectivity for PFOS.In regeneration tests, at an easy rate PFOS is washed off by acetone/NaOH mixed solution, use five times continuously after, the absorption property of chitosan molecule trace adsorbent does not almost descend.
In sum, outstanding advantage of the present invention is that the preparation method is simple and easy to do, and the prepared chitosan molecular imprinting adsorbing agent has selectivity and good regenerability efficiently to target contaminant.
Description of drawings
Fig. 1 chitosan molecule trace adsorbent (MIP) and the clearance of non-trace adsorbent (NIP) to different pollutants in the aqueous solution.
The specific embodiment
Among the present invention, prepare required adsorbent by crosslinked-trace-crosslinked again multistep reaction.The effect of first step cross-linking reaction is the shitosan bead is carried out slightly crosslinked, gives the characteristic that it is insoluble to acid.In the reaction of subsequently trace, the amino of little crosslinked shitosan bead is fully protonated in acid solution, and template molecule is adsorbed on the amino by electrostatic interaction.When crosslinked once more, the crosslinking agent of capacity can make chitosan molecule full cross-linked, thereby the space structure of polymer is fixed up.In last wash-out, alkaline solution can make the amino deprotonation of shitosan with comparalive ease, thereby template molecule is come out by wash-out from shitosan, and methyl alcohol, acetone etc. has the organic solvent of good solubility then can increase elute effect to PFOS.Because full cross-linked cause, the space structure of polymer is still kept behind the wash-out, and template molecule is sloughed left hole, back has just had Memorability and recognition reaction to target molecule, becomes the effective recognition site in the molecular imprinting adsorbing agent.
Concrete preparation method of the present invention is as follows:
1) shitosan is dissolved in makes chitosan solution in the diluted acid, splash into subsequently that granulation obtains gelatinous shitosan bead in the alkaline solution, at 40～60 ℃ of following and little cross-linking reaction 2～12h of epoxychloropropane, add epoxychloropropane the ratio of volume and the quality of shitosan bead be 0.0125～00278ml/g, at last little crosslinked shitosan bead is cleaned and is left in the deionized water standby;
2) little crosslinked shitosan bead is joined trace 5～24h in the acid solution that contains template molecule PFOS, add template molecule PFOS and little cross-linked chitosan bead mass ratio be 0.005: 1～0.06: 1, the pH value of solution value remains at 2～4; Trace finishes the back and reacts 2～12h with crosslinking agent down at 40～60 ℃, add crosslinking agent volume and trace after the ratio of quality of little cross-linked chitosan bead be 0.0125～0.119ml/g, used crosslinking agent is epoxychloropropane or glutaraldehyde;
3) with step 2) the shitosan bead that obtains removes template molecule with eluent wash-out 1～8h, washes repeatedly with deionized water again, and last freeze drying makes chitosan molecule trace adsorbent to constant weight; Eluent can adopt acetone/alkali mixed solution, methyl alcohol/alkali mixed solution and other that PFOS is had the organic solvent of good solubility and the mixed solution of alkali.
The present invention mainly compares by the PFOS adsorbance with non-trace adsorbent for the evaluation method of chitosan molecule trace adsorbent.Non-trace adsorbent does not add template molecule in preparation, other preparation methods and molecular imprinting adsorbing agent are just the same.
It is as follows to the experimental technique of PFOS adsorbance that the present invention measures adsorbent: add a certain amount of PFOS solution in the 250mL triangular flask, adjust the initial pH of solution, add adsorbent then, add behind the bottle stopper in the constant temperature shaking table that triangular flask is placed on 25 ℃ rotating speed absorption 36h (having arrived adsorption equilibrium) with 130rpm, use the membrane filtration of 0.22 μ m then, measure the content of residue PFOS in the filtrate, calculate the clearance of adsorbent pollutant with following formula:
R＝(C
0-C
e)/C
0×100％
Wherein: R is clearance (%); C
0Initial concentration (mg/L) for pollutant; C
eFor adsorbing the equilibrium concentration (mg/L) of back PFOS.
Embodiment 1: the 1.5g shitosan is dissolved in the acetum of 50ml (percent by volume 2%), splash into granulation in NaOH (0.5M) solution of 200ml after treating to dissolve fully, the shitosan bead that obtains is about 36g, at 60 ℃ down and 1ml epichlorohydrin reaction 12h afterwash and leave in the deionized water standby.Get the middle trace 5h of acidic aqueous solution (400mg/L) that the little cross-linked chitosan bead of 9g joins 500mL PFOS potassium, the pH value of solution value remains at about 4.To react 12h down at 60 ℃ in the shitosan bead adding epoxychloropropane solution after trace finishes, epoxychloropropane solution contains 0.3mL epoxychloropropane and 10ml deionized water.Subsequently with methyl alcohol/0.5M potassium hydroxide solution wash-out 1h to remove template molecule, wash repeatedly with deionized water at last, freeze drying obtains chitosan molecule trace adsorbent to constant weight.Non-trace adsorbent in kind prepares, but does not add template molecule.0.05g trace and non-trace adsorbent are put into the 250mL triangular flask, and adding 100mL concentration again is the PFOS solution (pH=5) of 200mg/L, adsorbs 36h (reaching balance) in rotating speed is the shaking table of 130rpm.Calculating the trace adsorbent is 62% to the clearance of PFOS, and non-trace adsorbent then is 52% to the clearance of PFOS.
Embodiment 2: the 3g shitosan is dissolved in the acetum of 100ml (percent by volume 2%), splash into granulation in NaOH (0.5M) solution of 400ml after treating to dissolve fully, the shitosan bead that obtains is about 72g, at 40 ℃ down and 0.9ml epichlorohydrin reaction 2h afterwash and leave in the deionized water standby.Get the middle trace 5h of acidic aqueous solution (400mg/L) that the little crosslinked shitosan bead of 4g joins 125mL PFOS potassium, the pH value of solution value remains at about 4.To react 5h down at 60 ℃ in the shitosan bead adding epoxychloropropane solution after trace finishes, epoxychloropropane solution contains 0.15mL epoxychloropropane and 10ml deionized water.Subsequently with acetone/0.5M sodium hydroxide solution wash-out 3h to remove template molecule, wash repeatedly with deionized water at last, freeze drying obtains chitosan molecule trace adsorbent to constant weight.Non-trace adsorbent in kind prepares, but does not add template molecule.0.05g trace and non-trace adsorbent are put into the 250mL triangular flask, and adding 100mL concentration again is the PFOS solution (pH=5) of 200mg/L, adsorbs 36h (reaching balance) in rotating speed is the shaking table of 130rpm.Calculating the trace adsorbent is 60% to the clearance of PFOS, and non-trace adsorbent then is 42% to the clearance of PFOS.
Embodiment 3: the 3g shitosan is dissolved in the acetum of 100ml (percent by volume 2%), splash into granulation in NaOH (0.5M) solution of 500ml after treating to dissolve fully, the shitosan bead that obtains is about 72g, at 40 ℃ down and 2ml epichlorohydrin reaction 12h afterwash and leave in the deionized water standby.Get the middle trace 13.5h of acidic aqueous solution (500mg/L) that the little crosslinked shitosan bead of 3.36g joins the 125mL PFOS, the pH value of solution value remains at about 4.To react 12h down at 40 ℃ in the shitosan bead adding epoxychloropropane solution after trace finishes, epoxychloropropane solution contains 0.4mL epoxychloropropane and 10ml deionized water.Subsequently with methyl alcohol/0.5M sodium hydroxide solution wash-out 3h to remove template molecule, wash repeatedly with deionized water at last, freeze drying obtains chitosan molecule trace adsorbent to constant weight.Non-trace adsorbent in kind prepares, but does not add template molecule.0.05g trace and non-trace adsorbent are put into the 250mL triangular flask, and adding 100mL concentration again is the PFOS solution (pH=5) of 200mg/L, adsorbs 36h (reaching balance) in rotating speed is the shaking table of 130rpm.Calculating the trace adsorbent is 50% to the clearance of PFOS, and non-trace adsorbent then is 31% to the clearance of PFOS.
Embodiment 4: the 3g shitosan is dissolved in the acetum of 100ml (percent by volume 2%), splash into granulation in NaOH (0.5M) solution of 500ml after treating to dissolve fully, the shitosan bead that obtains is about 72g, at 40 ℃ down and 2ml epichlorohydrin reaction 12h afterwash and leave in the deionized water standby.Get the middle trace 24h of acidic aqueous solution (400mg/L) that the little crosslinked shitosan bead of 4g joins 50mL PFOS potassium, the pH value of solution value remains at about 4.To react 12h down at 40 ℃ in the shitosan bead adding epoxychloropropane solution after trace finishes, epoxychloropropane solution contains 0.05mL epoxychloropropane and 10ml deionized water.Replace wash-out 8h to remove template molecule with acetone/0.5M sodium hydroxide solution subsequently, wash repeatedly with deionized water at last, freeze drying obtains chitosan molecule trace adsorbent to constant weight.Non-trace adsorbent in kind prepares, but does not add template molecule.0.05g trace and non-trace adsorbent are put into the 250mL triangular flask, and adding 100mL concentration again is the PFOS solution (pH=5) of 200mg/L, adsorbs 36h (reaching balance) in rotating speed is the shaking table of 130rpm.Calculating the trace adsorbent is 62% to the clearance of PFOS, and non-trace adsorbent then is 42% to the clearance of PFOS.
Embodiment 5: the 3g shitosan is dissolved in the acetum of 100ml (percent by volume 2%), splash into granulation in NaOH (0.5M) solution of 500ml after treating to dissolve fully, the shitosan bead that obtains is about 72g, at 40 ℃ down and 2ml epichlorohydrin reaction 12h afterwash and leave in the deionized water standby.Get the middle trace 24h of acidic aqueous solution (400mg/L) that the little crosslinked shitosan bead of 4g joins 500mL PFOS potassium, the pH value of solution value remains at about 3.To react 12h down at 40 ℃ in the shitosan bead adding glutaraldehyde solution after trace finishes, glutaraldehyde solution contains 0.2mL glutaraldehyde and 10ml deionized water.Subsequently with acetone/0.5M sodium hydroxide solution wash-out 8h to remove template molecule, wash repeatedly with deionized water at last, freeze drying obtains chitosan molecule trace adsorbent to constant weight.Non-trace adsorbent in kind prepares, but does not add template molecule.0.05g trace and non-trace adsorbent are put into the 250mL triangular flask, and adding 100mL concentration again is the PFOS solution (pH=5) of 200mg/L, adsorbs 36h (reaching balance) in rotating speed is the shaking table of 130rpm.Calculating the trace adsorbent is 55% to the clearance of PFOS, and non-trace adsorbent then is 54% to the clearance of PFOS.
Embodiment 6: the 3g shitosan is dissolved in the acetum of 100ml (percent by volume 2%), splash into granulation in NaOH (0.5M) solution of 500ml after treating to dissolve fully, the shitosan bead that obtains is about 72g, at 40 ℃ down and 2ml epoxy reaction 12h afterwash and leave in the deionized water standby.Get the middle trace 24h of acidic aqueous solution (480mg/L) that the little crosslinked shitosan bead of 2g joins 250mL PFOS potassium, the pH value of solution value remains at about 2.To react 12h down at 40 ℃ in the shitosan bead adding epoxychloropropane solution after trace finishes, epoxychloropropane solution contains 0.1mL epoxychloropropane and 5ml deionized water.Subsequently with pure acetone/0.5M sodium hydroxide solution wash-out 8h to remove template molecule, wash repeatedly with deionized water at last, freeze drying obtains chitosan molecule trace adsorbent to constant weight.Non-trace adsorbent in kind prepares, but does not add template molecule.0.05g trace and non-trace adsorbent are put into the 250mL triangular flask, and adding 100mL concentration again is the PFOS solution (pH=5) of 200mg/L, adsorbs 36h (reaching balance) in rotating speed is the shaking table of 130rpm.Calculating the trace adsorbent is 75% to the clearance of PFOS, and non-trace adsorbent then is 29% to the clearance of PFOS.
Embodiment 7: the 3g shitosan is dissolved in the acetum of 100ml (percent by volume 2%), splash into granulation in NaOH (0.5M) solution of 500ml after treating to dissolve fully, the shitosan bead that obtains is about 72g, down reacts the 12h afterwash and leaves in the deionized water standby with the 2ml crosslinking agent at 40 ℃.Get the middle trace 12h of acidic aqueous solution (450mg/L) that the little cross-linked chitosan bead of 4g joins 400mL PFOS potassium, the pH value of solution value remains at about 2.To react 12h down at 40 ℃ in the shitosan bead adding epoxychloropropane solution after trace finishes, epoxychloropropane solution contains 0.2mL epoxychloropropane and 10ml deionized water.Subsequently with acetone/0.5M sodium hydroxide solution wash-out 8h to remove template molecule, wash repeatedly with deionized water at last, freeze drying obtains chitosan molecule trace adsorbent to constant weight.Non-trace adsorbent in kind prepares, but does not add template molecule.
Embodiment 7 resulting traces and non-trace adsorbent 0.01g are put into the 250mL triangular flask, and adding 100mL concentration again is the PFOS solution (pH=5) of 50mg/L, adsorbs 36h (reaching balance) in rotating speed is the shaking table of 130rpm.PFOS concentration before and after the absorption in the solution is separated by Tianjin, island high performance liquid chromatography and is measured with electric conductivity detector.Calculating the trace adsorbent is 60% to the clearance of PFOS, and non-trace adsorbent then is 28% to the clearance of PFOS.
Embodiment 7 resulting trace adsorbent 0.01g are put into the 250mL triangular flask, add the PFOS, 2 that 100mL concentration is 100 μ mol/L more respectively, 4-dichlorphenoxyacetic acid, perfluoro caprylic acid, neopelex, penta sodium pentachlorophenate or phenol solution (pH=6) are adsorbed 36h (reaching balance) in rotating speed is the shaking table of 130rpm.Calculate the trace adsorbent and reach 47.9% for the clearance of PFOS, and for 2,4-dichlorphenoxyacetic acid (2,4-D), perfluoro caprylic acid (PFOA), neopelex (SDBS), penta sodium pentachlorophenate (PCP) and phenol (Phenol) waits the clearance of other common pollutant then to be respectively 4.7%, 4.2%, 17.0%, 11.5% and 5.1%, far below the clearance (Fig. 1) to PFOS.
Claims (3)
1. chitosan molecule trace preparation of adsorbent method is characterized in that this method carries out as follows:
1) shitosan is dissolved in makes chitosan solution in the diluted acid, splash into subsequently that granulation obtains gelatinous shitosan bead in the alkaline solution, at 40～60 ℃ of following and little cross-linking reaction 2～12h of epoxychloropropane, add epoxychloropropane the ratio of volume and the quality of shitosan bead be 0.0125～0.0278ml/g, at last little crosslinked shitosan bead is cleaned and is left in the deionized water standby;
2) little crosslinked shitosan bead is joined trace 5～24h in the acid solution that contains template molecule PFOS based compound, add template molecule PFOS based compound and little cross-linked chitosan bead mass ratio be 0.005: 1～0.06: 1, the pH value of solution value remains at 2～4; Trace finishes the back and reacts 2～12h with crosslinking agent down at 40～60 ℃, add crosslinking agent volume and trace after the ratio of quality of little cross-linked chitosan bead be 0.0125～0.119ml/g; Used crosslinking agent is epoxychloropropane or glutaraldehyde; Used template molecule PFOS based compound is PFOS, PFOS potassium or PFOS sodium;
3) with step 2) the shitosan bead that obtains removes template molecule with eluent wash-out 1～8h, washes repeatedly with deionized water again, and last freeze drying makes chitosan molecule trace adsorbent to constant weight.
2. chitosan molecule trace preparation of adsorbent method according to claim 1, it is characterized in that: used eluent is for to have the organic solvent of good solubility and the mixed solution of alkali to template molecule.
3. chitosan molecule trace preparation of adsorbent method according to claim 2 is characterized in that: described organic solvent adopts acetone or methyl alcohol.
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