CN1458072A - Crosslinking process for adsorption of dye with spherical chitosan bead - Google Patents
Crosslinking process for adsorption of dye with spherical chitosan bead Download PDFInfo
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Abstract
The preparation process of crosslinked spherical chitosan bead for adsorbing dye includes the following steps: dissolving chitosan in acetic acid to form chitosan solution; letting the solution stand for 24 hr; mixing the chitosan solution and tripolyphosphate solution and letting stand for 4 hr to form ionized and crosslinked chitosan bead; adding sodium hydroxide and crosslinking reagent to produce chemical crosslinking to produce crosslinked spherical chitosan bead; and vibrating the solution in water tank at 25-55 deg.c for 6 hr. The crosslinked spherical chitosan bead is used in adsorbing great amount of dye in acid or neutral waste water.
Description
Technical field
The present invention relates to a kind of dye adsorption method, particularly a kind of method of utilizing dyestuff in crosslinkedization spherical chitosan bead (the cross-linked chitosan beads) adsorption aqueous solution.
Background technology
The processing of waste water is very important in industry now, and particularly the new line of environmental consciousness and environmental regulation is strict day by day, so the wastewater treatment benefit of dyestuff becomes important.Part industry at present as dyestuff industry, textile raw material, leather, paper, plastic cement, or the like waste water comprise various synthetic dyestuff.Remain in the pollution that a small amount of dyestuff in the water jeopardizes the healthy of biology probably and causes environment.Therefore, from trade effluent, dyestuff therefrom adsorbed and become a kind of very important wastewater treatment project.The processing mode that comprises many kinds of physical properties or chemical at present, wherein adsorption method is one of wherein more effective method.For example have and adopt the activated carbon adsorption dyestuff to reduce the concentration of dyestuff in the aqueous solution, consult Allen, S.J., 1996.Types of adsorbent materials.In:McKay, G. (Ed.), Use of Adsorbents for the Removal of Pollutants fromWastewaters.CRC, Boca Raton, USA, pp.59-97.Utilize peat adsorption method such as Ramakrishna, K.R., Viraraghavan, T., 1997.Dye removal using low cost adsorbents.Wat.Sci.Tech.36,189-196 and Ho, Y.S., McKay, G., 1998.Sorption of dye fromaqueous solution by peat.Chem.Eng.J.70,115-124.Utilize chitin (chitin) absorbing dye, consult McKay, G., Blair, H.S., Gardner, J.R., 1983.Rate studies for the adsorption ofdyestuffs on chitin.J.Colloid and Interface Sci.95,108-119 or Juang R.S., Tseng, R.L., Wu, F.C., Lee, S.H., 1997.Adsorption behavior of reactive dyes from aqueoussolutions on chitosan.J.Chem.Technol.Biotechnol.70,391-399.Also comprise in addition with the method for tripoli absorption and can consult McKay, G., 1984.Analytical solution using a pore diffusionmodel for a pseudo irreversible isotherm for the adsorption of basic dye on silica.AIChE J.30,692-697.Other method comprises the method that following investigator proposes:
El-Geundi，M.S.，1991.Color?removal?from?textile?efluents?by?adsorptiontechniques.Wat.Res.25，271-273。
Hu，T.L.，1996.Removal?of?reactive?dyes?from?aqueous?solution?by?differentbacterial?genera.Wat.Sci.Tech.34，89-95。
Low，K.S.，Lee，C.K.，1997.Quaternized?rice?husk?as?sorbent?for?reactive?dyes.Bioresource?Tech.61，121-125。
Namasivayam?C.，Prabha，D.，Kumutha，M.，1998.Removal?of?direct?red?andacid?brilliant?blue?bV?adsorption?on?to?banana?pith.Biores.Technol.64，77-79。
Tsai，W.T.，Chang，C.Y.，Lin，M.C.，Chien，S.F.，Sun，H.F.，Hsieh，M.F.，2001.Adsorption?of?acid?dye?onto?activated?carbon?prepared?from?agricultural?wastebagasse?by?ZnCl
2?activation.Chemosphere.45，51-58。
Aksu，Z.，2001.Biosorption?of?reactive?dyes?by?dried?activated?sludge：equilibrium?and?kinetic?modelling.Biochem.Eng.J.7，79-84。
Yet, utilize the adsorbents adsorb effect of above-mentioned old technology can't reach our expectation, the adsorptive power of part is about 200-600g/kg and some even is lower than 50g/kg.Expectation at present can develop method or the processing procedure that has than high absorption capacity.
The purposes of chitin (chitin) and spherical chitosan (chitosan) is very extensive, and wherein the spherical chitosan heavy metal that can reduce waste water pollutes to reduce, and effectively reduces the suspended solids of waste water.Spherical chitosan (chitosan) is that (linear polymer of β-poly-D-glucosamine) is because of having two kinds of functional groups of amido and hydroxy, so also have wetting ability and a chemically reactive for a kind of poly-dextrose amine.Present a lot of research is to note with the dye sorbent of spherical chitosan as wastewater treatment.In addition, spherical chitosan is fit to do the fixing and affine absorption of ferment, other features comprise biocompatibility, can biological natural decomposition and antimicrobial characteristic, as can the mould fungus inhibition growth as sanitas.In the aqueous solution of neutrality, use spherical chitosan can represent powerful adsorptive power, adsorption effect is about 1000-1100g/kg, as described in document, consult Kumar, M.N.V.R., 2000.A review of chitinand chitosan applications.React.﹠amp; Funct.Polym.46,1-27.
In acidic solution, the amido of spherical chitosan (chitosan) is very easy of cationization, and attracts negatively charged ion.So research is an important problem at the DBC that is lower than spherical chitosan under the pH7, because acetic acid (acetic acid) often is used as the promotor of dyeing processing procedure, in this case, the pH value of dye solution often transfers to about 3 to 4.Spherical chitosan (chitosan) can be dissolved into colloid below the pH5.5 and can't bring into play its effect being lower than.Based on spherical chitosan easy dissolution characteristics in acidic solution, therefore, in acidic medium, limited spherical chitosan usually as the use range of sorbent material in order to removal dyestuff, metal ion.
In order in acidic solution, to stablize spherical chitosan, some crosslinkedization reagent just are used, disclose as prior art, see also Wei, Y.C., Hudson, S.M., Mayer, J.M., Kaplan, D.L., 1992.Thecrosslinking of chitosan fibers.J.Polym.Sci.:Polym.Chem.30,2187-2193.Zeng, X.F., Ruckenstein, E., 1996.Control of pore sizes in macroporous chitosan andchitin membranes.Ind.Eng.Chem.Res.35,4169-4175.Crosslinkedization spherical chitosan is not dissolved in the acidic solution, and people such as Yoshida use Denacol EX841 to have high absorption capacity to be about 1200-1700g/kg to Acid Orange II (matching stain pH is about 3 to 4) as the reagent of crosslinkedization in acidic solution.
Therefore, be badly in need of at present a kind ofly can using the process for adsorption of dye that under sour environment, has the superelevation adsorptive power.
Summary of the invention
The purpose of this invention is to provide a kind of process for adsorption of dye.
The present invention's a purpose again is for providing a kind of method that can be applied to utilize under the sour environment dyestuff in crosslinkedization spherical chitosan bead (cross-linked chitosan beads) the absorption acidic solution.
The present invention's a time purpose is for providing a kind of epichlorohydrin of utilization (ECH) in order to the poly-candy ball (cross-linked chitosan beads) of the crosslinkedization machine fourth that obtains high absorption capacity (1600-1900g/kg), can be applied to sour environment and be lower than the pH value below 3, in order to the method for dyestuff in the absorption acidic solution.
For achieving the above object, the present invention takes following design: a kind of with crosslinkedization spherical chitosan bead process for adsorption of dye, this method comprises the following step at least:
Provide spherical chitosan also this spherical chitosan to be dissolved to form spherical chitosan solution;
Form spherical chitosan bead, with state spherical chitosan solution and tri-polyphosphate (TPP on preparing; Tripolyphosphate) the solution mixing is beneficial to form ionic crosslinked spherical chitosan bead; And
Above-mentioned ionic crosslinked spherical chitosan bead is produced the chemically crosslinked reaction to form crosslinkedization spherical chitosan bead, wherein comprise adding sodium hydroxide and linking agent, first period in the tank of this solution between centigradetemperature 25-55 degree that vibrate afterwards; And
The spherical chitosan bead of above-mentioned crosslinkedization can be placed solution be beneficial to adsorb this dyestuff with dyestuff.
Above-mentioned spherical chitosan is dissolved in the acetic acid.
After finishing above-mentioned spherical chitosan and being dissolved in acidic solution, mixing solutions is left standstill about second period.
Above-mentioned second period is at least about 6 hours.
Above-mentioned spherical chitosan solution and above-mentioned tri-polyphosphate (TPP; Tripolyphosphate) solution leaves standstill about the 3rd period after mixing.
Above-mentioned the 3rd period is at least about 4 hours.
Produce above-mentioned linking agent and comprise ECH (epichlorohydrin).
Produce above-mentioned linking agent and comprise GA (glutaraldehyde).
Produce above-mentioned linking agent and comprise EGDE (ethylene glycol diglycidyl ether).
Above-mentioned first period is at least about 6 hours.
Above-mentioned spherical chitosan bead applicable in acidity or the neutral solution with absorption reaction dyestuff, matching stain or direct dyestuff.
A kind of method of formation spherical chitosan bead, this method comprises the following step at least:
Spherical chitosan is dissolved in the acetic acid to form spherical chitosan solution, again with above-mentioned spherical chitosan solution left standstill;
With state spherical chitosan solution and tri-polyphosphate (TPP on preparing; Tripolyphosphate) the solution mixing is beneficial to form ionic crosslinked spherical chitosan bead;
Wherein above-mentioned spherical chitosan solution and above-mentioned tri-polyphosphate (TPP; Tripolyphosphate) solution leaves standstill an about period after mixing.
Above-mentionedly leave standstill the period and be at least about 4 hours.
Above-mentioned spherical chitosan bead applicable in acidity or the neutral solution with absorption reaction dyestuff, matching stain and direct dyestuff.
A kind of method of crosslinkedization of formation spherical chitosan bead, this method comprises the following step at least:
Spherical chitosan is dissolved in the acetic acid to form spherical chitosan solution, again with above-mentioned spherical chitosan solution left standstill;
With state spherical chitosan solution and tri-polyphosphate (TPP on preparing; Tripolyphosphate) the solution mixing is beneficial to form the crosslinked spherical chitosan bead of ionization;
Wherein above-mentioned spherical chitosan solution and above-mentioned tri-polyphosphate (TPP; Tripolyphosphate) leave standstill about first period after solution mixes to form the crosslinked spherical chitosan bead of ionization;
The spherical chitosan bead that above-mentioned ionization is crosslinked produces the chemically crosslinked reaction to form the spherical chitosan bead of crosslinkedization, wherein comprises to add sodium hydroxide and chemical cross-linking agent, second period in the tank of this solution between centigradetemperature 25-55 degree that vibrate afterwards.
Produce above-mentioned chemical cross-linking agent and comprise ECH (epichlorohydrin).
Produce above-mentioned chemically crosslinkedization and comprise GA (glutaraldehyde).
Produce above-mentioned chemical cross-linking agent and comprise EGDE (ethylene glycol diglycidyl ether).
Above-mentioned spherical chitosan bead applicable in acidity or the neutral solution with absorption reaction dyestuff, matching stain and direct dyestuff.
A kind of spherical chitosan bead sorbent material, it is characterized in that: purchase with crosslinkedization spherical chitosan, wherein linking agent is selected one of ECH, GA, EGDE for use, above-mentioned spherical chitosan bead sorbent material applicable in acidity or the neutral solution with absorption reaction dyestuff, matching stain or direct dyestuff.
The mean diameter of spherical chitosan bead sorbent material is greater than 680 microns.
Advantage of the present invention is: the present invention discloses a kind of with the spherical chitosan bead process for adsorption of dye, and this method comprises the following step at least: spherical chitosan is provided and spherical chitosan is dissolved in the acetic acid to form spherical chitosan solution; After wherein finishing above-mentioned spherical chitosan and being dissolved in acidic solution, mixing solutions was left standstill about 6 hours; With state spherical chitosan solution and tri-polyphosphate (TPP on preparing; Tripolyphosphate) solution mixes, and is beneficial to form ionic crosslinked spherical chitosan bead in about 4 hours with leaving standstill after above-mentioned TPP (tripolyphosphate) solution mixes; Above-mentioned spherical chitosan bead is produced the chemically crosslinked reaction to form crosslinkedization spherical chitosan bead, wherein comprise and add sodium hydroxide and crosslinkedization reagent, in the tank of this solution between centigradetemperature 25-55 degree that vibrate afterwards 6 hours; And the spherical chitosan bead of above-mentioned crosslinkedization can be placed solution be beneficial to adsorb this dyestuff with dyestuff.Wherein produce above-mentioned crosslinkedization reagent and comprise ECH (epichlorohdrin), GA (glutaraldehyde) or EGDE (ethylene glycol diglycidyl ether).
Description of drawings
Fig. 1 is the present invention's absorbing dye flow process
Figure 1A is the chemical structure of RR189
Fig. 2 is the adsorptive power effect of the absorption RR189 that the spherical chitosan molecular ratio is presented with crosslinkedization of difference reagent, and the spherical chitosan granular size is about 2.3 to 2.5mm, temperature 30 degree Celsius approximately, and pH value of solution is about 3.0
Fig. 3 is the resultant adsorptive power of the spherical chitosan that utilizes different molecular weight (absorbing dye RR189), shows the molecular weight of spherical chitosan and goes second vinegarization (deacetylation) degree very little to the influence of adsorptive power
Fig. 4 is that pH-value 3.0 uses the effect of the crosslinkedization spherical chitosan absorbing dye RR189 of different size particles, also uses the spherical chitosan (pH-value 6.0) of uncrosslinkedization in addition in temperature 30 degree Celsius
Fig. 5 is shown as the different starting point concentrations of dyestuff RR189 to spend 3.0 times dynamic influences of crosslinkedization spherical chitosans absorption of pH-value in centigradetemperature 30
Fig. 6 displays temperature is for dye adsorption influence, and it adsorbs the dyestuff RR189 that initial dye strength is 4330 gram/cubic meters in pH-value 3.0 with crosslinkedization spherical chitosan.
Fig. 7 is that potential of hydrogen is to the influence of spherical chitosan absorbing dye when centigradetemperature 30 degree and initial dye strength 4571 gram/cubic meters, and this embodiment adopts RR189, right also non-limiting the present invention's absorption object.
Fig. 8 is as under the identical condition of Fig. 7, shows to use 48 hours adsorptive power of crosslinkedization spherical chitosan bead (pH1 to 9)
When Fig. 9 is presented at centigradetemperature 30 degree and initial dye strength 4571 gram/cubic meters, potential of hydrogen is 1.0 o'clock, the ability of the absorbing dye of the crosslinkedization spherical chitosan bead of both kenels of dry type and wet type
Embodiment
The invention relates to a kind of dye adsorption method, particularly spherical chitosan is formed soft ball and place 4 hours sodium hydroxide of TPP solution and ethanol to mix 24 hours.And utilize crosslinkedization reagent to comprise GA (glutaraldehyde), EGDE (ethylene glycol diglycidyl ether) or ECH (epichlorohydrin) finish chemistry as reagent crosslinkedization (cross linking).The present invention's method will be as following:
Prepare spherical chitosan
Prepare spherical chitosan at first in advance, for example can adopt the spherical chitosan of following ingredients, so it does an explanation, non-scope and spirit in order to limit the present invention.
Spherical chitosan: the α type, go second vinegarization (deacetylation) degree: 84.5% to 85.5%, 95%; Molecular weight: 150000,200000,220000,400000,600000.
Reagent: ECH (greater than 98%), GA (50%), EGDE (50%) and TPP (greater than 98%).
Use commercial reactive dyestuffs 189, as RR189, C.I.18210 is as the embodiment of absorption.The first figure A is shown as the chemical structure of RR189, comprises sodium-acetate (sodiumacetate-3-hydrate in order to the buffered soln of adjusting the pH value; Wt.＞99%, RDH) and acetic acid acetic acid (ACS grade, TEDIA).
Prepare spherical chitosan bead
Prepare the spirit of the step of spherical chitosan bead, the step that wherein comprises following (as shown in Figure 1) for the present invention:
1, spherical chitosan dissolving
2, ball is shaped
3 and chemically crosslinkedization
Data that following institute is old or physics or chemistry amount refer in order to non-in order to limit the present invention as an embodiment, spherical chitosan is dissolved in acetum, for example can adopt the spherical chitosan of 10 grams to be dissolved in 300 cubic centimeters of volumes, in the acetum of weight percent 5%, spherical chitosan in other words: acetum 1: 30.Again this aqueous solution is spent the night with violent stirring and be diluted to 1.0dm
3Afterwards, leave standstill 24 hours.
To the drop-burette with little transfer pipet point, splashing into 10 cubic centimeters of spherical chitosan solution afterwards in drop-burette is that 1%～10% volume is in 100 cubic centimeters the TPP aqueous solution 200 to weight percent by the perfusion of spherical chitosan solution that step 1 prepared.It should be noted that spherical chitosan solution: the TPP aqueous solution is about 1 to 10, and above-mentioned physical quantity only is an embodiment, and is non-in order to limit the present invention.In becoming the pearl process, utilize crosslinkedization of ionization reagent TPP to strengthen the structure of spherical chitosan bead.This advantage comprise since in acidic solution between P
3O
10 5-(TPP) with acidifying after spherical chitosan it-NH
3 +Ion between the functional group attracts to cause the more ball of rigidity.This names a person for a particular job and strengthens the mechanicalness intensity of spherical chitosan.The time that forms ball was reduced to 4 hours in required 24 hours by prior art, and the main cause prior art uses sodium hydroxide reagent.Moreover, will have hard and less spherule via the spherical chitosan bead of crosslinkedization and dryingization, it helps packing and transports.To recover original size when utilizing the present invention to become the spherical chitosan of pearl to be soaked in the water, and prior art will peel off after crosslinkedization and dryingization in the mode of NaOH making in flakes.
Step can form spherical chitosan bead on the foundation, and it was statically placed in the TPP aqueous solution 210 4 hours, can utilize the caliber size control spherical chitosan bead diameter of dropper.Afterwards spherical chitosan bead is filtered out with deionized water and cleaned, be stored in the distilled water standby 220 at last.Generally can prepare diameter and be about uncrosslinkedization of the wet type spherical chitosan bead (wetnon-cross-linked chitosan beads) of 2.3-2.5mm, 2.5-2.7mm, 3.5-3.8mm various size.
Next step is the spherical chitosan bead generation chemically crosslinked reaction with above-mentioned uncrosslinkedization of wet type.For an embodiment, can be with the uncrosslinked spherical chitosan bead that wets (comprise and be equivalent to the spherical chitosan that 0.1 gram is done), with 50 cubic centimeter 1 not the ear sodium hydroxide solution be placed in 125 cubic centimeters the Erlenmeyer flask 300.Then, linking agent ECH (greater than 98%) or GA (50%) or EGDE (50%) add in the above-mentioned solution 310, and this solution in the tank of 25-55 degree Celsius six hours 320 afterwards vibrates.
In this step, can obtain the not ear ratio of different crosslinkedization reagent/spherical chitosans, as crosslinkedization ratio 0.174,0.348,0.532,0.697,0.871.Afterwards spherical chitosan bead is filtered out with deionized water and cleaned 330, be stored in the distilled water standbyly at last, so obtain the wet curing spherical chitosan bead.Can be used for the absorption 340 of waste water from dyestuff.
With dyestuff RR189 as the object that utilizes present method to adsorb, its chemical structure show in Figure 1A, be about to dyestuff earlier be dissolved in the deionized water to obtain required concentration.Utilize acetic acid (acetic acid)/acetate (acetate) as the pH-value of buffered soln in order to the adjustment dye solution.In equilibrium adsorption isothermal (equilibrium adsorption isotherm) experiment, spherical chitosan bead (the dried spherical chitosan of 0.1 gram) to be inserted in 50 cubic centimeters the dye solution, the spherical chitosan granular size is about 2.3 to 2.5mm.Be placed on can the tank of temperature control in, controlled temperature to 30 degree Celsius also vibrated about five days.Can use dense hydrogenchloride to adjust pH-value to 1, or use sodium hydroxide to adjust pH-value to 9 to 2.This embodiment adopts its absorption value of wavelength 534nm ultraviolet flash ranging, and pH-value is transferred to 6.Adsorptive capacity q when equation (1) is calculated equilibrium
e(g/kg):
q
e＝(C
0-C
e)V/W (1)
C wherein
0With C
eStrength of solution when being respectively initial and balance, V is the volume (cubic meter) of solution, the amount that W is used by spherical chitosan (kilogram)
Figure 2 shows that ear is not than the adsorptive power effect of present to RR189 to spherical chitosan with different linking agents, the spherical chitosan granular size is about 2.3 to 2.5mm, temperature 30 degree Celsius approximately, and pH value of solution is about 3.0.Known among the figure, the equilibrium adsorption ability of maximum (equilibrium adsorption isotherm) q
e(g/kg) to ECH, GA, EGDE are respectively not ear than 0.871,0.174,0.871.The adsorptive power of use ECH maximum is higher than respectively uses GA or EGDE to reach 69% and 83%.It is main because the functional group of difference relates to chemically crosslinkedization.ECH mainly by the hydroxy of spherical chitosan linking spherical chitosan, and GA and EGDE mainly link spherical chitosan it-NH
2Base.Therefore, GA and EGDE have reduced the main absorption position (NH by electrostatic attraction dyestuff RR189 negatively charged ion on spherical chitosan
3 +).Therefore the present invention adopts the linking agent of reagent E CH as present method.
Figure 3 shows that the resultant adsorptive power (absorbing dye RR189) of spherical chitosan of utilizing different molecular weight, this figure shows the molecular weight of spherical chitosan and goes second vinegarization (deacetylation) degree little to the influence of adsorptive power.Certainly the spherical chitosan of other molecular weight can also adopt.Perceptible is that other variation does not break away from disclosed spirit.
Fig. 4 is shown in temperature 30 degree Celsius, and pH-value 3.0 uses the effect of the crosslinkedization spherical chitosan absorbing dye RR189 of variable grain, also uses uncrosslinked spherical chitosan (pH-value 6.0) in addition.When wherein being shown in pH-value 3.0, its crosslinked spherical chitosan saturated extent of adsorption is about 90% and is higher than the uncrosslinked spherical chitosan of pH-value 6.0.Not only in that to be lower than pH-value insoluble below 5.5, and increase the ability of absorbing dye RR189 greatly according to the present invention's the crosslinkedization spherical chitosan that method formed.Fig. 4 is also shown in less balance dye strength Ce (＜400g/m
3=, along with its adsorptive power of increase of spherical chitosan bead diameter slightly reduces thereupon.And at higher Ce (1500-2000g/m
3) then comparatively approaching.Fig. 4 demonstration reduces with person's ball diameter, and the time that reaches balance also reduces.Therefore the ball diameter of the present invention's suggestion is about 2.3 to 2.5mm in preferred embodiment.
Balance isothermal adsorption (equilibrium adsorption isotherm) is for describing the characteristic between solute and sorbent material, and the Langmuir isotherm of general use what is called or Freundlich isotherm are in order to the definition adsorptive power.Table one is depicted as Langmuir isotherm and Freundlich isotherm parameter, the spherical chitosan particle absorbing dye RR189 that shows the size of utilizing three kinds of differences in the table, wherein maximum monolayer adsorption ability is calculated with Langmuirisotherm and is about 1802 to 1840g/kg.
Langmuir isotherm is expressed as follows:
Wherein, Q (g/kg) is high balance dye strength (high equilibrium dye concentration) C
eThe time per unit spherical chitosan weight the maximum dye adsorption amount of individual layer, b is the Langmuir constant, and is relevant with the avidity (affinity) of binding site.When the Q representative all covers dye molecule when the surface, the actual upper bound adsorptive power.Q and b can be by calculating C
e/ q
eTo C
eThe slope of straight line and intercept (intercept) obtain.
Freundlich isotherm is expressed as follows:
Wherein, Q
fRepresent the summary index of adsorptive power, (1/n) intensity of representative absorption.The size of index (1/n) is adsorbed the index of tendency.When n greater than 1 the time, the representative deflection helps the condition of absorption and (consults McKay, G., Blair, H.S., Gardner, J.R., 1982.Adsorption of dyes on chitin-I:Equilibriumstudies.J.App.Poly.Sci.27 3043-3057), can utilize ln (q
e) to ln (C
e) linear graph decision Q
fAnd (1/n).
Relevant the present invention's excellent specific property can be consulted table two, the maximum monolayer adsorption ability (g/kg) that wherein shows the method gained that utilizes various differences, wherein utilize method the best of the present invention, in other words for using with the spherical chitosan bead of TPP as reagent place's formation.As mentioned above, the crosslinkedization spherical chitosan bead made by the present invention has preferable rigidity, and be not soft as if what make with sodium hydroxide.And prior art will peel off after crosslinkedization and dryingization in the mode of NaOH making in flakes.
For the mechanism of desorption, false first step absorption (pseudo first order adsorption), false second stage absorption (pseudo second order adsorption) and interior particle (intra-particle) diffusion model are used to test the dynamic experiment data.The first step speed type of Lagergren is given as (consults Lagergren, S., 1898.Zurtheorie der sogenannten adsorption geloster stoffe.Kungliga SvenskaVetenskapsakademiens.Handlingar, 24,1-39):
Wherein, q
eAnd q is respectively the adsorptive capacity of the sorbent material when balance and time t.k
1Rate constant for first step absorption (1/ minute).Log (q
e-q) slope to the t mapping determines first step rate constants k
1
Second stage kinetic energy model be given as (consult McKay, G., Ho, Y.S., 1999b.Pseudo-secondorder model for sorption processes.Process Biochem.34,451-465):
And
Wherein, k
2Be the rate constant of second stage absorption (kg/minute * g), and h is initial adsorption rate (initial adsorption rate; G/kg * min).T/q is to slope and the intercept decision second stage rate constants k of t figure
2And q
e
(intra-particle) diffusion model is as follows in the particle:
q＝k
it
0.5 (7)
Wherein, k
iBe particle internal diffusion rate constant (gkg
-1Min
-0.5).For q to t
0.5The slope of mapping line part branch.
The influence of initial dye strength:
Fig. 5 is shown as dyestuff RR189 concentration to spend 3.0 times dynamic influences of crosslinkedization spherical chitosans absorption of pH-value in centigradetemperature 30.The concentration increase of initial dyestuff causes the ability of spherical chitosan absorbing dye to increase.Be respectively the adsorptive capacity that ten hours adsorptive power of 5096 and 1910 gram/cubic meters is higher than starting point concentration 1999 gram/cubic meters for initial dye strength and be respectively 72% and 54%.Its meaning dyestuff starting point concentration adsorbs for crosslinkedization spherical chitosan plays the part of important role.What table three showed is for the rate constant of the initial dye strength of difference with (intra-particle) diffusion model in false first step absorption (pseudofirst order adsorption), false second stage absorption (pseudo second order adsorption) and the particle.Relation conefficient (correlation coefficient) R of false second stage Adsorption Model
2Has very high numerical value greater than 0.998.The result of table three shows that also rate constant (rate constant), initial adsorption rate (initial adsorption rate) and equilibrium adsorption ability (equilibrium adsorption capacity) are the equation of dyestuff starting point concentration.In the Adsorption Model of the false second stage, along with initial dye strength increases to 2900 gram/cubic meters by 1910, at last to 5096 gram/cubic meters, it increases with concentration and increases progressively.And the equilibrium adsorption ability (q of calculating
E, cal) then increase and increase along with initial dye strength.Equilibrium adsorption ability (q in starting point concentration 5096 gram/cubic meters and 2900 gram/cubic meters
E, cal) to be higher than respectively at starting point concentration be that the equilibrium adsorption ability of 1910 gram/cubic meters reaches 54% and 93%.
Temperature effect:
Fig. 6 displays temperature is for dye adsorption influence, and it adsorbs the dyestuff RR189 that initial dye strength is 4330 gram/cubic meters in pH-value 3.0 with crosslinkedization spherical chitosan.The increase of displays temperature causes the increase of initial adsorption rate among the figure, no matter what are six hours temperature still, its adsorptive power is suitable.General normal wastewater temperature changes and is unlikely to that whole removal dye colour ability is had too big influence.Table three has also shown the rate constant of the Model Calculation of utilizing above-mentioned three kinds of differences.False second stage Adsorption Model has higher relation conefficient (correlation coefficient) R
2Numerical value is greater than 0.997.The equilibrium adsorption ability of its calculating meets the equilibrium adsorption ability of experiment.It shows that the mechanism of dye adsorption process mainly is subjected to the domination and the influence of false second stage Adsorption Model.In the time of six hours, the adsorptive power (q of temperature 30,40 and 50 degree Celsius
t) reach it respectively and estimate 83%, 90% and 96% of equilibrium adsorption value, that is to say and understand and shortened the time that reaches trim point along with the increase of temperature.Its major cause is the density that higher temperature has increased speed of reaction and reduced grain, and this phenomenon forms and more easily make the dye molecule diffusion.In the Adsorption Model of the false second stage, along with temperature increases to 50 degree by 30 degree Celsius, rate constant and initial adsorption rate increase significantly.Be respectively at temperature 30 degree 4.66 times and 1.76 times in the rate constant of temperature 40 and 50 degree.Equilibrium adsorption ability (the q of calculating
E, cal) also follow the increase of temperature and successively decrease, at the equilibrium adsorption ability (q of the calculating of centigradetemperature 30 and 40 degree
E, cal) equilibrium adsorption ability when spending greater than temperature 50 respectively reaches 18% and 9%.
Thermodynamical coordinate such as free energy change (Δ G
0), enthalpy change (Δ H
0) and Entropy Changesization (Δ S
0) be to be subjected to following equation to determine:
ΔG
0＝-RTlnK
c (9)
Kc is the equilibrium constant, C
AeBe when trim point, every cubic metre of solution is adsorbed the amount of dye of agent absorption, C
eEquilibrium concentration for dyestuff in the solution.T is solution temperature (a triumphant formula temperature), and R is a gas law constant.(Δ H
0) and Entropy Changesization (Δ S
0) be slope and the intercept of van ' the t Hoff figure of 1/T to be decided by logKc.(the equilibrium adsorption ability by the false second stage model in the table three can obtain C to the results are shown in table four
Δ e), free energy change (Δ G
0) negative value represent that crosslinkedization spherical chitosan is idiopathic (spontaneous) to the absorption of dyestuff.Enthalpy change (Δ H
0) negative value represent that this is adsorbed as thermopositive reaction, Entropy Changesization (Δ S
0) negative value be illustrated in the spherical chitosan of crosslinkedization adsorption process and reduce at solid-state random degree with the solution interface to dyestuff.
The rate constant of false second stage reaction and the available Arrhenius equation of relation of inverse temperature are described below.
Wherein k is the rate constant of absorption, k
0Independent factor (kgg for temperature
-1Min
-1), E
AdBe the required activation energy (J/mol) of absorption.k
0And E
AdSystem obtains slope and the intercept of 1/T figure by ln (k), the results are shown in table four.Therefore, the relation of k and T can be represented with the Arrhenius form:
Activation energy of adsorption E
AdWith desorption (desorption) activation energy E
DeRelation can utilize following relation to represent:
ΔH
0＝E
ad-E
de (13)
According to the data of table four, the activation energy E of desorption
DeEstimate to be about 128.656kJ/mol, its data can be represented the dyestuff that self-crosslinking spherical chitosan surface is adsorbed, as RR189, and the degree of difficulty of desorption to the solution.
The influence of potential of hydrogen:
Fig. 7 is when centigradetemperature 30 degree and initial dye strength 4571 gram/cubic meters, and potential of hydrogen is to the influence of spherical chitosan absorbing dye, and this embodiment adopts RR189, right also non-limiting the present invention's absorption object.Show the reduction along with pH-value among the figure, its adsorptive power significantly increases.Under the identical condition of Fig. 7, Fig. 8 shows 48 hours adsorptive power of use crosslinkedization spherical chitosan bead (pH 1 to 9).The pH-value of solution influences the adsorptive power of crosslinkedization spherical chitosan bead consumingly, and the adsorptive power of non-crosslinked spherical chitosan almost remains unchanged.At crosslinkedization spherical chitosan bead with pH 1.0,3.0 and 6.0 through 48 hours absorption, amount of its absorption RR189 is higher than respectively uses uncrosslinked spherical chitosan in 118%, 78% and 32% of 6.0 times adsorptive capacitys of pH.Therefore, the potential of hydrogen of solution influences the degree of using the spherical chitosan absorbing dye, for example RR189 widely.Therefore the present invention's method is fit to be used in the wastewater treatment of acidity very much, improves prior art widely and is unfavorable for being used in shortcoming in the sour environment.
Table three shown different pH-values to rate constant respectively with three kinds of results that Model Calculation is resultant.False second stage Adsorption Model has very high association coefficient (correlation coefficient) R
2Numerical value is about 1.000.The equilibrium adsorption ability that meets experiment in the equilibrium adsorption ability of its calculating in 48 hours.It shows that the mechanism of dye adsorption process mainly is subjected to the domination and the influence of false second stage Adsorption Model.In table three, its rate constant increases progressively along with increasing progressively of pH value, and the initial adsorption rate increases progressively with the pH value and successively decrease, at Ph1.0 and be more or less the same in 3.0 o'clock.For crosslinkedization spherical chitosan bead, the calculated equilibrium adsorptive power in pH value 1.0 and 3.0 is higher than respectively and equals 6.0 o'clock adsorptive capacity in the pH value and reach 66% and 34%.
The influence of dryingization:
The above-mentioned crosslinkedization spherical chitosan bead that uses is what wet, being the influence for adsorptive power of the crosslinkedization spherical chitosan bead of understanding drying, is that 2.3 to 2.5 millimeters reduced to 8.777 is to 8.235 microns with the crosslinkedization spherical chitosan bead granular size of drying at hygrometric state.When the 9th figure is presented at centigradetemperature 30 degree and initial dye strength 4571 gram/cubic meters, potential of hydrogen is 1.0 o'clock, the ability of the absorbing dye of the crosslinkedization spherical chitosan bead of dried and wet both kenels, this embodiment adopts RR189, right also non-limiting the present invention's absorption object.The adsorption rate of visible wet curing spherical chitosan bead is faster than the adsorption rate of dry type among the figure, and the time that reaches approximate adsorptive power postpones to be about 18 hours.Main because dry type spherical chitosan bead must be taken time its expansion before beginning absorption, still, no matter through 48 hours being that the experiment adsorptive power of dry type or wet type spherical chitosan bead is suitable.
Table three has shown dry type and wet type spherical chitosan bead rate constant, respectively with three kinds of results that Model Calculation is resultant.Compare the equilibrium adsorption ability of association coefficient and calculating, the wet type spherical chitosan bead meets the result with the Adsorption Model calculating of the false second stage, tool association coefficients R
2Numerical value is about 1.000.Yet the dry type spherical chitosan bead meets the result with the calculating of false first step Adsorption Model, the association coefficients R
2Numerical value is about 0.999.
Spherical chitosan bead that it should be noted that the present invention applicable in acidity or the neutral solution with absorption reaction dyestuff, matching stain and direct dyestuff.Method according to the present invention can be purchased the spherical chitosan bead sorbent material, its feature system purchases with crosslinkedization spherical chitosan, wherein linking agent system selects one of ECH, GA, EGDE for use, the mean diameter of above-mentioned spherical chitosan bead sorbent material is greater than 8.5 microns, applicable in acidity or the neutral solution with absorption reaction dyestuff, matching stain or direct dyestuff.
The above is only for the present invention's preferred embodiment; it is intended to contain the spirit and the contained difference and the similar state of category of the present patent application claim; the present patent application claim should be with extensive interpretation to contain above-mentioned all and any improvement and so on like mode or structure; the present invention with the preferred embodiment explanation as above; and be familiar with this field skill person; in not breaking away from the present invention's spiritual scope; when can doing a little change retouching, its scope of patent protection more when on after attached claim and etc. same domain decide.The blue Mu Er of table 1. different-grain diameter under 30C and Fu Ruoyinlixi isothermal adsorption constant P article orchid are tried to gain Er Furuoyinlixi Sizes (mm)
Q (g/kg) b (rn
3/ g) R
2Q
fN R
2PH3.0 (crosslinked) is little: in 2.3～2.5 1,834 0.1459 1.000 1,147 15.00 0.553: 2.5～2.7 1,840 0.0655 0.999 891 9.76 0.742 is big: 3.5～3.8 1,802 0.0337 0.999 865 10.06 0.722pH6.0 (uncrosslinked) are little: it is (crosslinked that the various different sorbent materials of 2.3～2.5 950 0.0606 0.995 231 4.35 0.716 tables 2. can adsorb red 189 spherical chitosan beads of the different sorbent materials of comparison sheet Dyes maximum monolayer adsorption capacity gram/kilogram reactivity of the maximum monolayer adsorption capacity of different dyes, tri-polyphosphate) (end is crosslinked for reactive red 189 spherical chitosan beads of 1802-1840 the present invention, tri-polyphosphate) reactive red 189 spherical chitosan beads of 950 the present invention are (crosslinked, sodium hydroxide) reactive red 189 spherical chitosan beads of 1642-1936 are (uncrosslinked, sodium hydroxide) reactive red 222 spherical chitosan beads of 1189 acid tangerine 11 spherical chitosan fibers (crosslinked) 1226-1678 are (uncrosslinked, sodium hydroxide) reactive red 222 spherical chitosan beads of 1026-1106 are (uncrosslinked, sodium hydroxide) reactive red 222 chitins of 299-380～reactive blue 222 spherical chitosan beads in 100 reactive red 222 activated carbon～50 are (uncrosslinked, sodium hydroxide) reactive blue 145 spherical chitosan beads of 54-87 are (uncrosslinked, sodium hydroxide) reactive yellow 2 activated sludges of direct red 84 chitins, the 44 reactive yellow 2 mushroom 52-124 in 117-179 Tai Lunlan activated carbon～160 333 reactive blue 2 rice husks, 130 reactive blue 2 activated sludges, 250 reactive blue 2 earth, 260 dispersed red 1 mud coals, volcanic clay, slag, the different initial concentrations of flying dust 23-50 acid blue purple 17 orange peels, the 20 acid tangerine 10 activated carbon 2-6 tables 3. of acid gorgeous blue banana pith 4-5, temperature, pH value and dried/wet ball are first, reaction rate constant k in secondary and the particle internal diffusion Adsorption Model, balance is inhaled
Attached amount calculated value q
eAnd real dangerous adsorptive capacity q
t
First step kinetic model second stage kinetic model particle internal diffusion model parameter q
1k
1q
E, calR
2k
2H q
E, calR
2k
iR
2
(gram/kilogram) (divides
-1) (gram/kilogram) (kilogram gram
-1Divide
-1) (gram kilogram
-1Divide
-1) (gram/kilogram) (kilogram gram
-1Divide
-1) initial concentration t=10 hour (pH3.0) (g/m
3) 1,910 941 0.0186 573 0.889 4.269 * 10
-542.14 995 0.998 84.77 0.9792900 1,446 0.0116 986 0.998 2.028 * 10
-547.86 1,536 1.000 121.41 0.9805096 1,616 0.0139 1,070 0.938 1.912 * 10
-570.87 1,925 0.999 137.22 0.978 temperature (℃) t=6 hour (pH3.0) 30 1,680 0.0161 1,887 0.971 7.793 * 10
-631.81 2,020 0.997 120.80 0.99140 1,679 0.0221 1,813 0.987 1.593 * 10
-555.86 1,873 0.997 145.87 0.99650 1,652 0.0340 1,284 0.871 5.037 * 10
-5148.18 1,715 0.997 182.94 0.981 table 3 (continued on next page) pH t=48 hours 1.0 2,089 0.0069 1,179 0.924 1.559 * 10
-569.97 2,119 1.000 138.52 0.9663.0 1,706 0.0083 700 0.858 2.376 * 10
-569.56 1,711 1.000 113.06 0.9936.0 1,263 0.0028 385 0.688 2.454 * 10
-540.05 wet ball 2,089 0.0069 1,179 0.924 1.559 * 10 of 1,278 1.000 91.43 0.978 wet/dried t=48 hour (pH1.0)
-569.97 2,119 1.000 138.52 0.966 dried balls 2,160 0.0029 2,264 0.999 9.214 * 10
-76.16 parameters such as 2,585 0.952 79.42 0.961 table 4. thermodynamics and rate constant (pH3.0, grain Trail size 2.3-2.5 millimeter, first Concentrated degree 4330 gram/rice
3)
Thermodynamical coordinate rate constant temperature K
cΔ G
0Δ H
0Δ S
0R
2K
0E
AdR
2(℃) (thousand joule of ear not
-1) (thousand joule of ear not
-1) (joule is ear not
-1K
-1) (kilogram
-1Divide
-1) (thousand joule of ear not
-1) 30 13.974-6.64340 6.403-4.832-52.948-153.112 0.991 8.107 * 10
775.708 0.97750 3.813-3.594
Claims (21)
1, a kind of with crosslinkedization spherical chitosan bead process for adsorption of dye, this method comprises the following step at least:
Provide spherical chitosan also this spherical chitosan to be dissolved to form spherical chitosan solution;
Form spherical chitosan bead, with state spherical chitosan solution and tri-polyphosphate (TPP on preparing; Tripolyphosphate) the solution mixing is beneficial to form ionic crosslinked spherical chitosan bead; And
Above-mentioned ionic crosslinked spherical chitosan bead is produced the chemically crosslinked reaction to form crosslinkedization spherical chitosan bead, wherein comprise adding sodium hydroxide and linking agent, first period in the tank of this solution between centigradetemperature 25-55 degree that vibrate afterwards; And
The spherical chitosan bead of above-mentioned crosslinkedization can be placed solution be beneficial to adsorb this dyestuff with dyestuff.
2, according to claim 1 described with crosslinkedization spherical chitosan bead process for adsorption of dye, it is characterized in that: above-mentioned spherical chitosan is dissolved in the acetic acid.
3, according to claim 1 described with crosslinkedization spherical chitosan bead process for adsorption of dye, it is characterized in that: after finishing above-mentioned spherical chitosan and being dissolved in acidic solution, mixing solutions is left standstill about second period.
4, according to claim 3 described with crosslinkedization spherical chitosan bead process for adsorption of dye, it is characterized in that: above-mentioned second period is at least about 6 hours.
5, according to claim 1 described with crosslinkedization spherical chitosan bead process for adsorption of dye, it is characterized in that: above-mentioned spherical chitosan solution and above-mentioned tri-polyphosphate (TPP; Tripolyphosphate) solution leaves standstill about the 3rd period after mixing.
6, according to claim 5 described with crosslinkedization spherical chitosan bead process for adsorption of dye, it is characterized in that: above-mentioned the 3rd period is at least about 4 hours.
7, according to claim 1 described with crosslinkedization spherical chitosan bead process for adsorption of dye, it is characterized in that: produce above-mentioned linking agent and comprise ECH (epichlorohydrin).
8, according to claim 1 described with crosslinkedization spherical chitosan bead process for adsorption of dye, it is characterized in that: produce above-mentioned linking agent and comprise GA (glutaraldehyde).
9, according to claim 1 described with crosslinkedization spherical chitosan bead process for adsorption of dye, it is characterized in that: produce above-mentioned linking agent and comprise EGDE (ethylene glycol diglycidyl ether).
10, according to claim 1 described with crosslinkedization spherical chitosan bead process for adsorption of dye, it is characterized in that: above-mentioned first period is at least about 6 hours.
11, according to claim 1 described with crosslinkedization spherical chitosan bead process for adsorption of dye, it is characterized in that: above-mentioned spherical chitosan bead applicable in acidity or the neutral solution with absorption reaction dyestuff, matching stain or direct dyestuff.
12, a kind of method of formation spherical chitosan bead, this method comprises the following step at least:
Spherical chitosan is dissolved in the acetic acid to form spherical chitosan solution, again with above-mentioned spherical chitosan solution left standstill;
With state spherical chitosan solution and tri-polyphosphate (TPP on preparing; Tripolyphosphate) the solution mixing is beneficial to form ionic crosslinked spherical chitosan bead;
Wherein above-mentioned spherical chitosan solution and above-mentioned tri-polyphosphate (TPP; Tripolyphosphate) solution leaves standstill an about period after mixing.
13, according to the method for the described formation spherical chitosan bead of claim 12, it is characterized in that: above-mentionedly leave standstill the period and be at least about 4 hours.
14, according to the method for the described formation spherical chitosan bead of claim 12, it is characterized in that: above-mentioned spherical chitosan bead applicable in acidity or the neutral solution with absorption reaction dyestuff, matching stain and direct dyestuff.
15, a kind of method of crosslinkedization of formation spherical chitosan bead, this method comprises the following step at least:
Spherical chitosan is dissolved in the acetic acid to form spherical chitosan solution, again with above-mentioned spherical chitosan solution left standstill;
With state spherical chitosan solution and tri-polyphosphate (TPP on preparing; Tripolyphosphate) the solution mixing is beneficial to form the crosslinked spherical chitosan bead of ionization;
Wherein above-mentioned spherical chitosan solution and above-mentioned tri-polyphosphate (TPP; Tripolyphosphate) leave standstill about first period after solution mixes to form the crosslinked spherical chitosan bead of ionization;
The spherical chitosan bead that above-mentioned ionization is crosslinked produces the chemically crosslinked reaction to form the spherical chitosan bead of crosslinkedization, wherein comprises to add sodium hydroxide and chemical cross-linking agent, second period in the tank of this solution between centigradetemperature 25-55 degree that vibrate afterwards.
16, according to the method for described crosslinkedization of the formation spherical chitosan bead of claim 15, it is characterized in that: produce above-mentioned chemical cross-linking agent and comprise ECH (epichlorohydrin).
17, according to the method for described crosslinkedization of the formation spherical chitosan bead of claim 15, it is characterized in that: produce above-mentioned chemically crosslinkedization and comprise GA (glutaraldehyde).
18, according to the method for described crosslinkedization of the formation spherical chitosan bead of claim 15, it is characterized in that: produce above-mentioned chemical cross-linking agent and comprise EGDE (ethylene glycol diglycidyl ether).
19, according to the method for described crosslinkedization of the formation spherical chitosan bead of claim 15, it is characterized in that: above-mentioned spherical chitosan bead applicable in acidity or the neutral solution with absorption reaction dyestuff, matching stain and direct dyestuff.
20, a kind of spherical chitosan bead sorbent material, it is characterized in that: purchase with crosslinkedization spherical chitosan, wherein linking agent is selected one of ECH, GA, EGDE for use, above-mentioned spherical chitosan bead sorbent material applicable in acidity or the neutral solution with absorption reaction dyestuff, matching stain or direct dyestuff.
21, the spherical chitosan bead sorbent material according to claim 20, it is characterized in that: the mean diameter of spherical chitosan bead sorbent material is greater than 680 microns.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005080489A1 (en) * | 2004-02-23 | 2005-09-01 | Caiteng Zhang | A solution of metal-polymer chelate(s) and applications thereof |
| CN106630396A (en) * | 2016-11-23 | 2017-05-10 | 武汉轻工大学 | Simple process for treating wastewater containing various dyes |
-
2002
- 2002-05-15 CN CN 02117804 patent/CN1458072A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005080489A1 (en) * | 2004-02-23 | 2005-09-01 | Caiteng Zhang | A solution of metal-polymer chelate(s) and applications thereof |
| GB2429458A (en) * | 2004-02-23 | 2007-02-28 | Caiteng Zhang | A solution of metal-polymer chelate(s) and applications thereof |
| JP2007523096A (en) * | 2004-02-23 | 2007-08-16 | 張才騰 | Metal complex solution and its application |
| GB2429458B (en) * | 2004-02-23 | 2009-08-05 | Caiteng Zhang | A solution of metal-polymer chelate(s) and applications thereof(cleaner) |
| AU2005215846B2 (en) * | 2004-02-23 | 2011-01-27 | Caiteng Zhang | A solution of metal-polymer chelate(s) and applications thereof |
| US8193291B2 (en) | 2004-02-23 | 2012-06-05 | Caiteng Zhang | Solution of metal-polymer chelate(s) and applications thereof |
| EA018643B1 (en) * | 2004-02-23 | 2013-09-30 | Цайтэн Чжан | A solution of metal-containing polymer chelate(s) and applications thereof (variants) |
| CN106630396A (en) * | 2016-11-23 | 2017-05-10 | 武汉轻工大学 | Simple process for treating wastewater containing various dyes |
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