CN107175083A - A kind of FeCl3Chitosan polymer and preparation method and application - Google Patents

A kind of FeCl3Chitosan polymer and preparation method and application Download PDF

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CN107175083A
CN107175083A CN201710423287.2A CN201710423287A CN107175083A CN 107175083 A CN107175083 A CN 107175083A CN 201710423287 A CN201710423287 A CN 201710423287A CN 107175083 A CN107175083 A CN 107175083A
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fecl
cts
deposit
methylene blue
chitosan polymer
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郭俊元
陈诚
张萍
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Chengdu University of Information Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • B01J20/0229—Compounds of Fe
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry

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  • Water Treatment By Sorption (AREA)

Abstract

The invention discloses a kind of FeCl3Chitosan polymer and preparation method and application, wherein, preparation method comprises the following steps：A certain amount of natural chitosan of precise (N CTS), with FeCl3Solution is mixed, normal temperature magnetic agitation, then adds twice FeCl3The absolute ethyl alcohol of liquor capacity, and be slowly stirred, centrifugal treating is carried out after flocculent deposit to be generated, separation obtains deposit；After the iron ion that deposit surface is washed away with ethanol, deposit is mixed with glutaraldehyde solution, and carries out normal temperature magnetic power stirring, and centrifugal treating is carried out afterwards and obtains deposit, deposit washs with ethanol again, is dried afterwards, milled processed, acquisition FeCl3Chitosan polymer (FeCl3‑CTS).The FeCl that the present invention is prepared3Chitosan polymer can be used for handling methylene blue waste water.

Description

A kind of FeCl3- chitosan polymer and preparation method and application
Technical field
The invention belongs to field of environment engineering technology, specifically, it is related to a kind of FeCl3- chitosan polymer and its system Preparation Method and application.
Background technology
China's weaving, dye industry are developed rapidly, and a large amount of dyestuffs discharge into water body in the production and use process, make Into serious water body environment pollution.Content of organics is high in waste water from dyestuff, colourity is high, also contain poisonous and harmful substance, is typical case Difficult waste water.(Ren Nanqi, Zhou Xianjiao, Guo Wanqian wait dye wastewater treatment technologies progress [J] chemical industry to Ren Nanqi Journal, 2013,64 (1):84-93.), (Wang Hui, Zhou Yuexia, Bai Shijie wait grinding for waste water from dyestuff Biochemical method technologies to Wang Hui Study carefully progress [J] Xiamen University's journals (natural science edition), 2008,47 (2):Conventional method 286-290.) et al. be have studied to dye Expect the treatment effect of waste water, as a result find that treatment effect is undesirable, operating cost is higher, floor space is larger, and easily cause tight The secondary pollution of weight.Zhu Jing experimental study has then affirmed that materializing strategy is combined in processing waste water from dyestuff with bioengineering (Zhu Jing, Xu Dongliang, Wang Jiarong wait .A/O biochemistry-coagulation-settlement process processing dyeing waste water [J] Ningbo Engineering Colleges to high efficiency Journal, 2006,18 (2):38-40.).
During the materializing strategy of dyeing waste water, the natural organic high-molecular material by representative of chitosan can strengthen print Waste water quality processing is contaminated, particularly there is preferable decolorizing effect to water-soluble dye.Although chitosan is because of its unique molecule Structure, functional group, can be used in the removal of organic pollution and pigment in waste water from dyestuff, but because cationic is weaker, it is right The limit sorption potential of dyestuff is not high, and applicable pH value range is narrower, limits it in actual dying processing engineering Extensive use, therefore, it is necessary to using the molecular structure and functional group of chitosan, processing is modified to it, to change Kind chitosan absorption property, improves its effect for handling waste water from dyestuff.
The content of the invention
In view of this, there is provided a kind of FeCl for the problem of present invention is directed to above-mentioned3- chitosan polymer and its preparation side Method and application, this experiment for raw material, using cross-linked modification method, using glutaraldehyde as crosslinking agent, utilize shell with chitosan (CTS) Glycan aldehyde radical active group is crosslinked FeCl3, so as to obtain the FeCl of more decoloring ability3- chitosan polymer (FeCl3- CTS gathers Compound).Using 20-2000mg/L methylene blue solutions as process object, by investigating FeCl3- CTS dosages, wastewater pH, reaction The influence to methylene blue solution decolorizing effect such as time, obtains FeCl3The optimal procedure parameters that-CTS is removed to chroma in waste water.
In order to solve the above-mentioned technical problem, the invention discloses a kind of FeCl3The preparation method of-chitosan polymer, bag Include following steps：
A certain amount of chitosan of step 1, precise, with FeCl3Solution is mixed, normal temperature magnetic agitation, then is added twice In FeCl3The absolute ethyl alcohol of liquor capacity, and be slowly stirred, centrifugal treating is carried out after flocculent deposit to be generated, separation is sunk Product thing；
Step 2, washed away with ethanol after the iron ion of deposit surface, deposit is mixed with glutaraldehyde solution, and is carried out normal Warm magnetic agitation, carries out centrifugal treating and obtains deposit, deposit is washed with ethanol, dried, ground afterwards again afterwards Processing, obtains FeCl3- chitosan polymer.
Further, the chitosan and FeCl in step 13The solid-liquid ratio (m/V, mg/mL) of solution is 2:1-10:1；FeCl3 The concentration of solution is 0.05-0.25mol/L.
Further, the magnetic agitation time in step 1 is 0.5-4h.
Further, the centrifugal rotational speed in step 1 is 2000-4000r/min；Centrifugation time is 5-15min.
Further, the concentration of the glutaraldehyde solution in step 2 is 20%-30%；The addition of glutaraldehyde solution is FeCl3The 15%-25% of liquor capacity.
Further, the magnetic agitation time in step 2 is that the centrifugal rotational speed in 0.5-2h, step 2 is 2000-4000r/ min。
Further, the drying temperature in step 2 is 70-90 DEG C.
The invention also discloses a kind of FeCl prepared by above-mentioned preparation method3- chitosan polymer.
The invention also discloses a kind of above-mentioned FeCl3- chitosan polymer is removing methylene blue in waste dyestuff thing Application in matter.
Further, the application comprises the following steps：Adjust methylene blue waste water pH be 6-10 in the range of, will be above-mentioned The FeCl prepared3- chitosan polymer is 1 according to solid-liquid ratio (g/L):10-2:5 deliver into methylene blue waste water reaction 15-50min。
Compared with prior art, the present invention can be obtained including following technique effect：
1) this experiment is in chitosan, 0.1mol/L FeCl3Solution, 25% glutaraldehyde are with 25:5:1 (m/V/V, mg/ ML/mL it is) cross-linking modified under the conditions of ratio, obtain a kind of highly effective Fe/C l3-CTS。
2)FeCl3- CTS embodies more unmodified chitosan (N-CTS) percent of decolourization higher to methylene blue waste water and suction Attached capacity, works as FeCl3- CTS dosages be 0.1g/L, wastewater pH is 6, the reaction time be 50min under conditions of, FeCl3- CTS pairs Methylene blue decolorization rate of wastewater, adsorption capacity respectively reach 99.4%, 198.8mg/g, are above N-CTS.
3)FeCl3- CTS dynamics and thermoisopleth fitting result show, FeCl3- CTS handles the process of methylene blue waste water More meet the adsorption dynamics adsorption kinetics process of pseudo-second order kinetic description and the adsorption isotherm line process of Langmuir descriptions.
Certainly, any product for implementing the present invention it is not absolutely required to while reaching all the above technique effect.
Brief description of the drawings
Accompanying drawing described herein is used for providing a further understanding of the present invention, constitutes the part of the present invention, this hair Bright schematic description and description is used to explain the present invention, does not constitute inappropriate limitation of the present invention.In the accompanying drawings：
Fig. 1 is that the present invention prepares FeCl3- chitosan (FeCl3- CTS) process chart；
Fig. 2 is FeCl of the present invention3The influence of-CTS, N-CTS dosages to methylene blue decolorization rate of wastewater；
Fig. 3 is FeCl of the present invention3The influence of-CTS, N-CTS dosages to adsorption capacity；
Fig. 4 is influence of the wastewater pH of the present invention to methylene blue decolorization rate of wastewater；
Fig. 5 is wastewater pH of the present invention to FeCl3- CTS, N-CTS adsorption capacities influence；
Fig. 6 is influence of the reaction time of the invention to methylene blue decolorization rate of wastewater；
Fig. 7 is the reaction time of the invention to FeCl3- CTS, N-CTS adsorption capacities influence；
Fig. 8 is initial concentration of the present invention to decolorization rate of wastewater and FeCl3The influence of-CTS adsorption capacities；
Fig. 9 is influence of the initial concentration of the present invention to decolorization rate of wastewater and N-CTS adsorption capacities；
Figure 10 is pseudo-first-order kinetics equation fitting of the present invention；
Figure 11 is pseudo-second order kinetic equation model of the present invention；
Figure 12 is Langmuir Tellurium determinations fitting of the present invention；
Figure 13 is Freundlich Tellurium determinations fitting of the present invention.
Embodiment
Describe embodiments of the present invention in detail below in conjunction with embodiment, thereby to the present invention how application technology hand Section can fully understand and implement according to this to solve technical problem and reach the implementation process of technology effect.
The invention discloses a kind of FeCl3The preparation method of-chitosan polymer, as shown in figure 1, comprising the following steps：
A certain amount of chitosan of step 1, precise, the FeCl with 0.05-0.25mol/L3Solution is with 2:1-10:1(m/ V, mg/mL) mix, after normal temperature magnetic agitation 0.5-4h, then add twice FeCl3The absolute ethyl alcohol of liquor capacity, and slowly Stirring, after flocculent deposit to be generated, centrifuges 5-15min, separation obtains deposit under conditions of rotating speed 2000-4000r/min；
FeCl3Concentration be more than 0.25mol/L when, can because the increase of effects of ion intensity cause chitosan dissolubility become Difference, and the active group on its surface are limited by certain reaction, so that removing the efficiency of methylene blue dye material Reduction.
Step 2, washed away with ethanol after the iron ion of deposit surface, the mixing of deposit glutaraldehyde solution, wherein, glutaraldehyde The addition of solution is FeCl3The 15%-25% of liquor capacity, the mass concentration of glutaraldehyde solution is 20%-30% normal temperature magnetics After power stirring 0.5-2h, centrifugation obtains deposit under the conditions of rotating speed 2000-4000r/min, and deposit is washed with ethanol again, it 70-90 DEG C of drying afterwards, grinding obtains FeCl3- chitosan polymer.
Glutaraldehyde, as crosslinking agent, is to realize FeCl3The key of-chitosan polymer formation, ensure that chitosan aldehyde Base active group is crosslinked FeCl3Be smoothed out.The concentration of glutaraldehyde solution is 20%-30%, when glutaraldehyde consumption is less, The interchain of crosslinked resin arranges more loose, FeCl3The poor-performing of-chitosan polymer.When glutaraldehyde consumption is excessive, it can make Obtain FeCl3- chitosan polymer hydrophobicity increase so that FeCl3- chitosan removes the efficiency reduction of methylene blue dye material.
The invention also discloses a kind of FeCl3- chitosan polymer is in methylene blue in waste dye substance is removed Using comprising the following steps：Adjust methylene blue waste water pH be 6-10 in the range of, by the above-mentioned FeCl prepared3- shell gathers Glycopolymers are 1 according to solid-liquid ratio (g/L):10-2:5 dispensings react 15-50min into methylene blue waste water.
Embodiment 1
A kind of FeCl3The preparation method of-chitosan polymer, comprises the following steps：A certain amount of chitosan of precise, With 0.1mol/L FeCl3Solution is with 5:1 (m/V, mg/mL) is mixed, and after normal temperature magnetic agitation 4h, then adds twice FeCl3It is molten The absolute ethyl alcohol of liquid product, and be slowly stirred, after flocculent deposit to be generated, 10min is centrifuged under conditions of rotating speed 3000r/min, Separation obtains deposit；After the iron ion that deposit surface is washed away with ethanol, deposit and 1/5 is in FeCl3The penta of liquor capacity After dialdehyde solution (concentration of glutaraldehyde solution is 25%) mixing, normal temperature magnetic agitation 2h, centrifuged under the conditions of rotating speed 3000r/min Deposit is obtained, deposit is washed with ethanol again, afterwards 80 DEG C of drying, grinding obtains FeCl3- chitosan polymer.
The pH for adjusting methylene blue waste water is 6, by the above-mentioned FeCl prepared3- chitosan polymer is according to solid-liquid ratio (g/ L it is) 1:10 dispensings react 15min into methylene blue waste water.
Embodiment 2
A kind of FeCl3The preparation method of-chitosan polymer, comprises the following steps：
A certain amount of chitosan of step 1, precise, the FeCl with 0.05mol/L3Solution is with 10:1 (m/V, mg/mL) After mixing, normal temperature magnetic agitation 0.5h, then add twice FeCl3The absolute ethyl alcohol of liquor capacity, and be slowly stirred, it is to be generated After flocculent deposit, 5min is centrifuged under conditions of rotating speed 4000r/min, separation obtains deposit；
Step 2, washed away with ethanol after the iron ion of deposit surface, the mixing of deposit glutaraldehyde solution, wherein, glutaraldehyde The addition of solution is FeCl3The 25% of liquor capacity, after the mass concentration of glutaraldehyde solution is 20% normal temperature magnetic agitation 2h, Centrifugation obtains deposit under the conditions of rotating speed 4000r/min, and deposit is washed with ethanol again, afterwards 70 DEG C of drying, grinds, and obtains FeCl3- chitosan polymer.
The above-mentioned FeCl prepared3- chitosan polymer may apply to removal methylene blue in waste dye substance In, comprise the following steps：Adjust methylene blue waste water pH be 6 in the range of, by the above-mentioned FeCl prepared3- chitosan gathers Compound is 2 according to solid-liquid ratio (g/L):5 dispensings react 15min into methylene blue waste water.
Embodiment 3
A kind of FeCl3The preparation method of-chitosan polymer, comprises the following steps：
A certain amount of chitosan of step 1, precise, the FeCl with 0.25mol/L3Solution is with 2:1 (m/V, mg/mL) is mixed Close, after normal temperature magnetic agitation 4h, then add twice FeCl3The absolute ethyl alcohol of liquor capacity, and be slowly stirred, it is to be generated cotton-shaped After precipitation, 15min is centrifuged under conditions of rotating speed 2000r/min, separation obtains deposit；
Step 2, washed away with ethanol after the iron ion of deposit surface, the mixing of deposit glutaraldehyde solution, wherein, glutaraldehyde The addition of solution is FeCl3The 15% of liquor capacity, the mass concentration of glutaraldehyde solution is 30% normal temperature magnetic agitation 0.5h Afterwards, centrifugation obtains deposit under the conditions of rotating speed 2000r/min, and deposit is washed with ethanol again, afterwards 90 DEG C of drying, grinding, Obtain FeCl3- chitosan polymer.
The above-mentioned FeCl prepared3- chitosan polymer may apply to removal methylene blue in waste dye substance In, comprise the following steps：Adjust methylene blue waste water pH be 10 in the range of, by the above-mentioned FeCl prepared3- chitosan gathers Compound is 1 according to solid-liquid ratio (g/L):10 dispensings react 50min into methylene blue waste water.
Illustrate the technique effect of the present invention with reference to specific experimental result：
1FeCl3- CTS handles the performance of methylene blue waste water
1.1FeCl3- CTS is to the percent of decolourization of methylene blue waste water and the measure of adsorption capacity：Accurately weigh a certain amount of FeCl3- CTS, added in 20mL methylene blue waste water, under normal temperature condition after constant speed magnetic agitation 2h, in rotating speed 3000r/min Under conditions of centrifuge 10min, collect supernatant, determine methylene blue concentration therein.In experimentation, be kept stirring for speed and The conditions such as stirring intensity are constant.Shown in the calculating of percent of decolourization and adsorption capacity such as formula (1), (2)：
In formula：C0For methylene blue waste water initial concentration (mg/L)；C1For the concentration (mg/L) after adsorption equilibrium；M is FeCl3- CTS dosage (g)；V is waste water reaction volume (mL)；η is the percent of decolourization (%) of methylene blue；qeFor adsorption capacity (mg/g)。
1.2FeCl3Influence of-CTS the dosages to percent of decolourization and adsorption capacity
As shown in Figure 2, with FeCl3The increase of-CTS dosages, the percent of decolourization of methylene blue waste water is in first to rise to omit afterwards Downward trend, works as FeCl3When-CTS dosages increase to 0.2g/L by 0.05g/L, percent of decolourization rises to maximum by 52.2% 78.3%.Continue to increase FeCl3During-CTS to 0.4g/L, percent of decolourization slightly drops to 71.8%.Work as FeCl3- CTS dosages compared with When low there is provided adsorption site total amount it is less, the methylene blue molecule thus adsorbed is less, is presented as that percent of decolourization is relatively low, with Dosage increase, adsorption site total amount increases therewith, so as to improve percent of decolourization.However, with the continuation increase of dosage (more than 0.2g/L), percent of decolourization is declined slightly, and this is due to that excessive adsorbent surrounds methylene blue molecule so that reached Adsorption equilibrium is destroyed.In addition, and FeCl3Percent of decolourization 73.7% when-CTS dosages are 0.1g/L is compared, and is most preferably added Maximum percent of decolourization during amount 0.2g/L improve only 4.6%, but dosage is the former 2 times, and angle is used from economy and engineering Degree analysis, subsequent experimental should select FeCl3- CTS dosages are 0.1g/L.Fig. 2 can also be seen that without modified chitosan (N-CTS) process of processing methylene blue waste water also embodies similar rule, but N-CTS is to the decolorizing efficiency of methylene blue It is relatively low, only 35.9-54.2%.
From the figure 3, it may be seen that working as FeCl3When-CTS dosage changes in the range of 0.05-0.4g/L, methylene blue is put down The trend being gradually reduced is presented in weighing apparatus adsorption capacity, but reduction trend gradually slows down, when this is due to that dosage is smaller, FeCl3- Adsorption site on CTS almost can be occupied all by methylene blue molecule, however, with the increase of dosage, although FeCl3The methylene blue total amount of-CTS absorption gradually increases, but adsorption site total amount is also in increase so that adsorption site may Not exclusively occupied by methylene blue molecule, so as to reduce adsorption capacity, the process of N-CTS processing methylene blue waste water also embodies Go out similar rule.When dosage is 0.1g/L, FeCl3- CTS and N-CTS adsorption capacity be respectively 147.4mg/g and 97.8mg/g, FeCl3- CTS is far above magnetic modification of chitosan prepared by Pan Yuanyuan to the adsorption capacity of methylene blue.
Influence of 1.3 wastewater pHs to percent of decolourization and adsorption capacity
As shown in Figure 4, in FeCl3- CTS dosages is under conditions of 0.1g/L, methylene blue wastewater pH are in 4-10 scopes When interior, increase with pH, FeCl3- CTS is to the decolorizing efficiency of methylene blue waste water in downward trend after first rising.When pH is increased by 4 When being added to 6, percent of decolourization increases to 95.6%, pH of maximum by 10.1% and continues to increase, and percent of decolourization is gradually reduced, it follows that useless The enhancing of acidity of water and basicity is unfavorable for FeCl3Processing of-the CTS to methylene blue waste water.Chitosan is a kind of alkalescent thing Matter, pH is too low to cause chitosan to be dissolved in waste water, the quantity that dye molecule is shifted from liquid phase to solid phase is drastically reduced, Methylene blue decolorization rate of wastewater is substantially reduced.Strong basicity environment is then unfavorable for absorption of the chitosan to basic-dyeable fibre.Fig. 4 can be with Find out, the process of N-CTS processing methylene blue waste water also embodies similar rule, but its removal efficiency to methylene blue It is relatively low, only 4.1-54.5%.
As shown in Figure 5, when methylene blue wastewater pH changes in the range of 4-10, FeCl3- CTS is put down to methylene blue The trend of first increases and then decreases is presented in the adsorption capacity that weighs, and the process of N-CTS processing methylene blue waste water also embodies similar rule Rule.In pH=6, FeCl3- CTS and N-CTS adsorption capacity is respectively 191.2mg/g and 109.0mg/g.
Influence of 1.4 reaction time to percent of decolourization and adsorption capacity
It will be appreciated from fig. 6 that in FeCl3- CTS dosages are that 0.1g/L, wastewater pH are under conditions of 6, with prolonging for reaction time It is long, FeCl3- CTS to the first quick increase of the decolorizing efficiency of methylene blue waste water, after be slowly increased, finally tend to balance.During reaction Between when extending to 15min, percent of decolourization increases to rapidly 83.8%, and this is due in reaction starting stage, FeCl3There is absorption in-CTS Site is more, and absorption methylene blue molecule is very fast.When continuing to extend to 50min with the reaction time, FeCl3- CTS adsorption sites by It is decrescence few, it is presented as that percent of decolourization increases and slows down.After 50min, absorption reaches balance, and percent of decolourization keeps maximum 99.4%.Fig. 6 may be used also To find out, N-CTS processing methylene blue waste water during, adsorption time on decolorizing effect influence it is unobvious, this be probably by Less in N-CTS adsorption sites itself, avtive spot is occupied within the very fast time by methylene blue molecule, after 40min, is occurred Certain de- steady phenomenon, is presented as that percent of decolourization slightly has reduction, generally speaking, decolorizing effects of the N-CTS to methylene blue waste water Relatively low (maximum percent of decolourization is 66.8%).
As shown in Figure 7, when reacted between in 5-60min scopes, FeCl3Equilibrium adsorption capacities of-the CTS to methylene blue First quick increase, after be slowly increased, finally tend to balance, this is due to the adsorbent (FeCl for participating in reaction3- CTS) amount it is permanent It is set to 0.1g/L, therefore the trend that adsorption capacity is showed is consistent with percent of decolourization, FeCl3Absorption of-the CTS to methylene blue is held Amount is 198.8mg/g to the maximum, the 133.6mg/g higher than N-CTS.
Influence of the 1.5 methylene blue waste water initial concentrations to percent of decolourization and adsorption capacity
As shown in Figure 8, methylene blue in waste concentration is in 40mg/L, and percent of decolourization reaches maximum 96.3%.Certain dense In the range of degree, FeCl3- CTS to the adsorption capacity of methylene blue with initial waste concentration into positive correlation, in 120-160mg/ During L, FeCl3- CTS progressivelyes reach balance (820.0mg/g) to the adsorption capacity of methylene blue waste water, and this is due to overcome liquid Mutually the resistance to mass tranfer between solid phase, initial methylene blue concentration is got over there is provided important motive force, initial methylene blue concentration Greatly, it is bigger to adsorbing the motive force of methylene blue, therefore within the specific limits, the rise of initial concentration is conducive to improving FeCl3- Adsorption capacities of the CTS to methylene blue in waste molecule.N-CTS in Fig. 9 is shown and FeCl3Rule similar-CTS, and N-CTS is 408.0mg/g to the maximum adsorption capacity of methylene blue waste water.
2 adsorption dynamics adsorption kinetics, adsorption isotherm, Adsorption thermodynamics
2.1 adsorption dynamics adsorption kinetics
From Figure 10 and Figure 11, FeCl3- CTS and N-CTS more meets the adsorption process of methylene blue accurate two grades instead Answer dynamics, R2Respectively 0.99919>0.90、0.99925>0.90.It is dense for 20mg/L methylene blue under room temperature condition Waste water is spent, the theoretical maximum adsorbance that pseudo-first-order kinetics equation is predicted is respectively 81.3mg/g and 6.7mg/g, with testing Measured value 198.8mg/g in journey is compared with 133.6mg/g, relative error respectively 59.1%>10%th, 94.5%> 10%；The theoretical maximum adsorbance that pseudo-second order kinetic equation is predicted is respectively 210.5mg/g and 130.7mg/g, with experiment During measured value between relative error be respectively 5.9%<10%th, 2.2%<10%, further illustrate FeCl3- CTS and N-CTS more meets methylene blue waste water adsorption process the dynamic process (table 1) described by pseudo-second order kinetic equation.This Outside, predicting the outcome from pseudo-second order kinetic equation, FeCl3- CTS maximum adsorption capacity is about 1.6 times of N-CTS.
The pseudo-first-order of table 1 and pseudo-second order kinetic simulation relevant parameter
2.2 adsorption isotherm
As shown in Table 2, under normal temperature condition, being predicted the outcome according to Langmuir equation at constant temperature to obtain, and different methylene blues are dense Under the conditions of degree, FeCl3- CTS and N-CTS be respectively to the theoretical maximum adsorption capacity of methylene blue for 847.5mg/g and FeCl in 418.4mg/g, experimentation3- CTS and N-CTS maximum equilibrium adsorption capacities 820.0mg/g and 408.0mg/L, two Relative error between person is respectively 4.2%<10%th, 2.5<10%.It is pre- according to Freundlich equation at constant temperature under normal temperature condition Survey result to understand, FeCl3- CTS and N-CTS be respectively to the theoretical maximum adsorption capacity of methylene blue 1423.9mg/g and The relative error between maximum adsorption capacity in 650.3mg/g, with experimentation is respectively 73.6%>10%th, 59.4%> 10%；In addition, the R of Langmuir isotherm plots2Respectively 0.99949>0.90、0.99854>0.90, and Freundlich The R of isothermal curve2Respectively 0.83413<0.90、0.84166<0.90 (Figure 12 and Figure 13).It follows that Langmuir isothermals Line equation can preferably describe FeCl3- CTS and N-CTS handles the isothermal line process of methylene blue waste water.
Table 2FeCl3- CTS is to methylene blue adsorption number thermoisopleth constant
2.3 Adsorption thermodynamics
Under normal temperature condition, FeCl3- CTS and N-CTS adsorbs the thermodynamic parameter such as institute of table 3 of methylene blue in waste process Show, the process for showing to adsorb methylene blue is thermodynamics spontaneous process (Δ Gθ<0), adsorption reaction is exothermic reaction (Δ Hθ<0), FeCl3The reaction of-CTS and N-CTS absorption methylene blues adds the unordered degree of material (Δ S on solid-liquid interfaceθ<0)。
The thermodynamic parameter of table 3
Some preferred embodiments of invention have shown and described in described above, but as previously described, it should be understood that invention is not Form disclosed herein is confined to, the exclusion to other embodiment is not to be taken as, and available for various other combinations, modification And environment, and can be carried out in invention contemplated scope described herein by the technology or knowledge of above-mentioned teaching or association area Change., then all should be in the appended power of invention and the change and change that those skilled in the art are carried out do not depart from the spirit and scope of invention In the protection domain that profit is required.

Claims (10)

1. a kind of FeCl3The preparation method of-chitosan polymer, it is characterised in that comprise the following steps：
A certain amount of chitosan of step 1, precise, with FeCl3Solution is mixed, normal temperature magnetic agitation, then is added twice FeCl3The absolute ethyl alcohol of liquor capacity, and be slowly stirred, centrifugal treating is carried out after flocculent deposit to be generated, separation is deposited Thing；
Step 2, washed away with ethanol after the iron ion of deposit surface, deposit is mixed with glutaraldehyde solution, and carries out normal temperature magnetic Power is stirred, and centrifugal treating is carried out afterwards and obtains deposit, deposit washs with ethanol again, is dried afterwards, milled processed, Obtain FeCl3- chitosan polymer.
2. FeCl according to claim 13The preparation method of-chitosan polymer, it is characterised in that the shell in step 1 gathers Sugar and FeCl3The solid-liquid ratio (m/V, mg/mL) of solution is 2:1-10:1；FeCl3The concentration of solution is 0.05-0.25mol/L.
3. FeCl according to claim 13The preparation method of-chitosan polymer, it is characterised in that the magnetic force in step 1 Mixing time is 0.5-4h.
4. FeCl according to claim 13The preparation method of-chitosan polymer, it is characterised in that the centrifugation in step 1 Rotating speed is 2000-4000r/min；Centrifugation time is 5-15min.
5. FeCl according to claim 13The preparation method of-chitosan polymer, it is characterised in that penta 2 in step 2 The concentration of aldehyde solution is 20%-30%；The addition of glutaraldehyde solution is FeCl3The 15%-25% of liquor capacity.
6. FeCl according to claim 13The preparation method of-chitosan polymer, it is characterised in that the magnetic force in step 2 Mixing time is that the centrifugal rotational speed in 0.5-2h, step 2 is 2000-4000r/min.
7. FeCl according to claim 13The preparation method of-chitosan polymer, it is characterised in that the drying in step 2 Temperature is 70-90 DEG C.
8. the FeCl that the preparation method in a kind of 1-7 as claim described in any claim is prepared3- chitosan polymerize Thing.
9. the FeCl described in claim 83Application of-the chitosan polymer in methylene blue in waste dye substance is removed.
10. application according to claim 9, it is characterised in that the application comprises the following steps：Adjust methylene blue waste water PH be 6-10 in the range of, by the above-mentioned FeCl prepared3- chitosan polymer is 1 according to solid-liquid ratio (g/L):10-2:5 Deliver in methylene blue waste water and react 15-50min.
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