CN103272570A - Preparation method and application of hemicellulose/chitosan/nano TiO2 hybrid material - Google Patents
Preparation method and application of hemicellulose/chitosan/nano TiO2 hybrid material Download PDFInfo
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- CN103272570A CN103272570A CN2013102377347A CN201310237734A CN103272570A CN 103272570 A CN103272570 A CN 103272570A CN 2013102377347 A CN2013102377347 A CN 2013102377347A CN 201310237734 A CN201310237734 A CN 201310237734A CN 103272570 A CN103272570 A CN 103272570A
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Abstract
The invention discloses a preparation method of a hemicellulose/chitosan nano TiO2 hybrid material and application of the material in heavy metal adsorption. The method comprises the steps as follows: nano TiO2 modified by sodium dodecyl sulfate and chitosan are dispersed in a dilute acetic acid solution, and chitosan/nano TiO2 emulsion is obtained after sufficient dissolution; then moderate hemicellulose is added in the emulsion to obtain hemicellulose/chitosan nano TiO2 emulsion, and a reflux reaction is performed at the temperature of 100 DEG C for 30-60 min to obtain beige gel; the gel is further subjected to a thermo-crosslinking reaction for 6-9 hours under the condition of ordinary pressure and the temperature of 40 DEG C; and after freeze drying, the hemicellulose/chitosan nano TiO2 hybrid material is obtained. The material prepared by the method has a good absorbing effect on the heavy metals such as Cu, Cr, Hg, Ni and Cd, an absorbing action on trace amount of ClO4 in water, and wide application prospect in the field of sewage treatment, in particular to groundwater water quality purification.
Description
Technical field
The present invention relates to a kind of hemicellulose/shitosan/nano-TiO
2The preparation method of hybrid material and be used for heavy metal absorption belongs to material science and environmental science.
Background technology
Activity of human beings enters in the water a large amount of industry, agricultural and domestic refuse, causes that content of beary metal increases day by day in the water, serious threat human health and natural ecosystems.Heavy metal pollution mainly comes from industries such as clothes, petrochemical industry, toxic emission, sewage irrigation and metallurgy.The major technique of removal of heavy metal ions comprises chemical precipitation, redox, ion-exchange, counter-infiltration and biosorption process etc. in the water body at present.Adsorption technology has advantages such as chemical stability is good, non-secondary pollution, is the method for the most effectively removing heavy metal ion in the polluted-water, therefore, seeks the key problem that efficient cheap adsorbent just becomes adsorption technology.
Shitosan is unique alkaline polysaccharide that occurring in nature exists, and the source is abundant, has biocompatibility, and biodegradability, avirulence etc. has advantage, is widely used in fields such as medicine, food, chemical industry.Contain a large amount of free amine groups and hydroxyl in the chitosan molecule, can form stable chelate with heavy metal ion.Because shitosan is under the condition of sour environment, in the molecule-NH
2By protonated formation-NH
3 +And the water-soluble loss that causes adsorbent is unfavorable for regeneration, and-NH
3 +Produce repulsion with heavy metal cation, thereby limited its range of application.Existing technology is generally carried out crosslinked to shitosan so that shitosan reaches the insoluble purpose of acid by chemical cross-linking agents such as glutaraldehyde, formaldehyde, epoxychloropropane, but these chemical cross-linking agents itself can produce harm to natural environment, and can occupy the adsorption site of shitosan, reduce its absorption property, the substitute of therefore seeking these chemical cross-linking agents is even more important.
Hemicellulose content in plant kingdom is only second to cellulose, is a kind of inexhaustible, nexhaustible renewable plant resources, and its content accounts for 1/4～1/3 of plant material greatly, is present in widely in needlebush, leaf wood, careless class and the stalk.There are functional groups such as a large amount of carbonyls, aldehyde radical and hemiacetal in half fiber molecule, they can with the chitosan molecule chain on free amine group generation schiff base reaction, form cross-linked network structure, thereby overcome shitosan easily dissolving in acid, and increased chitosan molecule chain hydroxy radical content, improved the absorption property of shitosan to heavy metal.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of environmental protection, hemicellulose/shitosan/nano-TiO that adsorption efficiency is high
2The preparation method of hybrid material and the application on the absorption heavy metal.
The present invention utilizes on the chitosan molecule chain on amino and the hemicellulose strand functional groups such as carbonyl, aldehyde radical and hemiacetal to generate schiff base reaction and generates cross-linked network structure figure (1), and adds SDS modified Nano TiO
2Improve cross-linked network space structure figure (2), prepared the hemicellulose/shitosan/nano-TiO that can have the good adsorption effect to Cu, Cr, Hg, Ni and Cd
2Hybrid material, and to underwater trace ClO
4 -Has certain suction-operated.
Hemicellulose/shitosan of the present invention/nano-TiO
2The preparation method of hybrid material comprises the steps:
(1) with nano-TiO
2Add in 0.7wt% lauryl sodium sulfate (SDS) solution, regulating pH is 4.0, and magnetic agitation 6h filters, washing, and drying obtains modified Nano TiO
2Powder;
(2) with modified Nano TiO
2Be dispersed in the dilute acetic acid solution of 1～3wt%, add shitosan, used shitosan and nano-TiO
2Mass ratio is 1:0.01～1:0.05, stirs, and every ultrasonic dispersion half an hour 15min, obtains shitosan/nano-TiO behind the stirring 12h
2Emulsion;
(3) at above-mentioned shitosan/nano-TiO
2Add hemicellulose in the emulsion, used shitosan and hemicellulose mass ratio are 1:1～1:4, stir, and every ultrasonic dispersion half an hour 15min, obtain hemicellulose/shitosan/nano-TiO behind the stirring 4h
2Emulsion;
(4) with the hemicellulose/shitosan/nano-TiO that makes
2Emulsion obtains light brown gel at 100 ℃ of 30～60min that reflux, and with gel further heat cross-linking reaction 6～9h under 40 ℃ of conditions of normal pressure, obtains hemicellulose/shitosan/nano-TiO after the freeze drying
2Hybrid material.
Used nano-TiO
2Particle diameter is 5～30nm.
Raw materials used deacetylating degree of chitosan is more than 80%.
Used nano-TiO
2With SDS solution quality volume ratio be 0.25～0.75%.
With hemicellulose/shitosan/nano-TiO
2The sorbing material grind into powder is crossed 100 order aperture 0.15mm standard screens, obtains hemicellulose/shitosan/nano-TiO
2Powder places drier to be used for heavy metal Cu, Cr, Hg, Ni and Cd, and underwater trace ClO
4 -Mensuration.
Hemicellulose/shitosan/the nano-TiO that adopts this method to prepare
2Hybrid material has good selective absorption to Cu, Cr, Hg, Ni and Cd, and to underwater trace ClO
4 -Has certain suction-operated.
The inventive method utilizes nature content abundant renewable natural polymer chitosan and hemicellulose to be raw material, the utilization rate of hemicellulose has reached 80%, has environmental protection, biodegradable, alleviating raw material that synthetic high polymer faces peters out and causes the serious day by day advantages such as predicament of environmental pollution, the hemicellulose/shitosan of preparation/nano-TiO
2Hybrid material has significant adsorption effect to heavy metal Cu, Cr, Hg, Ni and Cd, and to underwater trace ClO
4 -Has certain suction-operated.This method has plurality of advantages such as environmental protection and the easy easy industrialization of technology, especially has broad application prospects in the underground water purification of water quality field in sewage disposal, and is significant to the high-valued and industrial applications of hemicellulose and shitosan.
Description of drawings
Fig. 1 hemicellulose/shitosan/nano-TiO
2The hybrid material chemical skeleton;
Fig. 2 hemicellulose/shitosan/nano-TiO
2The signal of hybrid material network structure;
Hemicellulose/shitosan/the nano-TiO of Fig. 3 embodiment 4 preparations
2The hybrid material stereoscan photograph.
The specific embodiment
Embodiment 1.
With 0.01g modified Nano TiO
2Be dispersed in the dilute acetic acid solution of 50mL2% (v/v), magnetic agitation 1h adds the 1.5g shitosan, magnetic agitation 7h, every half an hour with ultrasonic dispersions of solution 15min, stir to dissolve fully behind the 12h and obtain shitosan/nano-TiO
2Emulsion; Again at shitosan/nano-TiO
2Add the 6g hemicellulose xylan in the emulsion, magnetic agitation 1～2h, dissolving obtains hemicellulose/shitosan/nano-TiO fully
2Emulsion; With the hemicellulose/shitosan/nano-TiO that makes
2Emulsion obtains light brown gel at 100 ℃ of oil baths backflow 30～60min, with gel further heat cross-linking reaction 6～9h under 40 ℃ of conditions of normal pressure, obtains hemicellulose/shitosan/nano-TiO behind the freeze drying 24h
2Hybrid material.
Embodiment 2.
With 0.02g modified Nano TiO
2Be dispersed in the dilute acetic acid solution of 50mL2% (v/v), magnetic agitation 1h adds the 1.5g shitosan, magnetic agitation 7h, every half an hour with ultrasonic dispersions of solution 15min, stir to dissolve fully behind the 12h and obtain shitosan/nano-TiO
2Emulsion; Again at shitosan/nano-TiO
2Add the 6g hemicellulose xylan in the emulsion, magnetic agitation 1～2h, dissolving obtains hemicellulose/shitosan/nano-TiO fully
2Emulsion; With the hemicellulose/shitosan/nano-TiO that makes
2Emulsion obtains light brown gel at 100 ℃ of oil baths backflow 30～60min, with gel further heat cross-linking reaction 6～9h under 40 ℃ of conditions of normal pressure, obtains hemicellulose/shitosan/nano-TiO behind the freeze drying 24h
2Hybrid material.
Embodiment 3.
With 0.03g modified Nano TiO
2Be dispersed in the dilute acetic acid solution of 50mL2% (v/v), magnetic agitation 1h adds the 1.5g shitosan, magnetic agitation 7h, every half an hour with ultrasonic dispersions of solution 15min, stir to dissolve fully behind the 12h and obtain shitosan/nano-TiO
2Emulsion; Again at shitosan/nano-TiO
2Add the 6g hemicellulose xylan in the emulsion, magnetic agitation 1～2h, dissolving obtains hemicellulose/shitosan/nano-TiO fully
2Emulsion; With the hemicellulose/shitosan/nano-TiO that makes
2Emulsion obtains light brown gel at 100 ℃ of oil baths backflow 30～60min, with gel further heat cross-linking reaction 6～9h under 40 ℃ of conditions of normal pressure, obtains hemicellulose/shitosan/nano-TiO behind the freeze drying 24h
2Hybrid material.
Embodiment 4.
With 0.04g modified Nano TiO
2Be dispersed in the dilute acetic acid solution of 50mL2% (v/v), magnetic agitation 1h adds the 1.5g shitosan, magnetic agitation 7h, every half an hour with ultrasonic dispersions of solution 15min, stir to dissolve fully behind the 12h and obtain shitosan/nano-TiO
2Emulsion; Again at shitosan/nano-TiO
2Add the 6g hemicellulose xylan in the emulsion, magnetic agitation 1～2h, dissolving obtains hemicellulose/shitosan/nano-TiO fully
2Emulsion; With the hemicellulose/shitosan/nano-TiO that makes
2Emulsion obtains light brown gel at 100 ℃ of oil baths backflow 30～60min, with gel further heat cross-linking reaction 6～9h under 40 ℃ of conditions of normal pressure, obtains hemicellulose/shitosan/nano-TiO behind the freeze drying 24h
2Sorbing material.Fig. 3 hemicellulose/shitosan/nano-TiO
2The hybrid material stereoscan photograph, this hybrid material has the loose and porous structure of similar " cellular " as can be seen.With hemicellulose/shitosan/nano-TiO
2The sorbing material grind into powder is crossed 100 order aperture 0.15mm standard screens, obtains hemicellulose/shitosan/nano-TiO
2Powder places drier to be used for heavy metal Cu, Cr, Hg, Ni and Cd, and underwater trace ClO
4 -Mensuration.
Hemicellulose/shitosan/nano-TiO
2Hybrid material is to Cu
2+, Cr
6+, Hg
2+, Ni
2+And Cd
2+Staticadsorption experiment in the 50mL conical flask, carry out, add 20mL heavy metal ion solution in the bottle, adding dry weight then is 0.10g hemicellulose/shitosan/nano-TiO
2Adsorbent, concentration of heavy metal ion is measured with flame atomic absorption spectrophotometer (TAS-990F) in the aqueous solution, and pH value of solution is measured with 320S pH, regulates pH with 1M HCl or NaOH solution.
Underwater trace ClO
4 -Select determination of electrode with the COLE-PARMER perchlorate, draw the perchlorate storing solution of a certain amount of 100mg/L in the 100mL volumetric flask, add 10mL ionic strength adjustment-buffer (ISA) (1M sodium acetate) separately respectively, be diluted to scale with deionized water, be mixed with 0.5mg/L respectively, 1mg/L, 3mg/L, 5mg/L, 10mg/L, the standard liquid of 15mg/L, reading potential under the magnetic agitation condition.Be abscissa with the current potential, the concentration logarithm is ordinate, the drawing standard curve.Pipette water sample to be measured with the 5mL pipette, place the 50mL volumetric flask, add 5mL ionic strength adjustment-buffer (ISA), with selecting its potential value of determination of electrode, calculate ClO in the water sample
4 -Concentration.
Experimental result is as follows:
Hemicellulose/shitosan under table 1. condition of different pH/nano-TiO
2Hybrid material is to the saturated extent of adsorption of ion
Table 2. hemicellulose/shitosan/nano-TiO
2Hybrid material is to ion maximal absorptive capacity and clearance
As can be seen from the above table, hemicellulose/shitosan/nano-TiO
2Hybrid material has heavy metal adsorption effect widely, in wide pH scope to Hg
2+, Cr
6+Still have the good adsorption performance, it is removed efficient and has all arrived 100%, be higher than silica gel and chitosan, diatomite and the hemicellulose base adsorbent of some bibliographical informations to Hg
2+, Cr
6+Removal efficient; And overcome the deficiency that existing chitosan-based adsorbent can only be applied to heavy metal absorption at neutrality or alkali condition, have concurrently simultaneously underwater trace ClO
4 -Absorption property.
Claims (6)
1. hemicellulose/shitosan/nano-TiO
2The preparation method of hybrid material is characterized in that, comprises the steps:
(1) with nano-TiO
2Add in the 0.7wt% sodium dodecyl sulfate solution, regulating pH is 4.0, and magnetic agitation 6h filters, washing, and drying obtains modified Nano TiO
2Powder;
(2) with modified Nano TiO
2Be dispersed in the dilute acetic acid solution of 1 ~ 3wt%, add shitosan, used shitosan and nano-TiO
2Mass ratio is 1:0.01 ~ 1:0.05, stirs, and every ultrasonic dispersion half an hour 15min, obtains shitosan/nano-TiO behind the stirring 12h
2Emulsion;
(3) at above-mentioned shitosan/nano-TiO
2Add hemicellulose in the emulsion, used shitosan and hemicellulose mass ratio are 1:1 ~ 1:4, stir, and every ultrasonic dispersion half an hour 15min, obtain hemicellulose/shitosan/nano-TiO behind the stirring 4h
2Emulsion;
(4) with the hemicellulose/shitosan/nano-TiO that makes
2Emulsion obtains light brown gel at 100 ℃ of 30 ~ 60min that reflux, and with gel further heat cross-linking reaction 6 ~ 9h under 40 ℃ of conditions of normal pressure, obtains hemicellulose/shitosan/nano-TiO after the freeze drying
2Hybrid material.
2. preparation method according to claim 1 is characterized in that, used nano-TiO
2Particle diameter is 5 ~ 30nm.
3. preparation method according to claim 1 is characterized in that, raw materials used deacetylating degree of chitosan is more than 80%.
4. preparation method according to claim 1 is characterized in that, used nano-TiO
2With SDS solution quality volume ratio be 0.25 ~ 0.75%.
5. each prepared hemicellulose/shitosan/nano-TiO of claim 1 ~ 4
2Hybrid material.
6. the described hemicellulose/shitosan of claim 5/nano-TiO
2The application of hybrid material on the absorption heavy metal.
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| CN104086787A (en) * | 2014-07-04 | 2014-10-08 | 武汉大学 | Corncob straight chain hemicellulose/chitosan or carboxymethyl chitosan/TO2 hybrid material as well as preparation method and application thereof |
| CN104610566A (en) * | 2015-01-15 | 2015-05-13 | 陕西科技大学 | Preparation method of nano-TiO2-modified composite hydrogel |
| CN108236927A (en) * | 2016-12-27 | 2018-07-03 | 海门市源美美术图案设计有限公司 | A kind of modified pomelo peel and its preparation method and application |
| CN112095228A (en) * | 2020-09-08 | 2020-12-18 | 蒋小芳 | Preparation method of cultivation film and cultivation bag for agricultural production |
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Denomination of invention: Preparation and application of a hemicellulose/chitosan/nano-TiO2hybrid material Effective date of registration: 20230509 Granted publication date: 20141001 Pledgee: Agricultural Bank of China Limited Qianjiang Branch Pledgor: HUA SHAN TECHNOLOGY CO.,LTD. Registration number: Y2023420000198 |
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