CN104148025B - The preparation of polysaccharide-modified nano silicon and the application in treatment of dyeing wastewater - Google Patents
The preparation of polysaccharide-modified nano silicon and the application in treatment of dyeing wastewater Download PDFInfo
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- CN104148025B CN104148025B CN201310561530.9A CN201310561530A CN104148025B CN 104148025 B CN104148025 B CN 104148025B CN 201310561530 A CN201310561530 A CN 201310561530A CN 104148025 B CN104148025 B CN 104148025B
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Abstract
The invention discloses a kind of preparation aoxidizing the polysaccharide-modified nano silicon of dialdehyde and the application in dye wastewater treatment, belong to nano silicon material technical applications.Utilizing periodic acid hydrochlorate to be selectively oxidized chitosan, a certain amount of nano silicon adds in toluene solution after ultrasonic disperse, adds oxidation dialdehyde chitosan, is gradually added into silicone couplet amine propyl group ethyoxyl siloxanes under stirring.After 60 90 DEG C of reaction a period of times, acetone precipitation, filter, washing with alcohol, lyophilization, obtain aoxidizing the silicon dioxide nanocomposite of dialdehyde chitosan silicon coupling, and for the process of dyeing waste water.Raw material of the present invention is cheap and easy to get, and preparation method is simple, and has superior adsorbed dye performance.It is 2g/L 12g/L when using modified manometer silicon dioxide concentration.Percent of decolourization can reach the effect of more than 98%, considerably reduces the colourity of dyeing waste-water.There is in terms of the removal of dyeing waste water the biggest using value.
Description
Technical field
The present invention relates to the process of waste water from dyestuff in a kind of nano-silicon dioxide modified method and application dyeing and printing process.
Background technology
Along with industrial development, wastewater discharge increases day by day, and wherein environment is caused substantial pollution and is difficult to by dyeing waste water
Process.Its feature is complicated component, stability is strong, be difficult to degrade, discharge capacity is huge.The light degradation of latest development, chemical oxidation
The methods such as reduction, biologic treating technique because cost is high, easily produce harmful little molecule residue, to process wastewater flow rate little etc. lack
Put and be difficult to apply.Comparatively speaking, adsorption treatment technology can process big flow, complicated component well, be difficult to the useless of degraded
Water, is important sewage water treatment method for a long time.Natural macromolecule adsorbent is in widespread attention recently.Natural polymer and
Its modified adsorbent has that raw material sources are wide, low cost, toxicity are little, and the advantages such as synthesis technique is simple, product is degradable, so grinding
Study carefully exploitation modified natural polymer trapping agent and become the focus of research the most both at home and abroad.In numerous natural macromolecular materials, shell
Polysaccharide wide material sources, modification with low cost, nontoxic, degradable, easy and there is excellent absorption property and receive much concern.But
It is that chitosan is water insoluble not as good as organic solvent, some Low acid aqueous solutions can be dissolved in, significantly limit its range of application.Nothing
Machine nano silicon medium has good chemical characteristic and surface easy rhetorical function group.Owing to its surface area is big, very
Easily reunite, in order to make it disperse the most very well, generally its particle surface is carried out graft modification.Conventional modifying agent has
Silane coupler such as γ-(2,3-glycidoxy) propyl trimethoxy silicane, titanate coupling agent, hyper-dispersant, organic
Macromolecule etc..At present, organic polymer and the composite modified composite of inorganic matter are important field of research.Use Organic substance
Compound modified manometer silicon dioxide material has the advantages such as applicable pH wide ranges, good stability, high adsorption capacity, is suitable for
The adsorption treatment of sewage.And existing research work mostly concentrates on esters of acrylic acid synthesis to the polymer that nanometer two SiClx is modified
High molecular polymer, and use natural sugar analog derivative to work in coordination with silicone couplet to nano-silicon dioxide modified and for dyeing waste water
Process is less.
Summary of the invention
In view of this, the invention provides the preparation of the chitin modified nano silicon of the dialdehyde of a kind of ecological, environmental protective
Method and the specifically application in dyeing waste water, thus solve the most tractable difficult problem of dye wastewater.
The preparation method of polysaccharide-modified nano silicon and the application in treatment of dyeing wastewater, it is characterised in that bag
Include following steps:
1), the periodic acid hydrochlorate that mol ratio is 1:0.5-2 is selectively oxidized with chitosan, underlying 30 DEG C of conditions
In constant temperature oscillation dye model machine, lucifuge is reacted 1-3 hour, and the ethylene glycol adding 30-60 milliliter 0.1mol/L continues reaction 0.5-
2h, takes out suspension, with circulating water type vacuum pump sucking filtration, takes out filtrate, adds 150ml acetone in filtrate, and lucifuge precipitates 2h,
Oxidation dialdehyde chitosan is obtained after sucking filtration；
2), by nano silicon add ultrasonic disperse in toluene solution, be slowly stirred, add nano silicon quality
10-30% oxidation dialdehyde chitosan after, under nitrogen protection, 60-90 DEG C (rotating speed 2000rpm-10000 rpm) stir
0.5-2 hour, adding silicone couplet, 70-90 DEG C is stirred 3-5 hour, obtains acetone precipitation and filter, and washing with alcohol is freezing
Be dried, obtain bis oxide chitosan silicon coupling-silicon dioxide nanocomposite.
As the further optimization of this programme, the periodic acid hydrochlorate in described step 1) is in sodium metaperiodate, Potassium metaperiodate.
One or both compositionss.
As the further optimization of this programme, described step 2) in silicone couplet be amine propyl group ethyoxyl siloxanes, use
Amount is the 20-50% of nano silicon.
As the further optimization of this programme, described nanometer titanium dioxide silicon concentration is 2g/L-12g/L.
As the further optimization of this programme, described nano silicon nanometer size range is at 10nm-80nm.
Obtain bis oxide chitosan silicon coupling-silicon dioxide nanocomposite, this nano-complex is faint yellow.
Modified manometer silicon dioxide adsorbent prepared by described method is straight for adsorbing the dye type in dyeing waste water
Connect dyestuff and reactive dye.
The method have the benefit that
The chitosan low in raw material price that invention is used is easy to get, and synthesis technique is ripe, side of the present invention
Modified manometer silicon dioxide adsorbent prepared by method is for adsorbing the dyestuff in dyeing waste water, when using modified manometer silicon dioxide
Concentration is 2g/L-12g/L, and under ultrasound condition, percent of decolourization can reach the effect of more than 98%.Modified manometer silicon dioxide of the present invention
Adsorbent is energy-conservation, ecological environment-friendly type adsorbent, and environment is not resulted in secondary pollution.
Accompanying drawing explanation
Below in conjunction with the accompanying drawings the present invention is described in further detail:
Fig. 1 is that adsorption temp of the present invention affects structural representation to modified manometer silicon dioxide adsorption rate；
Fig. 2 is that adsorption time of the present invention affects structural representation to modified manometer silicon dioxide absorption property.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail:
Embodiment one:
The preparation method of polysaccharide-modified nano silicon and the application in treatment of dyeing wastewater, comprise the following steps:
1), the periodic acid hydrochlorate that mol ratio is 1:0.5-2 is selectively oxidized with chitosan, wherein, in sodium iodate, Potassium metaperiodate.
One or both compositionss, be placed under the conditions of 30 DEG C constant temperature oscillation dye model machine in lucifuge react 1-3 hour, add 30-
The ethylene glycol of 60 milliliters of 0.1mol/L continues reaction 0.5-2h, takes out suspension, with circulating water type vacuum pump sucking filtration, takes out filter
Liquid, adds 150ml acetone, lucifuge precipitation 2h in filtrate, obtains oxidation dialdehyde chitosan after sucking filtration；
2), by particle size range at 10nm-80nm, concentration is that the nano silicon of 2g/L-12g/L adds in toluene solution
Ultrasonic disperse, is slowly stirred, and after the oxidation dialdehyde chitosan of the 10-30% adding nano silicon quality, protects at nitrogen
Under, 60-90 DEG C (rotating speed 2000rpm-10000 rpm) stirs 0.5-2 hour, adds silicone couplet, and wherein, silicone couplet is
Amine propyl group ethyoxyl siloxanes, consumption is the 20-50% of nano silicon, and 70-90 DEG C is stirred 3-5 hour, obtain acetone precipitation
And filter, washing with alcohol, lyophilization, obtain bis oxide chitosan silicon coupling-silicon dioxide nanocomposite.
Obtain bis oxide chitosan silicon coupling-silicon dioxide nanocomposite, this nano-complex is faint yellow.Modified
Nano silicon adsorbent is direct dyes and reactive dye for adsorbing the dye type in dyeing waste water.
Embodiment two:
A kind of preparation aoxidizing the modified nano silicon water treatment agent of dialdehyde chitin
By 5g particle size range at 30nm Nano-meter SiO_22Ultrasonic disperse, in 150ml toluene solvant, adds in dispersion
The oxidation dialdehyde chitosan of certain mass mark 30%, N2Under protection, 90 DEG C of high-speed stirred 1 hour, add the amine propyl group of 20%
Ethyoxyl siloxanes, 90 DEG C are stirred 4 hours, obtain yellow solution, acetone precipitation reactant, sucking filtration, and nanoparticle is with anhydrous
Ethanol repeatedly washs, lyophilization 12h, obtains faint yellow modified manometer silicon dioxide particle.
Embodiment three:
The preparation of oxidation dialdehyde chitin
By in chitosan 0.3mol/L sodium periodate solution, keep IO4-: CS mol ratio is 1:0.62, under the conditions of 30 DEG C
Being placed in lucifuge reaction 2h in constant temperature oscillation dye model machine, the ethylene glycol adding 40 milliliters of 0.1mol/L continues reaction 0.5h, with following
Ring ability of swimming vacuum pump sucking filtration, takes out filtrate, adds 150ml acetone, lucifuge precipitation 2h, obtain after sucking filtration in filtrate.
Embodiment four:
Modified manometer silicon dioxide adsorbent is for adsorbing the dyestuff in dyeing waste water
Being 2g/L-12g/L when using modified manometer silicon dioxide concentration, waste water from dyestuff pH is 2.56, adsorbs 60 minutes,
Dye decolored rate be can reach the effect of more than 98%.
As it is shown in figure 1, adsorption temp is to modified Nano SiO2Absorption property affect structural representation.Active red M3B's
Absorbance is up to 98%.And the raising of temperature, modified Nano SiO2The adsorption rate of dyestuff is increased the most therewith, but the amplitude increased
Seldom, from the angle of environmental protection and energy saving, modified nano silicon suitably processes dyestuff with 30 DEG C.As in figure 2 it is shown, adsorption time
To modified Nano SiO2The impact of absorption property, increase over time, the adsorption rate of dyestuff is increased by modified manometer silicon dioxide
Greatly, and initial adsorption rate quickly.
The above, the only detailed description of the invention of the present invention, but protection scope of the present invention is not limited thereto, and any
Those of ordinary skill in the art in the technical scope that disclosed herein, the change that can expect without creative work or
Replace, all should contain within protection scope of the present invention.Therefore, protection scope of the present invention should be limited with claims
Fixed protection domain is as the criterion.
Claims (5)
- The preparation method of the most polysaccharide-modified nano silicon, it is characterised in that described nano silicon raw material particle size model It is trapped among 10nm-80nm；Utilize oxidation dialdehyde chitosan, with silicone couplet, nano silicon is carried out surface modification；Described polysaccharide Modified manometer silicon dioxide is prepared by the method comprised the following steps:1), the periodate that mol ratio is 1:0.5-2 is selectively oxidized with chitosan, under the conditions of 30 DEG C, is placed in constant temperature In oscillating specimen dyeing machine, lucifuge is reacted 1-3 hour, and the ethylene glycol adding 30-60 milliliter 0.1mol/L continues reaction 0.5-2h, takes Go out suspension, with circulating water type vacuum pump sucking filtration, take out filtrate, filtrate adds 150ml acetone, lucifuge precipitation 2h, sucking filtration Rear acquisition aoxidizes dialdehyde chitosan；2), by nano silicon add ultrasonic disperse in toluene solution, be slowly stirred, add nano silicon quality After the oxidation dialdehyde chitosan of 10-30%, under nitrogen protection, at 60-90 DEG C, rotating speed is 2000rpm-10000 rpm stirring 0.5-2 hour, adding silicone couplet, 70-90 DEG C is stirred 3-5 hour, after adding acetone precipitation reactant, filters, and ethanol is washed Wash, lyophilization, obtain aoxidizing dialdehyde chitosan and the nanometer silica composite of silicone couplet modification.
- The preparation method of polysaccharide-modified nano silicon the most as claimed in claim 1, it is characterised in that: in described step 1) , periodate used is one or both compositionss in sodium metaperiodate, Potassium metaperiodate., periodate used and chitosan Mol ratio be 1:0.5-2.
- The preparation method of polysaccharide-modified nano silicon the most as claimed in claim 1, it is characterised in that: described step 2) in Silicone couplet be amine propyl group ethyoxyl siloxanes, consumption is the 20-50% of nano silicon.
- The preparation method of polysaccharide-modified nano silicon the most as claimed in claim 1, it is characterised in that: described nano-silica SiClx concentration is 2g/L-12g/L.
- 5. prepared polysaccharide-modified nano silicon at dyeing waste water by the preparation method described in Claims 1-4 any one Application in process, it is characterised in that: modified manometer silicon dioxide adsorbent prepared by described method is for adsorbing dyeing waste water In dyestuff, dye type is direct dyes and reactive dye.
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| CN104785214B (en) * | 2015-03-27 | 2017-12-01 | 安徽大学 | Chitosan-coated magnetic mesoporous silica core-shell structured nanoparticle and preparation method and application thereof |
| JP2019512447A (en) * | 2016-03-31 | 2019-05-16 | ダウ グローバル テクノロジーズ エルエルシー | Method of preparing hydrophobic silica particles |
| CN106700006B (en) * | 2017-01-05 | 2018-11-27 | 昆明理工大学 | A kind of nanometer silica composite material and its preparation method and application |
| CN109908876B (en) * | 2019-04-22 | 2022-04-08 | 盐城工学院 | Preparation method and application of chitosan-based bionic adsorption gel doped with polysaccharide nano-crystallites |
| CN110638033B (en) * | 2019-09-29 | 2023-01-31 | 安徽大学 | Organic silicon/palmetto sansevieria polysaccharide nano-composite, preparation method and application |
| CN114804537B (en) * | 2022-05-17 | 2023-08-08 | 安徽浩悦环境科技股份有限公司 | Method and device for treating glycol-containing waste liquid |
| CN116808311B (en) * | 2023-01-10 | 2024-04-12 | 亿科吉互联网科技(南京)有限公司 | Preparation method of medical catheter with anticoagulation antibacterial coating |
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Inventor after: He Xuemei Inventor after: Zheng Chenghui Inventor after: Zhou Tianchi Inventor before: Zheng Chenghui Inventor before: He Xuemei Inventor before: Zhou Tianchi |
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Effective date of registration: 20190313 Address after: Room B502-1, 505-2, No. 150 Renai Road, Suzhou Industrial Park, Jiangsu Province Patentee after: Jiangsu Hai Pu functional materials company limited Address before: No. 9 Hope Avenue, Tinghu District, Yancheng City, Jiangsu Province Patentee before: Yangcheng Institute of Technology |