CN104148025A - Preparation of nanosilicon dioxide modified by polysaccharide and application of nanosilicon dioxide to treatment of printing and dyeing wastewater - Google Patents
Preparation of nanosilicon dioxide modified by polysaccharide and application of nanosilicon dioxide to treatment of printing and dyeing wastewater Download PDFInfo
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Abstract
The invention discloses a preparation of nanosilicon dioxide modified by oxydic dialdehyde polysaccharide and an application of the nanosilicon dioxide to treatment of printing and dyeing wastewater and belongs to the technical field of application of nanosilicon materials. The preparation of the nanosilicon dioxide modified by oxydic dialdehyde polysaccharide comprises the following steps: selectively oxidizing chitosan by using periodate, adding a certain amount of nanosilicon dioxide into a methylbenzene solution and carrying out ultrasonic dispersion, subsequently adding oxydic dialdehyde chitosan, gradually adding a silicon coupling agent which is amino propyl ethoxy siloxane while stirring, reacting at 60-90 DEG C for a period of time to obtain acetone sediment, filtering and washing by using ethyl alcohol, freezing and drying to obtain silicon dioxide nano-composite coupled by oxydic dialdehyde chitosan silicon, and applying the silicon dioxide nano-composite to the treatment of the printing and dyeing wastewater. The nanosilicon dioxide modified by oxydic dialdehyde polysaccharide has the advantages that raw materials are low-cost and easily available; the preparation method is simple; and the nanosilicon dioxide modified by oxydic dialdehyde polysaccharide has excellent dye adsorption property. When the concentration of modified nanosilicon dioxide is 2g/L-12g/L, the decolourization ratio can reach more than 98%, so that the chromaticity of the dyeing wastewater is greatly reduced; and the nanosilicon dioxide modified by oxydic dialdehyde polysaccharide has a great application value in removal of the printing and dyeing wastewater.
Description
Technical field
The present invention relates to the processing 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 dyeing waste water causes substantial pollution to environment and is difficult to and processes.Its feature be complicated component, stability strong, be difficult to degraded, discharge capacity is huge.The methods such as the light degradation of latest development, chemistry redox, biologic treating technique are because the harmful little molecule residue of high, the easy generation of cost, process the shortcomings such as wastewater flow rate is little and be difficult to application.Comparatively speaking, adsorption treatment technology can be processed well large flow, complicated component, is difficult to the waste water of degraded, is important sewage water treatment method for a long time.Natural macromolecule adsorbent is in widespread attention recently.Natural polymer and modified adsorbent thereof have that raw material sources are wide, cost is low, toxicity is little, and synthesis technique is simple, the easy advantage such as degraded of product, so research and development modified natural polymer trapping agent becomes the focus of studying at present both at home and abroad.In numerous natural macromolecular materials, shitosan wide material sources, with low cost, nontoxic, easy degraded, easily modification and there is good absorption property and receive much concern.But shitosan is water insoluble, not as good as organic solvent, can be dissolved in some low acidity aqueous solution, greatly limit its range of application.Inorganic nano silica dioxide medium has the easy rhetorical function group of good chemical characteristic and surface.Because its surface area is large, be easy to reunite, in order to make its fine dispersion in solution, conventionally its particle surface is carried out to graft modification.Conventional modifier has silane coupler as γ-(2,3-glycidoxy) propyl trimethoxy silicane, titanate coupling agent, hyper-dispersant, organic polymer etc.At present, the composite modified composite of organic polymer and inorganic matter is important field of research.Adopt the compound modified manometer silicon dioxide material of organic matter to there is the advantages such as applicable pH wide ranges, good stability, high adsorption capacity, be suitable for the adsorption treatment of sewage.And existing research work mostly concentrates on esters of acrylic acid synthesising macromolecule copolymer to the polymer of nanometer two SiClx modifications, and adopt the collaborative silicone couplet of natural sugar analog derivative to nano-silicon dioxide modified and less for treatment of dyeing wastewater.
Summary of the invention
In view of this, the invention provides preparation method and the specifically application in dyeing waste water of the chitin modified nano silicon of a kind of dialdehyde of ecological, environmental protective, thereby solve the not tractable difficult problem of dye wastewater.
The preparation method of polysaccharide-modified nano silicon and the application in treatment of dyeing wastewater, is characterized in that, comprises the following steps:
1) the periodic acid hydrochlorate that is, 1:0.5-2 by mol ratio and shitosan carry out selective oxidation, under 30 ℃ of conditions, be placed in constant temperature oscillation and dye model machine lucifuge reaction 1-3 hour, add again the ethylene glycol of 30-60 milliliter 0.1mol/L to continue reaction 0.5-2h, take out suspension, with circulating water type vavuum pump suction filtration, take out filtrate, in filtrate, add 150ml acetone, lucifuge precipitation 2h, obtains oxidation dialdehyde shitosan after suction filtration;
2), nano silicon is added to ultrasonic dispersion in toluene solution; slowly stir; add after the oxidation dialdehyde shitosan of 10-30% of nano silicon quality, under nitrogen protection, 60-90 ℃ (rotating speed 2000rpm-10000 rpm) stirs 0.5-2 hour; add again silicone couplet; 70-90 ℃ is stirred 3-5 hour, obtains acetone precipitation and filters, ethanol washing; freeze drying, obtain the coupling of bis oxide shitosan silicon-silicon dioxide nanocomposite.
As the further optimization of this programme, the periodic acid hydrochlorate in described step 1) is one or both compositions in sodium metaperiodate, potassium metaperiodate.
As the further optimization of this programme, described step 2) in silicone couplet be amine propyl group ethyoxyl siloxanes, the 20-50% that consumption is 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 particle size scope is at 10nm-80nm.
Obtain the coupling of bis oxide shitosan silicon-silicon dioxide nanocomposite, this nano-complex is faint yellow.
Modified manometer silicon dioxide adsorbent prepared by described method is direct dyes and reactive dye for adsorbing the dye type of dyeing waste water.
Beneficial effect of the present invention:
Cheap being easy to get of the present invention's shitosan cost of material used in the present invention, synthesis technique is ripe, modified manometer silicon dioxide adsorbent prepared by the method for the invention is for adsorbing the dyestuff of dyeing waste water, when using modified manometer silicon dioxide concentration, be 2g/L-12g/L, under ultrasound condition, percent of decolourization can reach more than 98% effect.Modified manometer silicon dioxide adsorbent of the present invention is energy-conservation, ecological environment-friendly type adsorbent, to environment, can not cause secondary pollution.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, 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 the affect structural representation of adsorption time of the present invention on modified manometer silicon dioxide absorption property.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
embodiment mono-:
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 is 1:0.5-2 by mol ratio and shitosan carry out selective oxidation, wherein, sodium iodate, one or both compositions in potassium metaperiodate, under 30 ℃ of conditions, be placed in constant temperature oscillation and dye model machine lucifuge reaction 1-3 hour, add again the ethylene glycol of 30-60 milliliter 0.1mol/L to continue reaction 0.5-2h, take out suspension, with circulating water type vavuum pump suction filtration, take out filtrate, in filtrate, add 150ml acetone, lucifuge precipitation 2h, after suction filtration, obtain oxidation dialdehyde shitosan,
2), by particle size range at 10nm-80nm, concentration is that the nano silicon of 2g/L-12g/L adds ultrasonic dispersion in toluene solution, slowly stir, add after the oxidation dialdehyde shitosan of 10-30% of nano silicon quality, under nitrogen protection, 60-90 ℃ (rotating speed 2000rpm-10000 rpm) stirs 0.5-2 hour, add again silicone couplet, wherein, silicone couplet is amine propyl group ethyoxyl siloxanes, consumption is the 20-50% of nano silicon, 70-90 ℃ is stirred 3-5 hour, obtain acetone precipitation and filter, ethanol washing, freeze drying, obtain the coupling of bis oxide shitosan silicon-silicon dioxide nanocomposite.
Obtain the coupling of bis oxide shitosan silicon-silicon dioxide nanocomposite, this nano-complex is faint yellow.Modified manometer silicon dioxide adsorbent is direct dyes and reactive dye for adsorbing the dye type of dyeing waste water.
Embodiment bis-:
A kind of preparation that is oxidized the nano silicon water treatment agent of dialdehyde chitin modification
By 5g particle size range at 30nm nanometer SiO
2ultrasonic being scattered in 150ml toluene solvant, to the oxidation dialdehyde shitosan that adds certain mass mark 30% in dispersion, N
2under protection, 90 ℃ of high-speed stirred 1 hour, then add 20% amine propyl group ethyoxyl siloxanes, 90 ℃ are stirred 4 hours; obtain yellow solution, acetone precipitation reactant, suction filtration; nano particle repeatedly washs with absolute ethyl alcohol, and freeze drying 12h obtains faint yellow modified manometer silicon dioxide particle.
Embodiment tri-:
The preparation of oxidation dialdehyde chitin
By in shitosan 0.3mol/L sodium periodate solution, keep IO4
-: CS mol ratio is 1:0.62, is placed in constant temperature oscillation and dyes model machine lucifuge reaction 2h, then add the ethylene glycol of 40 milliliters of 0.1mol/L to continue reaction 0.5h under 30 ℃ of conditions,, with circulating water type vavuum pump suction filtration, take out filtrate, in filtrate, add 150ml acetone, lucifuge precipitation 2h, obtains after suction filtration.
Embodiment tetra-:
Modified manometer silicon dioxide adsorbent is for adsorbing the dyestuff of dyeing waste water
When using modified manometer silicon dioxide concentration, be 2g/L-12g/L, waste water from dyestuff pH is 2.56, adsorbs 60 minutes, to dye decolored rate, can reach more than 98% effect.
As shown in Figure 1, adsorption temp is to modified Nano SiO
2absorption property affect structural representation.The absorptivity of active red M3B is up to 98%.And the raising of temperature, modified Nano SiO
2the adsorption rate of dyestuff is also increased thereupon, but the amplitude increasing is few, from the angle of environmental protection and energy saving, 30 ℃ of processing dyestuffs of the suitable use of the nano silicon of modification.As shown in Figure 2, adsorption time is to modified Nano SiO
2the impact of absorption property, along with the increase of time, modified manometer silicon dioxide increases the adsorption rate of dyestuff, and initial adsorption rate is very fast.
The above; it is only the specific embodiment of the present invention; but protection scope of the present invention is not limited to this; any those of ordinary skill in the art are in the disclosed technical scope of the present invention; the variation that can expect without creative work or replacement, within all should being encompassed in protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain that claims were limited.
Claims (6)
1. the preparation method of polysaccharide-modified nano silicon, is characterized in that, comprises the following steps:
1) the periodic acid hydrochlorate that is, 1:0.5-2 by mol ratio and shitosan carry out selective oxidation, under 30 ℃ of conditions, be placed in constant temperature oscillation and dye model machine lucifuge reaction 1-3 hour, add again the ethylene glycol of 30-60 milliliter 0.1mol/L to continue reaction 0.5-2h, take out suspension, with circulating water type vavuum pump suction filtration, take out filtrate, in filtrate, add 150ml acetone, lucifuge precipitation 2h, obtains oxidation dialdehyde shitosan after suction filtration;
2), nano silicon is added to ultrasonic dispersion in toluene solution; slowly stir; add after the oxidation dialdehyde shitosan of 10-30% of nano silicon quality, under nitrogen protection, rotating speed is that 2000rpm-10000 rpm stirs 0.5-2 hour at 60-90 ℃; add again silicone couplet; 70-90 ℃ is stirred 3-5 hour, obtains acetone precipitation and filters, ethanol washing; freeze drying, obtain the coupling of bis oxide shitosan silicon-silicon dioxide nanocomposite.
2. the preparation method of polysaccharide-modified nano silicon as claimed in claim 1, is characterized in that: the periodic acid hydrochlorate in described step 1) is one or both compositions in sodium metaperiodate, potassium metaperiodate.
3. the preparation method of polysaccharide-modified nano silicon as claimed in claim 1, is characterized in that: the silicone couplet described step 2) is amine propyl group ethyoxyl siloxanes, the 20-50% that consumption is nano silicon.
4. the preparation method of the polysaccharide-modified nano silicon as described in claim 1 or 3 any one, is characterized in that: described nanometer titanium dioxide silicon concentration is 2g/L-12g/L.
5. the preparation method of the polysaccharide-modified nano silicon as described in claim 1 or 3 or 4 any one, is characterized in that: described nano silicon nanometer particle size scope is at 10nm-80nm.
6. by the preparation method described in claim 1 to 5 any one, make to obtain the application of polysaccharide-modified nano silicon in treatment of dyeing wastewater, it is characterized in that: modified manometer silicon dioxide adsorbent prepared by described method is direct dyes and reactive dye for adsorbing the dye type of dyeing waste water.
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Cited By (7)
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| CN104785214A (en) * | 2015-03-27 | 2015-07-22 | 安徽大学 | Chitosan-coated magnetic mesoporous silica core-shell structured nanoparticle and preparation method and application thereof |
| CN106700006A (en) * | 2017-01-05 | 2017-05-24 | 昆明理工大学 | Nano-silica compound material, and preparation method and application thereof |
| WO2017166173A1 (en) * | 2016-03-31 | 2017-10-05 | Dow Global Technologies Llc | Method of making hydrophobic silica particles |
| CN109908876A (en) * | 2019-04-22 | 2019-06-21 | 盐城工学院 | A kind of preparation method and application of the chitosan-based bionical attractive gel of polysaccharide nano microcrystalline doping |
| CN110638033A (en) * | 2019-09-29 | 2020-01-03 | 安徽大学 | Organic silicon/palmetto sansevieria polysaccharide nano-composite, preparation method and application |
| CN114804537A (en) * | 2022-05-17 | 2022-07-29 | 安徽浩悦环境科技有限责任公司 | Method and device for treating waste liquid containing ethylene glycol |
| CN116808311A (en) * | 2023-01-10 | 2023-09-29 | 张峰 | Preparation method of medical catheter with anticoagulation antibacterial coating |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104785214A (en) * | 2015-03-27 | 2015-07-22 | 安徽大学 | Chitosan-coated magnetic mesoporous silica core-shell structured nanoparticle and preparation method and application thereof |
| 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 |
| WO2017166173A1 (en) * | 2016-03-31 | 2017-10-05 | Dow Global Technologies Llc | Method of making hydrophobic silica particles |
| CN106700006A (en) * | 2017-01-05 | 2017-05-24 | 昆明理工大学 | Nano-silica compound material, and preparation method and application thereof |
| CN109908876A (en) * | 2019-04-22 | 2019-06-21 | 盐城工学院 | A kind of preparation method and application of the chitosan-based bionical attractive gel of polysaccharide nano microcrystalline doping |
| CN110638033A (en) * | 2019-09-29 | 2020-01-03 | 安徽大学 | Organic silicon/palmetto sansevieria polysaccharide nano-composite, preparation method and application |
| CN110638033B (en) * | 2019-09-29 | 2023-01-31 | 安徽大学 | Organic silicon/palmetto sansevieria polysaccharide nano-composite, preparation method and application |
| CN114804537A (en) * | 2022-05-17 | 2022-07-29 | 安徽浩悦环境科技有限责任公司 | Method and device for treating waste liquid containing ethylene glycol |
| 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 |
| CN116808311A (en) * | 2023-01-10 | 2023-09-29 | 张峰 | Preparation method of medical catheter with anticoagulation antibacterial coating |
| 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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