CN102583634A - Nanometer silver-doped titanium dioxide/chitosan composite microspheres for photolyzing phenol in source water - Google Patents
Nanometer silver-doped titanium dioxide/chitosan composite microspheres for photolyzing phenol in source water Download PDFInfo
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- CN102583634A CN102583634A CN2012100098852A CN201210009885A CN102583634A CN 102583634 A CN102583634 A CN 102583634A CN 2012100098852 A CN2012100098852 A CN 2012100098852A CN 201210009885 A CN201210009885 A CN 201210009885A CN 102583634 A CN102583634 A CN 102583634A
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Abstract
The invention relates to nanometer silver-doped titanium dioxide/chitosan composite microspheres, which is source water cleaning agent. The source water cleaning agent is the composite microspheres prepared by using nanometer silver-doped titanium dioxide as a catalyst and using chitosan as a carrier and is used for treating phenol in source water, wherein the nanometer titanium dioxide is doped with silver, then is mixed with the chitosan, is embedded by polyvinyl alcohol and sodium alginate and is prepared into the nanometer silver-doped titanium dioxide/chitosan microspheres. According to the cleaning agent, the phenol in the source water is effectively reduced, and the removal rate of the phenol in the source water can reach 95.3 percent.
Description
Technical field
The present invention relates to the source water process field, the Application Areas of particularly utilizing mixed nanometer silver titanium oxide/chitosan compound microsphere that phenol in the source water is handled.
Background technology
Phenol is one type of industrial chemicals that generally uses, and the pollution of phenolic wastewater is very serious, has had a strong impact on drinking water safety, and the improvement of phenolic wastewater is extremely urgent.Domestic and international method to its processing has a lot like biological process, extraction process, absorption method etc., but these method treatment effects are relatively poor, cost of investment is high, and enterprise is difficult to bear, and deals with improperly sometimes and can cause secondary pollution.Therefore, to have the phenolic waste water facture that widespread use is worth extremely urgent in research.Titanium oxide (TiO
2) have nontoxic, good stability just, production cost is low and characteristics such as non-secondary pollution, is a kind of more satisfactory photocatalyst.Have in recent years and much utilize nano-TiO
2The research of treating water, it has become a kind of novel Pollution abatement technology in environmental protection field.But, TiO
2The low principal element that becomes this skilled industry application of restriction of photo-quantum efficiency.How to improve TiO
2Effective rate of utilization become an important research project.Doping metals can improve the catalytic performance of catalyzer effectively, can be at semi-conductor TiO like doped metal ion Fe, Au, Pt, Pd etc.
2The surface introduce defective locations or change percent crystallinity, make it obtain visible light catalysis activity.With Au, Pt compares with Pd, and the Ag cost is lower, and toxicity is less, and the Ag particle of proper concn has killing action to bacterium and virus, is a kind of active substance that carries out deep purifying.Therefore the modification of Ag is to improving TiO
2Degerming functions active and the enhancing catalyzer is significant.Utilize chitosan loaded mixed nanometer silver titanium dioxide microballoon sphere to handle that phenol also never sets foot in the source water.
Summary of the invention
The objective of the invention is to: handle the deficiency that phenol pollutes in the source water to above-mentioned prior art, this research is intended and is being guaranteed nano-TiO
2Under the situation of chitosan compound microsphere advantage, overcome dusty material and be prone to assemble, be prone to shortcomings such as inactivation, more difficult recovery and reuse, draw up into complex microsphere, and be used for handling the phenol of source water, to improve processing efficiency, to strengthen the Separation and Recovery effect.
The object of the present invention is to provide the good source water scavenging agent of a kind of treatment effect, this scavenging agent treatment effect is good.
Another object of the present invention is to provide the preparation method of the phenol scavenging agent in the above-mentioned source water.
Another purpose of the present invention is to provide the method for use of the phenol scavenging agent in the above-mentioned source water.
The objective of the invention is to realize through following technical measures:
Phenol scavenging agent in a kind of source water is characterized in that: it is to be that catalyzer, chitosan are the complex microsphere that carrier makes with titanium oxide; Said nano titanium oxide is at first wanted silver-doped, carries out embedding, processes mixed nanometer silver titanium oxide/chitosan compound microsphere through Z 150PH and sodium-alginate with chitosan then, and be used for handling the phenol of source water.Z 150PH and sodium-alginate are the commercially available prod.
In order further to improve the photodissociation performance and the stability of complex microsphere, also the above-mentioned complex microsphere that makes is cured processing; What adopt in the said solidification treatment to complex microsphere is to contain 1～10% (being preferably 2%) CaCl
2Saturated BAS, in the quality percentage composition.(contain CaCl
2Saturated BAS by following configuration: as contain 2%CaCl
2Saturated BAS be to take by weighing 2 parts of CaCl
2Join in 98 parts of saturated BASs)
The preparation method of the phenol scavenging agent in a kind of source water is characterized in that: at first nano titanium oxide is carried out pre-treatment;
Take by weighing a certain amount of Ti (SO
4)
2Dissolving in 100mL zero(ppm) water in the solid, is slowly to add AgNO at 100～10: 3 by the ratio of amount of substance
3Solid (the amount ratio of preferred substance is 100: 3) forms Ti (SO under rotating speed 100～200r/min (being preferably 150r/min) magnetic agitation
4)
2Solution; After leaving standstill slightly, pours solution the autoclave of the cleaning of 100mL stainless steel (interior cup is tetrafluoroethylene) into; The maximum volume of solution is no more than 75% of autoclave volume, and baking oven begins to warm to from envrionment temperature and reaches 150～250 ℃ of (being preferably 200 ℃) post-heating reaction 2～6h (preferred 4h), and reaction finishes to cut off the electricity supply baking oven is lowered the temperature naturally; Take out glass substrate after being cooled to room temperature, wash (with BaCl through de-ionized
2Solution check SO
4 2-Existence), after absolute ethyl alcohol washes, seasoning obtains the nano-titanium dioxide powder of silver-doped.The nano-titanium dioxide powder that takes out silver-doped fully grinds, and places 50～300 ℃ of retort furnaces (preferred 450 ℃) calcination 2～6h (preferred 3h) again, just makes Ag/TiO after the cooling
2Photocatalyst.
With the nano-TiO that is mixed with silver
2Powder and chitosan add 2～10molL by 1: 1～10 (being preferably 1: 6) mixed
-1(be preferably 6molL
-1) NaOH place on the magnetic stirring apparatus rotating speed 100～200r/min (being preferably 150r/min) fully to stir to make it uniform mixing.Mixed solution is moved in the autoclave, put into baking oven after the sealing, 100～250 ℃ of design temperatures (being preferably 180 ℃), isothermal reaction 12～36h (being preferably 24h).Reaction product is taken out the back centrifuge washing to neutral, use the absolute ethyl alcohol centrifuge washing again instead 2～3 times.Product is put into baking oven at 40～100 ℃ (being preferably 60 ℃) oven dry, 1～6h (being preferably 3h), put in the moisture eliminator again or seasoning 24h, it is subsequent use to make composite granule.
And then prepare mixed nanometer silver titanium oxide/chitosan compound microsphere as follows:
With Z 150PH and sodium-alginate by mass ratio 10～6: 1 (being preferably 6: 1) mixed; Heating for dissolving 10～25min, be preferably 15min; Add a certain amount of composite granule (said Z 150PH: sodium-alginate: composite granule mass ratio 2～8: 1: 3～9 that stirs immediately; Be preferably 6: 1: 6), cooling 10～60min, be preferably behind the 30min with constant flow pump with constant flow rate continuously with hanging drop to (preferred 2%, in the quality percentage composition) CaCl that contains 1～10%
2Saturated BAS in solidify, be 5～40h set time, be preferably 15～25h, further be preferably 24h, after leach and make complex microsphere, put into 40～100 ℃ in baking oven (being preferably 70 ℃) dry for standby.
The present invention has following beneficial effect:
Utilize scavenging agent of the present invention to reduce phenol in the source water effectively, can make that the clearance of phenol reaches 95.3% in the water, be significantly higher than direct with titanium oxide and chitosan decontamination effect improving under equal conditions.
Description of drawings
Fig. 1 is that the complex microsphere consumption is to phenol photodissociation effect synoptic diagram in the source water
Fig. 2 is that the pH value is to phenol effect synoptic diagram in the complex microsphere purified water source water
Fig. 3 is that intensity of illumination is to phenol effect synoptic diagram in the complex microsphere purified water source water
Fig. 4 is that light application time is to phenol effect synoptic diagram in the complex microsphere purified water source water
Embodiment
Through embodiment the present invention is carried out concrete description below; Be necessary to be pointed out that at this following examples only are used for the present invention is further specified; Can not be interpreted as the restriction to protection domain of the present invention, the technician in this field can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment 1
One, the preparation of phenol scavenging agent in a kind of source water makes as follows:
1, titanium oxide silver-doped
At the Ti of 6g (SO
4)
2After adding 100mL zero(ppm) water formation solution in the solid, slowly add the AgNO of 100: 3 (ratio of amount of substance)
3Form 0.15molL under the solid, magnetic agitation
-1Ti (SO
4)
2Solution; After leaving standstill slightly, pours solution the autoclave of the cleaning of 100mL stainless steel (interior cup is tetrafluoroethylene) into; The maximum volume of solution is no more than 75% of autoclave volume, and baking oven begins to warm to from envrionment temperature and reaches 200 ℃ of post-heating reaction 4h, and reaction finishes to cut off the electricity supply baking oven is lowered the temperature naturally; Take out glass substrate after being cooled to room temperature, wash (with BaCl through de-ionized
2Solution check SO
4 2-Existence), after absolute ethyl alcohol washes, seasoning is fully ground again, then in retort furnace in 450 ℃ of roasting 3h, just make after the cooling and carry the Ag amount and be Ag/TiO
2Powder body material.
2, the preparation of mixed nanometer silver titanium oxide/chitosan compound microsphere
With the nano-TiO that is mixed with silver
2Powder and chitosan were by 1: 5 mixed, and the NaOH that adds 10mol/L places fully to stir on the magnetic stirring apparatus and makes it uniform mixing.Mixed solution is moved in the autoclave, put into baking oven after the sealing, 180 ℃ of design temperatures, isothermal reaction 24h.Reaction product is taken out the back centrifuge washing to neutral, use the absolute ethyl alcohol centrifuge washing again instead 2～3 times.Product is put into baking oven, and 70 ℃ of oven dry 2h are put in the moisture eliminator or seasoning 48h again, and it is subsequent use to make composite granule.
With the composite powder material of Z 150PH, sodium-alginate and above-mentioned preparation in (Z 150PH: sodium-alginate: composite granule mass ratio 6: 1: 6) ratio prepares microballoon; Preparation earlier with sodium-alginate and Z 150PH heating for dissolving 15min, adds mixed powder immediately and stirs during microballoon, cool off behind the 30min with constant flow pump with constant flow rate continuously with hanging drop to containing 2%CaCl
2Saturated BAS in solidify, leach bead after solidifying 24h, dry subsequent use after water is rinsed well.
Application implementation example 1
Mixed nanometer silver titanium oxide/chitosan compound microsphere is handled phenol in the source water
1, the removal of phenol in the source water is tested
Get 100mL 1 * 10
-4Contain the phenol water sample in the 250mL Erlenmeyer flask; Add an amount of complex microsphere; With the fluorescent lamp is that experimental light sources is handled water sample, and reaction finishes the concentration that phenol in the water is measured in the back, can draw mixed nanometer silver titanium oxide/chitosan compound microsphere to containing the purification efficiency of phenol water sample through calculating.Concrete steps are undertaken by following:
At the dosage 2.2195g of mixed nanometer silver titanium oxide/chitosan compound microsphere, pH value of solution value 6, reaction times 118.77min, intensity of illumination 1164.0 (x10 lux), with this understanding, the phenol clearance can reach 95.3% in the water.
Claims (5)
1. source water scavenging agent is characterized in that: it is to be that catalyzer, chitosan are the complex microsphere that carrier makes with mixed nanometer silver titanium oxide; Said catalyst nano titanium oxide at first will carry out embedding, process mixed nanometer silver titanium oxide/chitosan microball with Z 150PH and sodium-alginate through silver-doped to guarantee catalytic effect again.
2. phenol scavenging agent in the source water as claimed in claim 1 is characterized in that: said Z 150PH: sodium-alginate: composite granule mass ratio 6:1:6.
3. like claim 1,2 described scavenging agents, it is characterized in that: want silver-doped before nano titanium oxide is prepared microballoon; What adopt in the said solidification treatment to complex microsphere is to contain 1～10%CaCl
2Saturated BAS, in the quality percentage composition.
4. drink water purifying agent as claimed in claim 3 is characterized in that: what adopt in the said solidification treatment to complex microsphere is to contain 2%CaCl
2Saturated BAS, in the quality percentage composition.
5. like claim 1,2 or 3 described scavenging agents, it is characterized in that: nano titanium oxide at first will pass through pre-treatment, specifically is with Ti (SO
4)
2Solid and AgNO
3By the amount of substance ratio is 100～10:3 mixing silver-doped.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210009885.2A CN102583634B (en) | 2012-01-12 | 2012-01-12 | Phenol in mixed nanometer silver titanium dioxide/chitosan compound microsphere photodissociation source water |
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|---|---|---|---|
| CN201210009885.2A CN102583634B (en) | 2012-01-12 | 2012-01-12 | Phenol in mixed nanometer silver titanium dioxide/chitosan compound microsphere photodissociation source water |
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| CN102583634B CN102583634B (en) | 2015-11-18 |
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Cited By (10)
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| CN105727901A (en) * | 2016-04-29 | 2016-07-06 | 河海大学 | Preparation method of titanium dioxide photocatalytic adsorbing material |
| CN105833917A (en) * | 2016-03-24 | 2016-08-10 | 济南大学 | Preparation method of silver-loaded titania nanotube-magnetic chitosan/beta-cyclodextrin composite material and application thereof |
| CN106345442A (en) * | 2016-08-30 | 2017-01-25 | 渤海大学 | Preparation method of nanometer titanium dioxide |
| CN106561710A (en) * | 2016-11-08 | 2017-04-19 | 佛山市铁人环保科技有限公司 | Titanium dioxide sol capable of degrading pesticide residues, and preparation method of titanium dioxide sol |
| CN108855233A (en) * | 2018-07-03 | 2018-11-23 | 南通纺织丝绸产业技术研究院 | It is a kind of can light degradation dyestuff microfluidic control for copper-loaded nano-titanium dioxide chitosan compound microsphere method |
| CN108996709A (en) * | 2018-08-28 | 2018-12-14 | 重庆文理学院 | A kind of round-the-clock composite photocatalyst collaboration system and preparation method thereof |
| CN110054370A (en) * | 2019-04-15 | 2019-07-26 | 广东开源环境科技有限公司 | A kind of river bottom mud solidification is stable to repair medicament and preparation method thereof |
| CN110102267A (en) * | 2019-05-27 | 2019-08-09 | 华南理工大学 | A kind of aluminium base MOFs/ chitosan compound microsphere and its preparation method and application |
| CN112479392A (en) * | 2020-11-23 | 2021-03-12 | 纳琦绿能工程有限公司 | Composite sewage treatment agent and preparation method and application thereof |
| CN114713293A (en) * | 2022-05-02 | 2022-07-08 | 滨州学院 | Polyacrylonitrile nanofiber membrane loaded with composite photocatalyst as well as preparation method and application of polyacrylonitrile nanofiber membrane |
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|---|---|---|---|---|
| CN105833917A (en) * | 2016-03-24 | 2016-08-10 | 济南大学 | Preparation method of silver-loaded titania nanotube-magnetic chitosan/beta-cyclodextrin composite material and application thereof |
| CN105727901A (en) * | 2016-04-29 | 2016-07-06 | 河海大学 | Preparation method of titanium dioxide photocatalytic adsorbing material |
| CN105727901B (en) * | 2016-04-29 | 2018-11-09 | 河海大学 | A kind of preparation method of optically catalytic TiO 2 sorbing material |
| CN106345442A (en) * | 2016-08-30 | 2017-01-25 | 渤海大学 | Preparation method of nanometer titanium dioxide |
| CN106561710A (en) * | 2016-11-08 | 2017-04-19 | 佛山市铁人环保科技有限公司 | Titanium dioxide sol capable of degrading pesticide residues, and preparation method of titanium dioxide sol |
| CN108855233B (en) * | 2018-07-03 | 2021-02-19 | 南通纺织丝绸产业技术研究院 | Method for preparing copper-loaded nano titanium dioxide chitosan composite microspheres by using microfluidic technology through photodegradable dye |
| CN108855233A (en) * | 2018-07-03 | 2018-11-23 | 南通纺织丝绸产业技术研究院 | It is a kind of can light degradation dyestuff microfluidic control for copper-loaded nano-titanium dioxide chitosan compound microsphere method |
| CN108996709A (en) * | 2018-08-28 | 2018-12-14 | 重庆文理学院 | A kind of round-the-clock composite photocatalyst collaboration system and preparation method thereof |
| CN110054370A (en) * | 2019-04-15 | 2019-07-26 | 广东开源环境科技有限公司 | A kind of river bottom mud solidification is stable to repair medicament and preparation method thereof |
| CN110054370B (en) * | 2019-04-15 | 2021-08-20 | 广东开源环境科技有限公司 | River sediment curing, stabilizing and repairing agent and preparation method thereof |
| CN110102267A (en) * | 2019-05-27 | 2019-08-09 | 华南理工大学 | A kind of aluminium base MOFs/ chitosan compound microsphere and its preparation method and application |
| CN110102267B (en) * | 2019-05-27 | 2021-10-01 | 华南理工大学 | Aluminum-based MOFs/chitosan composite microsphere and preparation method and application thereof |
| CN112479392A (en) * | 2020-11-23 | 2021-03-12 | 纳琦绿能工程有限公司 | Composite sewage treatment agent and preparation method and application thereof |
| CN114713293A (en) * | 2022-05-02 | 2022-07-08 | 滨州学院 | Polyacrylonitrile nanofiber membrane loaded with composite photocatalyst as well as preparation method and application of polyacrylonitrile nanofiber membrane |
| CN114713293B (en) * | 2022-05-02 | 2023-09-15 | 滨州学院 | Polyacrylonitrile nanofiber membrane loaded with composite photocatalyst and preparation method and application thereof |
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