CN104226239A - Hydrotalcite/cuprous oxide nanocomposite material and application thereof - Google Patents
Hydrotalcite/cuprous oxide nanocomposite material and application thereof Download PDFInfo
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- CN104226239A CN104226239A CN201410534656.1A CN201410534656A CN104226239A CN 104226239 A CN104226239 A CN 104226239A CN 201410534656 A CN201410534656 A CN 201410534656A CN 104226239 A CN104226239 A CN 104226239A
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- hydrotalcite
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- sodium thiosulfate
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Abstract
The invention discloses a hydrotalcite/cuprous oxide nanocomposite material and application thereof. Hydrotalcite is added into a mixed water solution prepared by copper acetate and sodium thiosulfate to be stirred, glucose is added into the mixed water solution to be evenly stirred, a sodium hydroxide solution is added under the ultrasonic stirring condition after standing, and the hydrotalcite/cuprous oxide nanocomposite material is obtained through centrifugation, washing and drying. The molar concentrations of the copper acetate and the sodium thiosulfate in the mixed water solution are 0.2-0.3mol/L and 0.4-0.6mol/L respectively. The hydrotalcite accounts for 25%-35% of total mass of the copper acetate and the sodium thiosulfate. The glucose accounts for 4%-5% of total mass of the copper acetate, the sodium thiosulfate and the hydrotalcite. Blue-green algae treatment and handling efficiency is high, the handling efficiency can be higher than 80%, and the hydrotalcite/cuprous oxide nanocomposite material is low in cost, convenient to operate and easy to apply widely. After frustules killing, no influence on total hardness, Al concentration, total nitrogen and organic content in the solution occurs, and 90% of phosphorus in a water body can be absorbed.
Description
Technical field
The invention belongs to water-treatment technology field, be specifically related to a kind of hydrotalcite/cuprous nano composite and the application in water treatment thereof.
Background technology
In recent years, along with the increasing of china natural resources using degree, each Big Lakes eutrophication is day by day serious.Ecosystem degradation, wawter bloom frequently break out, and have a strong impact on the productive life of the mankind, and this becomes the great environmental problem of restriction Chinese society and national sustained economic development.
In all fresh water algaes, toxicity is the strongest, pollution range is the widest is Cyanophyta, and microcystis kutz especially wherein, Anabaena, Aphanizomenon and Oscillatoria are the algae that common are potential hazard in fresh water.In common algae-removing method, what be most widely used is the alga removalby coagulation technology that process equipment is simple, disposal cost is low.Absorption method wherein based on environment mineral material is considered to one of effective administering method.Mineral material because of its wide material sources, to be cheaply easy to get, to regenerate easily, can to repeatedly use and the feature such as non-secondary pollution, in wawter bloom treatment research, be subject to extensive concern.The clay mineral material that document is reported mainly contains zeolite, imvite, attapulgite, kaolin, bentonite, hydrotalcite etc., because of in its natural minerals except hydrotalcite other materials surface is all electronegative, so some scholars carry out modification to natural minerals, the modified clay material obtaining surface band positive charge improves the flocculation ability of clay material to frustule, but prepares and material modifiedly there will be that cost increases, operating process is complicated, produce secondary pollution problems.
Summary of the invention
The object of the invention is to provide a kind of preparation technology simple, the nano composite material of low in raw material price, and it can either have and kills algae efficiency efficiently and can ensure environment friendly again.
For achieving the above object, adopt technical scheme as follows:
A kind of hydrotalcite/cuprous nano composite, adopts following methods preparation:
In the mixed aqueous solution of Schweinfurt green and sodium thiosulfate, add hydrotalcite stir, then add glucose and stir evenly rear leaving standstill, under ultrasonic agitation condition, add sodium hydroxide solution, centrifugal, washing, dry and obtain hydrotalcite/cuprous nano composite.
By such scheme, in described mixed aqueous solution, the molar concentration of Schweinfurt green and sodium thiosulfate is respectively 0.2 ~ 0.3mol/L and 0.4 ~ 0.6mol/L.
By such scheme, the quality of described hydrotalcite accounts for 25 ~ 35% of Schweinfurt green and sodium thiosulfate gross mass.
By such scheme, described in add hydrotalcite mixing time be 20 ~ 40min.
By such scheme, the consumption of described glucose accounts for 4 ~ 5% of Schweinfurt green, sodium thiosulfate and hydrotalcite gross mass.
By such scheme, the molar concentration of described sodium hydroxide solution is 0.4 ~ 0.6mol/L, and consumption accounts for 8 ~ 9% of Schweinfurt green, sodium thiosulfate and hydrotalcite gross mass.
By such scheme, the described ultrasonic agitation time is 20 ~ 40min.
By such scheme, described bake out temperature is 50 ~ 60 DEG C.
Above-mentioned hydrotalcite/the application of cuprous nano composite in water treatment.
Above-mentioned hydrotalcite/the application of cuprous nano composite in wawter bloom process.
The present invention utilizes hydrotalcite/cuprous nano composite absorption frustule, the hydroxyl radical free radical that recycling nano cuprous oxide produces under excited by visible light is to kill frustule, anion simultaneously in adsorbed water body, makes composite can ensure again the environment friendly of material by efficient algae removal under field conditions (factors).The coupling technique of this integration achieves the fully effectively utilization of natural mineral resource and solar energy, for the thorough efficient-decomposition of the algae in lake provides new principle and method.
Beneficial effect of the present invention:
The present invention's raw material hydrotalcite used is natural minerals, and cheap, wide material sources, utilize the composite that it is prepared, and process is simple, is again environmental friendliness shaped material.
First the present invention utilizes the suction-operated of hydrotalcite frustule to be adsorbed on the surface of composite, and then utilizes cuprous oxide to excite the hydroxyl radical free radical of lower generation strong oxidizing property thus oxidative degradation frustule at sunshine, finally reaches effective degradation effect.
Outburst due to blue-green algae is under the condition of summer high temperature, illumination abundance, and hydrotalcite/cuprous nano composite also utilizes sufficient sunshine to reach best algae killing effect just, thus the phenomenon avoiding " first polluting; rear improvement " occurs, and fundamentally solves the problem of bloom blue algae.
Blue-green algae administered by hydrotalcite of the present invention/cuprous nano composite, and treatment effeciency is high, and treatment effeciency can reach more than 80%, and cost is low, easy to operate, and is easy to extensive enforcement.
After hydrotalcite/frustule killed by cuprous oxide composite, on total hardness, Al concentration, total nitrogen and content of organics in solution without impact, and can 90% phosphorus in adsorbed water body.
Accompanying drawing explanation
Fig. 1: embodiment 3 hydrotalcites/cuprous nano composite XRD schemes.
Fig. 2: embodiment 3 hydrotalcites/cuprous nano composite FTIR schemes.
Fig. 3: embodiment 3 hydrotalcites/cuprous nano composite is to the removal effect of algae.
Fig. 4: embodiment 3 hydrotalcites/cuprous nano composite is to the removal effect of organic matter and inorganic matter.
Detailed description of the invention
Following examples explain technical scheme of the present invention further, but not as limiting the scope of the invention.
A kind of hydrotalcite/cuprous nano composite, adopts following methods preparation:
In the mixed solution of Schweinfurt green and sodium thiosulfate, add hydrotalcite stir, add glucose again to stir, add under ultrasonic agitation condition heat sodium hydroxide solution, temperature at 30-50 DEG C, centrifugal, washing, dry obtain hydrotalcite/cuprous nano composite.
Optimally, in mixed aqueous solution, the molar concentration of Schweinfurt green and sodium thiosulfate is respectively 0.2 ~ 0.3mol/L and 0.4 ~ 0.6mol/L.
Optimally, the quality of hydrotalcite accounts for 25 ~ 35% of Schweinfurt green and sodium thiosulfate gross mass.
Optimally, adding hydrotalcite mixing time is 20 ~ 40min.
Optimally, the consumption of glucose accounts for 4 ~ 5% of Schweinfurt green, sodium thiosulfate and hydrotalcite gross mass.
Optimally, the molar concentration of sodium hydroxide solution is 0.4 ~ 0.6mol/L, and consumption accounts for 8 ~ 9% of Schweinfurt green, sodium thiosulfate and hydrotalcite gross mass.
Optimally, the ultrasonic agitation time is 20 ~ 40min.
Optimally, bake out temperature is 50 ~ 60 DEG C.
The present invention's raw material hydrotalcite used is natural minerals, and cheap, wide material sources, utilize the composite that it is prepared, and process is simple, is again environmental friendliness shaped material.
First its operation principle utilizes the suction-operated of hydrotalcite frustule to be adsorbed on the surface of composite, and then utilize cuprous oxide to excite the hydroxyl radical free radical of lower generation strong oxidizing property thus oxidative degradation frustule at sunshine, finally reach effective degradation effect.And due to the outburst of blue-green algae be under the condition of summer high temperature, illumination abundance, and hydrotalcite/cuprous nano composite also utilizes sufficient sunshine to reach best algae killing effect just, thus the phenomenon avoiding " first polluting; rear improvement " occurs, and fundamentally solves the problem of bloom blue algae.
Hydrotalcite of the present invention/cuprous nano composite can effectively be applied in water treatment.Process for wawter bloom is effective especially.
Particularly be applied in wawter bloom process.The present invention administers blue-green algae, and treatment effeciency is high, and treatment effeciency can reach more than 80%, and cost is low, easy to operate, and is easy to extensive enforcement.And after killing frustule, on total hardness, Al concentration, total nitrogen and content of organics in solution without impact, and can 90% phosphorus in adsorbed water body.
The preparation of embodiment 1 hydrotalcite/cuprous nano composite
The ratio being 1:1.5 in the mol ratio of Schweinfurt green and sodium thiosulfate gets 20mL 0.2mol/L Schweinfurt green in conical flask, slowly add 15mL 0.4mol/L hypo solution, add 0.57g hydrotalcite and stir 20min, add 0.11g glucose again to stir, the sodium hydroxide solution of 15mL 0.4mol/L is slowly added under ultrasound condition, temperature is at 30-50 DEG C, and ultrasonic 20min, centrifugal, washing, 50 DEG C of oven dry obtain hydrotalcite/cuprous nano composite.
Embodiment 2
The ratio being 1:1.75 in the mol ratio of Schweinfurt green and sodium thiosulfate gets 100mL 0.225mol/L Schweinfurt green in conical flask, slowly add 88mL 0.45mol/L hypo solution, add 4.0g hydrotalcite and stir 25min, add 0.77g glucose again to stir, the sodium hydroxide solution of 87mL 0.45mol/L is slowly added under ultrasound condition, temperature is at 30-50 DEG C, and ultrasonic 25min, centrifugal, washing, 55 DEG C of oven dry obtain hydrotalcite/cuprous nano composite.
Embodiment 3
The ratio being 1:2 in the mol ratio of Schweinfurt green and sodium thiosulfate gets 200mL 0.25mol/L Schweinfurt green in conical flask, slowly add 200mL 0.5mol/L hypo solution, add 10.0g hydrotalcite and stir 30min, add 2g glucose again to stir, the sodium hydroxide solution of 200mL 0.5mol/L is slowly added under ultrasound condition, temperature is at 30-50 DEG C, and ultrasonic 30min, centrifugal, washing, 55 DEG C of oven dry obtain hydrotalcite/cuprous nano composite.
Shown in accompanying drawing 1,2, be respectively the present embodiment hydrotalcite/cuprous nano composite XRD and scheme and FTIR figure.
Dilute to mix with the nutrient solution after sterilizing and algae sample and prepare the algae suspension that microcystic aeruginosa mass concentration is 1 mg/L (in frustule Determination of Chlorophyll a mass concentration), this algae suspension is placed in conical flask, add hydrotalcite/cuprous nano composite that mass concentration is 1 g/L, under conical flask is placed in outdoor sunshine, under stirring aeration condition, carry out light-catalyzed reaction, every 2h carries out the concentration of sampling and measuring frustule Determination of Chlorophyll a.Arrange simultaneously one do not add the blank sample similarity condition of hydrotalcite/cuprous nano composite under carry out Experimental comparison.Result shows, along with the carrying out in processing time, the concentration of microcystic aeruginosa Determination of Chlorophyll a constantly reduces, and after 8h, degradation rate still continues to rise, and 8h degradation rate reaches 80%.
Method with degraded microcystic aeruginosa carries out the experiment of photocatalytic degradation synnema algae, and result shows, along with the carrying out in processing time, synnema concentration of algae constantly reduces, and after 8h, degradation rate still continues to rise, and within 8 hours, degradation rate reaches 85%.With reference to shown in accompanying drawing 3, the present embodiment hydrotalcite/cuprous nano composite is to the removal effect of algae.
Compound concentration is the reactive brilliant red solution of 160 mg/L and the humic acid solution 250mL of 50mg/L respectively, and be placed in conical flask, in conical flask, add 0.25g hydrotalcite/cuprous nano composite carry out light-catalyzed reaction, every 20min sampling, centrifugal, get supernatant and survey its absorbance, get 2h altogether, its concentration calculates from calibration curve.Result shows, after photocatalysis 2h, reactive brilliant red degradation rate reaches 91%, and humic acid degradation rate reaches 95%, and therefore hydrotalcite/cuprous nano composite all has good photocatalysis performance to reactive brilliant red humic acid.
Compound concentration is the nitrogen standard liquid solution of 5mg/L and the phosphorus standard liquid 250mL of 0.5mg/L respectively, and be placed in two conical flasks, 0.25g hydrotalcite/cuprous nano composite is added in conical flask, photocatalytically carry out reaction 2h, every 20min sampling, centrifugal, get supernatant and use " the mensuration alkaline chitinase of water quality total nitrogen clears up ultraviolet spectrophotometry " (GB11894-89) and " the mensuration ammonium molybdate spectrophotometric method of water quality total phosphorus " (GB11893-89) method to carry out measuring the concentration of total nitrogen and total phosphorus respectively.Result shows, after hydrotalcite/cuprous nano composite reaction 2h, nitrogen removal rate is 70%, and total tp removal rate is 92%, and therefore hydrotalcite/cuprous nano composite can control body eutrophication well.
Hydrotalcite/cuprous oxide composite, except in algae process, measures total hardness, Al concentration, total nitrogen, total phosphorus and content of organics in solution before and after photocatalysis.Result shows, hydrotalcite/cuprous oxide composite on total hardness, Al concentration, total nitrogen and content of organics in solution without impact, and can 90% phosphorus in adsorbed water body.With reference to shown in accompanying drawing 4, the present embodiment hydrotalcite/cuprous nano composite is to the removal effect of organic matter and inorganic matter.
Embodiment 4
The ratio being 1:2.25 in the mol ratio of Schweinfurt green and sodium thiosulfate gets 500mL 0.275mol/L Schweinfurt green in conical flask, slowly add 562mL 0.55mol/L hypo solution, add 34.3g hydrotalcite and stir 35min, add 6.6g glucose again to stir, the sodium hydroxide solution of 576mL 0.55mol/L is slowly added under ultrasound condition, temperature is at 30-50 DEG C, and ultrasonic 35min, centrifugal, washing, 60 DEG C of oven dry obtain hydrotalcite/cuprous nano composite.
Embodiment 5
The ratio being 1:2.5 in the mol ratio of Schweinfurt green and sodium thiosulfate gets 1000mL 0.3mol/L Schweinfurt green in conical flask, slowly add 1250mL 0.6mol/L hypo solution, add 86.0g hydrotalcite and stir 40min, add 16.5g glucose again to stir, the sodium hydroxide solution of 1306mL 0.6mol/L is slowly added under ultrasound condition, temperature is at 30-50 DEG C, and ultrasonic 40min, centrifugal, washing, 60 DEG C of oven dry obtain hydrotalcite/cuprous nano composite.The concrete data of embodiment 1-5 performance characterization are in table 1:
Table 1 different hydrotalcite/cuprous nano composite is to the removal effect of various pollutant
Claims (10)
1. hydrotalcite/cuprous nano composite, is characterized in that adopting following methods preparation:
In the mixed aqueous solution of Schweinfurt green and sodium thiosulfate, add hydrotalcite stir, then add glucose and stir evenly rear leaving standstill, under ultrasonic agitation condition, add sodium hydroxide solution, centrifugal, washing, dry and obtain hydrotalcite/cuprous nano composite.
2. hydrotalcite/cuprous nano composite as claimed in claim 1, is characterized in that the molar concentration of Schweinfurt green and sodium thiosulfate in described mixed aqueous solution is respectively 0.2 ~ 0.3mol/L and 0.4 ~ 0.6mol/L.
3. hydrotalcite/cuprous nano composite as claimed in claim 1, is characterized in that the quality of described hydrotalcite accounts for 25 ~ 35% of Schweinfurt green and sodium thiosulfate gross mass.
4. hydrotalcite/cuprous nano composite as claimed in claim 1, adding hydrotalcite mixing time described in it is characterized in that is 20 ~ 40min.
5. hydrotalcite/cuprous nano composite as claimed in claim 1, is characterized in that the consumption of described glucose accounts for 4 ~ 5% of Schweinfurt green, sodium thiosulfate and hydrotalcite gross mass.
6. hydrotalcite/cuprous nano composite as claimed in claim 1, it is characterized in that the molar concentration of described sodium hydroxide solution is 0.4 ~ 0.6mol/L, consumption accounts for 8 ~ 9% of Schweinfurt green, sodium thiosulfate and hydrotalcite gross mass.
7. hydrotalcite/cuprous nano composite as claimed in claim 1, is characterized in that the described ultrasonic agitation time is 20 ~ 40min.
8. hydrotalcite/cuprous nano composite as claimed in claim 1, is characterized in that described bake out temperature is 50 ~ 60 DEG C.
9. the hydrotalcite according to claim 1/application of cuprous nano composite in water treatment.
10. the hydrotalcite according to claim 1/application of cuprous nano composite in wawter bloom process.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104261547A (en) * | 2014-10-10 | 2015-01-07 | 武汉工程大学 | Hydrotalcite magnetite composite water treatment material |
| CN104857990A (en) * | 2015-04-29 | 2015-08-26 | 武汉工程大学 | Magnetite hydrotalcite/cuprous oxide composite photocatalyst and preparation and applications thereof |
| CN110078186A (en) * | 2019-05-17 | 2019-08-02 | 上海大学 | A kind of dual-functional nanometer removes the preparation method and application of algae material |
| CN110496624A (en) * | 2019-08-22 | 2019-11-26 | 四川建筑职业技术学院 | A kind of composite material and preparation method for sewage treatment |
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| WO2009014392A2 (en) * | 2007-07-26 | 2009-01-29 | Lg Chem, Ltd. | Preparation method of copper particle composition |
| CN103372434A (en) * | 2012-04-27 | 2013-10-30 | 陈金毅 | Preparation method and application of rectorite/cuprous oxide nanocomposite |
| CN103623821A (en) * | 2013-11-28 | 2014-03-12 | 常州大学 | Method for preparing supported cuprous oxide catalyst |
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2014
- 2014-10-10 CN CN201410534656.1A patent/CN104226239A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2009014392A2 (en) * | 2007-07-26 | 2009-01-29 | Lg Chem, Ltd. | Preparation method of copper particle composition |
| CN103372434A (en) * | 2012-04-27 | 2013-10-30 | 陈金毅 | Preparation method and application of rectorite/cuprous oxide nanocomposite |
| CN103623821A (en) * | 2013-11-28 | 2014-03-12 | 常州大学 | Method for preparing supported cuprous oxide catalyst |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104261547A (en) * | 2014-10-10 | 2015-01-07 | 武汉工程大学 | Hydrotalcite magnetite composite water treatment material |
| CN104261547B (en) * | 2014-10-10 | 2016-03-02 | 武汉工程大学 | Hydrotalcite magnetite compound material for water treatment |
| CN104857990A (en) * | 2015-04-29 | 2015-08-26 | 武汉工程大学 | Magnetite hydrotalcite/cuprous oxide composite photocatalyst and preparation and applications thereof |
| CN110078186A (en) * | 2019-05-17 | 2019-08-02 | 上海大学 | A kind of dual-functional nanometer removes the preparation method and application of algae material |
| CN110496624A (en) * | 2019-08-22 | 2019-11-26 | 四川建筑职业技术学院 | A kind of composite material and preparation method for sewage treatment |
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Application publication date: 20141224 |