CN101601990A - A kind of preparation method of effective environment friendly water body dephosphorizing material - Google Patents
A kind of preparation method of effective environment friendly water body dephosphorizing material Download PDFInfo
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- CN101601990A CN101601990A CNA2009101579595A CN200910157959A CN101601990A CN 101601990 A CN101601990 A CN 101601990A CN A2009101579595 A CNA2009101579595 A CN A2009101579595A CN 200910157959 A CN200910157959 A CN 200910157959A CN 101601990 A CN101601990 A CN 101601990A
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Abstract
A kind of preparation method of effective environment friendly water body dephosphorizing material.The present invention relates to the preparation method of a kind of low cost, efficient, environment friendly water body dephosphorizing material.Body eutrophication is one of important environmental problem of facing of present China, and the content that reduces P is the key of control body eutrophication.As the water body dephosphorized absorption method that is suitable for the most, face limitation such as dephosphorization material absorption property low (most below 30-40mg/g), cost height, preparation complexity.The natural water allophane that absorption property is strong is restricted at aspects such as distribution, exploitation and modification processing, and the method for existing artificial synthetic water allophane has limitation such as cost height or preparation condition harshness, is difficult to satisfy the needs of extensive use.The present invention at room temperature directly mixes cheap common silicate solutions by certain Al/Si ratio with aluminum salt solution mutually, stirred 2-24 hour, can prepare efficient, environmental protection, amorphous silicon-aluminum oxide material cheaply, its phosphorus removal property can be up to 80-100mg/g.
Description
Technical field
The present invention relates to the preparation method of water body dephosphorizing material.The present invention be more particularly directed to amorphous silicon aluminum oxide class water body dephosphorizing material efficient, environmental protection.
Background technology
Since 20 beginnings of the century, the discharging of a large amount of industrial wastewaters and sanitary sewage, applying quantity of chemical fertilizer increase and fertilizer loss have caused body eutrophication and have been on the rise.Body eutrophication has become one of global most important environmental problem.Eutrophication problem has appearred in the lake of China more than 50%.Body eutrophication can directly influence water quality on the one hand, and the harm people are healthy, on the other hand also can be by influencing health, the balanced growth of aquatic ecosystem, the sustainable development of remote-effects human society.Therefore, the control of body eutrophication has become the focus that people pay close attention to.Body eutrophication mainly is by due to N, the increase of P concentration in the water body.Studies show that, can not effectively control the eutrophication (Schindleret al.PNAS, 2008) of water body after the input of control N, and the content of minimizing P is the key (Carpenter, PNAS, 2008) of control body eutrophication.At present, water body dephosphorized technology mainly contains chemical precipitation method, bio-absorbable is removed method and absorption method.Factors such as synthesized environmental protection, cost, efficient consider that absorption method has become the water body dephosphorized method that is suitable for the most.
Using the absorption method dephosphorization mainly is the preparation of sorbing material.At present, people have inquired into multiple natural material or have adsorbed the phosphorus of removing in the water body through the natural material of physics, chemical modification and manually synthetic material.Most materials are the highest all below 30-40mg/g to the adsorbance of phosphorus in the existing report, and the material of adsorbance higher relatively (the about 100mg/g of high phosphorus adsorbance) is because preparation cost is higher or complicated process of preparation has certain limitation.Amorphous allophane specific surface is big, and absorption property is strong, and its application at environmental area has been subjected to people and has paid close attention to.Yet there is certain limitation in the natural water allophane at aspects such as distribution, exploitation and modification processing.Therefore, artificial synthetic water allophane and relevant nature research having caused people's attention thereof.Now disclosed allophane preparation method has: under control pH 5 conditions, with a certain amount of K
2SiO
3Solution is added dropwise to a certain amount of AlCl with the speed of 0.2mL/s
3Prepared in reaction allophane in the solution (Mora M L, Escudey C M, Galindo G G.Bol.Soc.Chil.Quim, 1994,39,237-243).Or with organic aluminium salt and organosilicate be blended in by a certain percentage 35 ℃ of reactions prepare over 1-2 days allophane (Lindner G G, Nakazawa H, Hayashi S.Microporous and MesoporousMaterials, 1998,21,381-386).Or with Na
4SiO
4Direct and the AlCl of solution
3Solution reaction, after the centrifugal washing of product again under 100 ℃ of hydrothermal fluid conditions the reaction 2 days, also can prepare allophane (Ohashi F, Wada S I, Suzuki M, et al.ClayMinerals, 2002,37,451-456).Or with organosilicate TEOS and Al (NO
3)
3Solution reaction, the suspension that generates was 95 ℃ of following heat treated 7 days, obtain allophane (Montagres-Pelletier E after the product washing, Bogenez S, Pelletier M, et al.Colloids and Surfaces A:Physicochem.Eng.Aspects, 2005,255,1-10).In addition, with Na
2SiO
3, NaAlO
2And CsNO
3Or CsOH by Na/Cs than 2.4 hybrid reactions also can obtain containing Cs allophane (Mon J, Deng Y, Flury M, et al.Microporous and Mesoporous Materials, 2005,86,277-286).The above-mentioned method for preparing allophane has limitation such as cost height (reagent costs an arm and a leg) or preparation condition harshness, and these are difficult to satisfy the needs to its extensive use.
Summary of the invention
The present invention aims to provide a kind of efficient, environmental protection, low cost and the simple amorphous silicon aluminum oxide of preparation method water body dephosphorizing material.
Method of the present invention relates at room temperature cheap common silicate solutions is directly mixed by certain Al/Si ratio mutually with aluminum salt solution, stirs 2-24 hour, can obtain amorphous silicon aluminum oxide water body dephosphorizing material after the centrifugal washing of product.
Said silicate can be Li
+, Na
+, K
+Deng water-soluble silicates such as alkali metal or quaternary ammonium ions.
Said aluminium salt can be to select in chloride, nitrate, sulfate or the acetate.
Said Al/Si than scope 0.2～2
Said mixing can be that two kinds of solution are directly mixed, and also can both be mixed friction speed mutually.
Using this method can be at the synthetic next time a large amount of amorphous silicon aluminum oxide water body dephosphorizing material of simple and easy condition.Preparation technology is simple for this method, and cost is low, and product is to the good and environmental protection of removal performance of phosphorus in the water body, and is easy to carry out physics, chemical modification and further improves its phosphorus removal property.In water body dephosphorized, can be used widely.
Application as the water systems'phosphorus adsorbent: the concentration range of phosphorus is at 1mg/L～10000mg/L in the water body; The pH value scope of water body is 3～10; The solid-to-liquid ratio scope of dephosphorization material and water body was at 1: 100～1: 10000.
Description of drawings
Fig. 1 is the X-ray diffracting spectrum of dephosphorization material of the present invention.
Fig. 2 is the pattern electromicroscopic photograph of dephosphorization material of the present invention.
Fig. 3 is the infrared absorption pattern of dephosphorization material of the present invention.
Fig. 4 is the thermomechanical curve of dephosphorization material adsorbed water body phosphorus of the present invention.
The specific embodiment
Embodiment 1: with the Na of distilled water configuration 1.6mol/L
2SiO
3The AlCl of solution 100mL and 0.3mol/L
3Solution 300mL, under stirring condition with Na
2SiO
3Solution directly adds AlCl fast
3In the solution, continue stirring 12 hours, the centrifugal washing of product back obtains the amorphous silicon aluminum oxide like allophane 60 ℃ of oven dry down, grindings.
Fig. 1 is the X-ray diffracting spectrum of amorphous sieve and silica-sesquioxide, and 0.34nm and 0.22nm diffraction maximum are the characteristic diffraction peak of allophane among the figure, wherein the characteristic diffraction peak intensity of 0.22nm a little less than, illustrate that product has like the allophane structure.Fig. 2 is the pattern electromicroscopic photograph of amorphous sieve and silica-sesquioxide, and product mainly is a graininess, and size is in several nanometer to tens nanometers.Fig. 3 is the infrared absorption pattern of amorphous sieve and silica-sesquioxide, among the figure 3448 and 1642cm
-1Be the OH absworption peak of adsorbed water, 2369cm
-1Be CO
2Absworption peak, 1044,889,570 and 456cm
-1Characteristic absorption peak for allophane.
Take by weighing amorphous silicon aluminum oxide powder 0.05g in the 50mL centrifuge tube, add 30mL respectively and contain 0.1,0.2,0.5,1,2,5,10,20,50 and 100mmol/L KH
2PO
4With the mixed solution of 0.1mol/L KCl, transfer solution to pH5.5 ± 0.1 with HCl or KOH, after at room temperature vibrating 24 hours, the content of phosphorus in the supernatant is measured in centrifugation, calculates the adsorbance of amorphous silicon aluminum oxide to phosphorus with minusing.The isothermal adsorption curve is seen Fig. 4, and the amorphous silicon aluminum oxide of this method preparation can reach about 100mg/g to the maximal absorptive capacity of phosphorus, is better than the performance of most dephosphorization materials of natural allophane and other report.
Embodiment 2: the Al (NO of configuration 0.3mol/L
3)
3The K of solution 300mL and 1.6mol/L
2SiO
3Solution 60mL.Under stirring condition with K
2S
iO
3Solution directly adds Al (NO
3)
3Solution continues to stir 24 hours, and the centrifugal washing of product, oven dry obtain the amorphous silicon aluminum oxide.Product to the adsorption treatment of phosphorus with embodiment 1.
Claims (9)
1, a kind of preparation method of effective environment friendly water body dephosphorizing material is characterized in that: described material environment friendly, and phosphorus removal property is good, and the preparation method is simple, and its preparation and phosphorus removing method are as follows:
1) silicate solutions is directly mixed by certain Al/Si ratio mutually with aluminum salt solution, stirred 2-24 hour, can obtain the capable sieve and silica-sesquioxide of amorphous after the centrifugal washing of product, the chemical composition that generates product is xAl
2O
3YSiO
2, 0.1＜x/y＜1 wherein.
2) dephosphorization material with preparation adds in the content of phosphorus-containing water body, and it is centrifugal after 0.5-24 hour vibrate, and the residual quantity of phosphorus in the clear liquid analytically is with the adsorbance of minusing calculating phosphorus.
2, the described preparation method of claim 1 is characterized in that: said silicate can be Li
+, Na
+, K
+Deng water-soluble silicates such as alkali metal or quaternary ammonium ions.
3, the described preparation method of claim 1 is characterized in that: said aluminium salt can be to select in chloride, nitrate, sulfate or the acetate.
4, the described preparation method of claim 1 is characterized in that: said Al/Si than scope 0.2～2
5, the described preparation method of claim 1 is characterized in that: said mixing can be direct mixing, also mixes mutually with friction speed.
6, the described preparation method of claim 1 is characterized in that: as the application of water systems'phosphorus adsorbent.
7, the described phosphorus removing method of claim 1, it is characterized in that: the concentration range of phosphorus is at 1mg/L～10000mg/L in the water body.
8, the described phosphorus removing method of claim 1 is characterized in that: the pH value scope of water body is 3～10.
9, the described phosphorus removing method of claim 1 is characterized in that: the solid-to-liquid ratio scope of dephosphorization material and water body was at 1: 100～1: 10000.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104525137A (en) * | 2014-12-04 | 2015-04-22 | 安徽农业大学 | Defluorination biological adsorbent made by tea residue modification, preparation method and application thereof |
| CN106219692A (en) * | 2016-08-26 | 2016-12-14 | 上海润溪环保科技有限公司 | A kind of electrochemical stone as water body dephosphorized filtrate and preparation method thereof |
| CN108569773A (en) * | 2018-04-22 | 2018-09-25 | 扬州工业职业技术学院 | A kind of cultivation water scavengine agent |
| CN109248652A (en) * | 2018-08-30 | 2019-01-22 | 中国科学院广州地球化学研究所 | A kind of diatomite with multi-stage artery structure/allophane composite material and preparation method |
-
2009
- 2009-07-20 CN CNA2009101579595A patent/CN101601990A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104525137A (en) * | 2014-12-04 | 2015-04-22 | 安徽农业大学 | Defluorination biological adsorbent made by tea residue modification, preparation method and application thereof |
| CN106219692A (en) * | 2016-08-26 | 2016-12-14 | 上海润溪环保科技有限公司 | A kind of electrochemical stone as water body dephosphorized filtrate and preparation method thereof |
| CN106219692B (en) * | 2016-08-26 | 2022-10-21 | 上海润溪环保科技有限公司 | Tourmaline used as water body dephosphorization filter material and preparation method thereof |
| CN108569773A (en) * | 2018-04-22 | 2018-09-25 | 扬州工业职业技术学院 | A kind of cultivation water scavengine agent |
| CN109248652A (en) * | 2018-08-30 | 2019-01-22 | 中国科学院广州地球化学研究所 | A kind of diatomite with multi-stage artery structure/allophane composite material and preparation method |
| CN109248652B (en) * | 2018-08-30 | 2020-04-07 | 中国科学院广州地球化学研究所 | Diatomite/allophane composite material with hierarchical pore structure and preparation method thereof |
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Application publication date: 20091216 |