CN105858787B - A kind of dephosphorization filler X-Phos matrix and preparation method thereof - Google Patents

A kind of dephosphorization filler X-Phos matrix and preparation method thereof Download PDF

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Publication number
CN105858787B
CN105858787B CN201610269334.8A CN201610269334A CN105858787B CN 105858787 B CN105858787 B CN 105858787B CN 201610269334 A CN201610269334 A CN 201610269334A CN 105858787 B CN105858787 B CN 105858787B
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China
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matrix
phos
filler
water
attapulgite clay
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CN201610269334.8A
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Chinese (zh)
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CN105858787A (en
Inventor
柯凡
李文朝
周峰
潘继征
何延召
范帆
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中国科学院南京地理与湖泊研究所
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/281Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/288Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents

Abstract

The present invention relates to a kind of dephosphorization filler X-Phos matrix and preparation method thereof, can be applied to material for water treatment preparation field.The main of the filler prepares raw material are as follows: CaO2, attapulgite clay, adhesive and water surplus.The preparation method comprises the following steps: above-mentioned various raw material to be carried out to the pretreatment of particular step respectively, then uniformly mixed according to special ratios, and add water and stir;The certain cylindrical body particle of diameter, height is made in the slurry being stirred;It is air-dried under certain temperature after molding.Raw material of the present invention easily obtain, finished product phosphor-removing effect efficient stable, can be used for the deep phosphorous removal of the systems such as artificial swamp, biofilter, tail water purification.

Description

A kind of dephosphorization filler X-Phos matrix and preparation method thereof

Technical field

The present invention relates to Water Pollution Control Engineering fields, and in particular, to one kind is used for water body dephosphorized filler X-Phos base Matter and preparation method thereof.

Background technique

Wawter bloom or red tide as caused by water eutrophication will lead to deteriorating water quality, and aquatic ecosystem is seriously broken It is bad, and then economic development, social stability and human health can be threatened.Water eutrophication is primarily due to Water, phosphorus etc. Caused by nutriment is more, and wherein phosphorus is considered as the key for controlling eutrophication, therefore studies the application of dephosphorization filler It is of great significance to the control of water eutrophication.Sewage relatively low to non-industrial wastewater, that is, pollution level at present, it is raw The technologies such as object filter tank, artificial swamp are more common, and in such technology, the selection of filler is one of key problem, is directly affected The removal effect of nitrogen phosphorus.At present in the filler for being applied to sewage treatment, majority there are dephosphorization mechanism is single, ask by low efficiency etc. Topic, it is less to deep phosphorous removal, quick matrix report.

Wang Changbo et al. is that raw material invents one kind and can reduce phosphorus content in water body with Fe, active carbon and some catalytic elements The filler (application number 201310315294.2) that coloration in removal water body can be synchronized again, has achieved the purpose that synchronous decoloration dephosphorization, But manufacturing process is complex, higher to temperature requirement, and Determination of multiple metal elements, Yi Yinqi secondary pollution are contained in catalytic elements. Construction waste cement brick is crushed by Liu Chaoxiang etc., little particle is made as dephosphorization adsorbent (application number 201310420535.X), Make construction waste resource utilization, but its dephosphorization principle is mainly physical absorption, under certain condition may after adsorption saturation Phosphorus is discharged into water body.Liu Zhijun etc. has invented a kind of renewable modified haydites of book structure dephosphorization filler (application number 201510190580.X), has reuse ability, but more demanding to pH in preparation process, and filler saturated extent of adsorption phase It is 20 ~ 25mg/g to lower.Li Xudong etc. using flyash, gypsum, ardealite, cement, aluminium powder and water as raw material according to a certain ratio A kind of reinforced sewage dephosphorization filler (application number 201410005588.X) is prepared, but dephosphorization mechanism is equally with physical absorption It is main, phosphorus removal functional is just lost after saturation to be adsorbed, in order to solve this problem, Li Xudong etc. improves filler, invents A kind of novel polymeric aluminium chloride dephosphorization filler (application number 201410784847.3) makes phosphorus adsorption function efficient stable, but raw material The weight proportion of middle polyaluminium chloride is excessive, up to 60% ~ 90%, easily causes Al content in water body excessive.

Applicant's early-stage study shows natural attapulgite clay internal porous road, and large specific surface area has good absorption It can be shown efficient phosphorus adsorption function after 700 DEG C or more heat treatment by performance.Ca2+It can be raw with the phosphorus reaction in water body At precipitating, wherein calcium hydroxy phosphate is the most stable, so when containing Ca and P ingredient in water body, it finally mostly can be with di Calcium speciation exists.Calcium hydroxy phosphate is a kind of novel inorganic high molecular material, and calcium constituent is mainly with calcium hydroxy phosphate crystalline substance in human body The form of body exists, and will not cause damages influence on environment on human health in the presence of it is in water body, can be considered a kind of life State friendly substance.So can not only guarantee the high efficiency of dephosphorization but also not when containing attapulgite clay and Ca in certain filler Any adverse effect can be caused to ecological environment.

Summary of the invention

To achieve the effect that deep phosphorous removal, the object of the present invention is to provide a kind of dephosphorization filler X-Phos matrix and its preparations Method, X are defined as " removing ", and Phos represents phosphate, utilizes CaO2, attapulgite clay, adhesive and water surplus be by certain ratio Example, which be mixed, is pressed into cylindrical pellet, can be used as dephosphorization filler.Primary raw material: CaO2Powder (CaO2Content 50% ~ 60%), attapulgite clay, adhesive, water.Filler weight constituent are as follows: CaO2Powder 50% ~ 55%, natural attapulgite clay 5% ~ 10%, modified attapulgite clay 30% ~ 35%, adhesive 3% ~ 6%, water 3% ~ 6%.It is cylindrical body when filler finally forms, bottom surface is straight Diameter is 5 ~ 50mm, is highly 5 ~ 50mm.Maximum phosphorus adsorption capacity is 200mg/g.

The adhesive is one or both of sodium metasilicate, polyvinyl alcohol gluing agent.

In addition to above-mentioned primary raw material, a small amount of MgO can also be added in filler manufacturing process2, active carbon, the objects such as flyash Matter.MgO2, active carbon or flyash content be 1%.

Application method: the present invention be directed to the advanced treatings of phosphorus, so to be used cooperatively with other type fillers when use, To reach to water quality comprehensive purifying effect.Usage amount is preferably the 1% of total filler dosage.

Specific production step:

(1) CaO2Powder and attapulgite clay cross 200 mesh screens.

(2) part attapulgite clay is subjected to 800 DEG C of high temperature modified processing.

(3) under room temperature, each component is mixed by a certain percentage.

(4) by the slurry being stirred be pressed into cylindrical body particle under certain temperature air-dry.

Dephosphorization mechanism: natural attapulgite clay has good adsorptivity and water swelling, after 700 DEG C or more heat treatments Phosphorus absorption property can further enhance;CaO2Powder, which meets water, can react generation Ca+, generation precipitating can be reacted with phosphate radical;It is natural recessed Convex stick clay water-swellable will increase CaO2With the contact area of water, in being total to for natural attapulgite clay and modified attapulgite clay With under suction-operated, phosphate radical can constantly with Ca+Reaction generates di calcium precipitate, and the function of concave convex rod is " trade and investment promotion ", CaO2Function be " taking root ", achieve the effect that deep phosphorous removal.

Advantage:

(1) raw materials are environmentally friendly material, will not cause secondary pollution.

(2) dephosphorization is carried out under the comprehensive function of two kinds of approach of physical absorption and chemical reaction, it is ensured that the high efficiency of dephosphorization.

(3) filler production cost is low, the period is short, mechanization degree is high, can bear water flow and impact for a long time, engineering is facilitated to answer With.

(4) CaO2It is reacted with water and produces O2, dephosphorization while can increase content of oxygen dissolved in water.

Specific embodiment

Embodiment 1: laboratory Static simulation test I

In laboratory, configuration potassium dihydrogen phosphate makes its TP 1.2mg/L, selects cylindrical body filler, and diameter 5mm is high 10mm, filler preparation step is the same as above-mentioned, material composition weight proportion: CaO2Powder 50%, natural attapulgite clay 8%, modification are recessed Convex stick clay 31%, sodium metasilicate 1%, polyvinyl alcohol gluing agent 3%, water 4%, MgO2 1%, active carbon 1%, flyash 1%.Take 1L phosphoric acid Dihydro potassium solution adds two fillers, and water sampling is detected after 8h, the results are shown in Table 1.

1 water quality of table compares

pH TP Initial water quality 6.8 1.24mg/L Water quality after 8h 10.5 0.21mg/L

Embodiment 2: laboratory Static simulation test II

In laboratory, configuration potassium dihydrogen phosphate makes its TP 1.2mg/L, selects cylindrical body filler, and diameter 10mm is high 20mm, filler preparation step is the same as above-mentioned, material composition weight proportion: CaO2Powder 50%, natural attapulgite clay 6%, modification are recessed Convex stick clay 30%, active carbon 5%, sodium metasilicate 1%, polyvinyl alcohol gluing agent 4%, water 4%.5L potassium dihydrogen phosphate is taken, adds two Filler, water sampling is detected after 12h, the results are shown in Table 2.

2 water quality of table compares

pH TP Initial water quality 6.9 1.22mg/L Water quality after 8h 9.8 0.20mg/L

Embodiment 3: laboratory matrix dephosphorization experiment I

In laboratory, configuration potassium dihydrogen phosphate makes its TP 1.2mg/L, selects cylindrical body filler, and diameter 10mm is high 50mm, filler preparation step is the same as above-mentioned, material composition weight proportion: CaO2Powder 52%, natural attapulgite clay 6%, modification are recessed Convex stick clay 32%, sodium metasilicate 2%, polyvinyl alcohol gluing agent 2%, water 6%.

Using internal diameter 10cm, the Organic glass column of high 20cm puts filler 20g as reaction vessel in reactor, keeps Inflow 50L/d, water sampling is detected after three days, the results are shown in Table 3.

3 water quality of table compares

pH TP Influent quality 6.8 1.22mg/L Effluent quality 10.0 0.26mg/L

Embodiment 4: laboratory matrix dephosphorization experiment II

In laboratory, configuration potassium dihydrogen phosphate makes its TP 1.2mg/L, selects cylindrical body filler, and diameter 20mm is high 20mm, filler preparation step is the same as above-mentioned, material composition weight proportion: CaO2Powder 51%, natural attapulgite clay 10%, modification are recessed Convex stick clay 31%, flyash 1%, sodium metasilicate 2%, polyvinyl alcohol gluing agent 1%, water 4%.

Using internal diameter 10cm, the Organic glass column of high 20cm puts filler 30g as reaction vessel in reactor, keeps Inflow 80L/d, water sampling is detected after three days, the results are shown in Table 4.

4 water quality of table compares

pH TP Influent quality 6.8 1.18mg/L Effluent quality 10.3 0.23mg/L

Embodiment 5: artificial swamp simulated experiment

Select cylindrical body filler, diameter 50mm, high 5mm, filler material composition proportion: CaO2Powder 52%, natural concave convex rod Clay 5%, modified attapulgite clay 35%, sodium metasilicate 2%, polyvinyl alcohol gluing agent 3%, water 3%.It is used for obtained filler to simulate people Purification of the work wetland to sanitary sewage, dosage are the 1% of total filler weight.Water sampling is monitored after wetland is stable, as a result It is shown in Table 5.

5 Inlet and outlet water water quality of table

pH TP Initial water inlet 7.8 2.00mg/L No X-Phos matrix water outlet 8.1 0.28mg/L There is the water outlet of X-Phos matrix 8.9 0.12mg/L

Embodiment 6: artificial swamp engineer application

Select cylindrical body filler, diameter 40mm, high 30mm, filler material composition proportion: CaO2Powder 55%, it is natural concave-convex Stick clay 7%, modified attapulgite clay 30%, sodium metasilicate 1%, polyvinyl alcohol gluing agent 2%, water 4%, active carbon 1%.By obtained filler For in the artificial swamp demonstration project of somewhere, for the artificial swamp applied to the purification to bad V class river water, dosage to be total filler weight The 1% of amount.Water sampling is monitored after wetland is stable, the results are shown in Table 6.

6 Inlet and outlet water water quality of table

pH TP Influent quality 7.8 1.92mg/L Effluent quality 8.3 0.13mg/L

Claims (7)

1. a kind of dephosphorization filler X-Phos matrix, which is characterized in that the dephosphorization filler X-Phos matrix components composition are as follows: CaO2 Powder 50% ~ 55%, natural attapulgite clay 5% ~ 10%, modified attapulgite clay 30% ~ 35%, adhesive 3% ~ 6%, water 3% ~ 6%;Institute It states matrix and also contains MgO2, one or more of active carbon or flyash.
2. dephosphorization filler X-Phos matrix according to claim 1, which is characterized in that the modified attapulgite clay is by day Right attapulgite clay carries out 800 DEG C and high temperature modified is prepared.
3. dephosphorization filler X-Phos matrix according to claim 1, which is characterized in that dephosphorization filler X-Phos matrix is Cylindrical body, basal diameter are 5 ~ 50mm, are highly 5 ~ 50mm, and maximum phosphorus adsorption capacity is 200mg/g.
4. dephosphorization filler X-Phos matrix according to claim 1, which is characterized in that the CaO2CaO in powder2Contain Amount 50% ~ 60%.
5. dephosphorization filler X-Phos matrix according to claim 1, which is characterized in that the adhesive is sodium metasilicate, gathers One or both of vinyl alcohol adhesive.
6. dephosphorization filler X-Phos matrix according to claim 1, which is characterized in that MgO2, active carbon or flyash Content is 1%.
7. a kind of preparation method of dephosphorization filler X-Phos matrix as described in claim 1, which is characterized in that specifically include with Lower step:
1) CaO2Powder and attapulgite clay cross 200 mesh screens;
2) the 800 DEG C of high temperature modified processing of progress of natural attapulgite clay are prepared into modified attapulgite clay;
3) under room temperature, each component is mixed in proportion;
4) it is air-dried after the slurry being stirred being pressed into cylindrical body particle.
CN201610269334.8A 2016-04-27 2016-04-27 A kind of dephosphorization filler X-Phos matrix and preparation method thereof CN105858787B (en)

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CN106430504B (en) * 2016-08-23 2018-02-09 安徽兴安电气设备股份有限公司 A kind of sanitary sewage dephosphorization agent
CN106946309A (en) * 2017-04-27 2017-07-14 安徽大学 A kind of oxygen sustained release, the preparation method and applications for inhaling phosphate material

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