CN102872819A - Composite adsorbing material for removing nitrate from water and preparation method of same - Google Patents
Composite adsorbing material for removing nitrate from water and preparation method of same Download PDFInfo
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- CN102872819A CN102872819A CN2012103221613A CN201210322161A CN102872819A CN 102872819 A CN102872819 A CN 102872819A CN 2012103221613 A CN2012103221613 A CN 2012103221613A CN 201210322161 A CN201210322161 A CN 201210322161A CN 102872819 A CN102872819 A CN 102872819A
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Abstract
The invention discloses a composite adsorbing material for removing nitrate from water, and a preparation method of the composite adsorbing material. The composite adsorbing material is particularly applicable to perform advanced treatment on sewage containing nitrate with high concentration. The eggshell film-micropore ceramic composite adsorbing material can be prepared by combining modified micropore ceramic with an eggshell film material; in addition, the particular application method of the composite adsorbing material is very simple and comprises the steps of adding 10 g of composite adsorbing material to 200 mL of sewage with the nitrate concentration of 5 mg/L, adjusting pH to be 6.5-7.5, and standing and absorbing for 2-4h; the nitrate content in effluent is stable; and the effluent reaches the second level of Environmental Quality Standard for Surface Water. The composite adsorbing material has the characteristics that the composite adsorbing material is high in adsorption efficiency, simple and convenient to operate, low in cost and wide in application scope, and the effluent is stable and comes up to the standard.
Description
Technical field
The present invention is a kind of composite adsorbing material of removing nitrate anion in the water and preparation method thereof, is specifically related to be rich in the processing of the sewage of nitrate anion, belongs to the dirty water decontamination handles field in the environmental protection.
Background technology
In recent years, the concentration of nitrate anion in water body constantly increases.The nitrate of water body middle and high concentration is mainly derived from agrochemical, the pond system of corruption and the excreta of animal etc.Nitrate itself is safe from harm to the mankind, partly is reduced into nitrite behind the human body under the effect of reducing bacteria but nitrate is ingested.Hemoglobin reaction in nitrite and the blood generates ferrihemoglobin, thereby affects blood to the transmittability of oxygen.And nitrogen excessive in the water body also can cause the body eutrophications such as ocean and lake, therefore must the strict content of controlling the nitrate anion in the water body.
At present, development the multiple water treatment denitride technology, mainly contain hyperfiltration, electro-osmosis method, chemical reduction method, biological denitrificaion method and absorption method etc.What generally adopt on the engineering is chemical reduction method, and the medicament expense that this method is used need specific medicament delivery device, and energy consumption is very large with high.Hyperfiltration needs high-tension apparatus, and former water use efficiency only has 75～80%, and usefulness, and permeable membrane needs periodic cleaning.Electro-osmosis method, the shortcomings such as aeration effect that have in its process that electric weight and consumption of electrode are large, cost is relatively high, overflow in the electric osmose process, it is not yet used in Practical Project on a large scale.And bioanalysis has efficient characteristics, but investment is large, and process is long.Thereby said method all is not very good.
Micropore ceramics refers to that its aperture is generally micron order or submicron order at the inner or surperficial ceramic body that contains a large amount of openings or the small pore of remaining silent of pottery.It is a kind of structural ceramics of functional form.Micropore ceramics has adsorptivity, corrosion resistance, Environmental compatibility, biocompatibility etc., is widely used in the filtration of various liquid, filtration and fixed biologically zymophore and the biocompatibility carrier of gas, has obtained a large amount of application in environmental project.And the micropore ceramics of load cetrimonium bronmide improves a lot to the clearance to nitrate anion in the water.
Egg shell membrane is the middle film that forms that is present between eggshell and the albumen, is highly cross-linked water-insoluble fibrous protein, is a kind of biologically active sorbing material of macroporous type, has larger specific area, thereby shows good absorption property.
The present invention utilizes a kind of egg shell membrane-micropore ceramics composite adsorbing material, provide a kind of degree of depth effectively to process the new approaches that contain the nitrate anion water body, take full advantage of that the egg shell membrane specific area is large, micropore ceramics is as the characteristics such as stability of carrier, successfully manage the situation that sewage is rich in nitrate anion, have broad application prospects.
Summary of the invention
The shortcoming of with high investment, the high energy consumption that the present invention be directed to that the chemical reduction method that generally adopts on the nowadays engineering exists and a kind of new processing method of proposing.The present invention have the adsorption efficiency height, simple to operation, cost is low, energy consumption is low, stable water outlet reach the country characteristics such as " water environment quality standards ".
The objective of the invention is to be achieved through the following technical solutions:
(1) gets first common Fresh Egg eggshell 50～100g, with tweezers egg shell membrane is peeled from eggshell, join the 100mL mass fraction and be soak 2h in 15～20% the oxalic acid solution after, in 5～10% the NaOH that the 100mL mass fraction is, soak 1h, be dried to constant weight, grind into powder with putting into baking oven (50～60 ℃) after the distilled water washes clean;
(2) get again above-mentioned egg shell membrane powder 10～15g, mix jointly placing constant-temperature table with micropore ceramics 40～50g after the modification, at 20～30 ℃, fully behind the vibration contact 3h, leave standstill 30min under the 200r/min condition;
(3) get at last mixed liquor after leaving standstill, with the physiological saline washing, wash-out does not stick to the egg shell membrane on the micropore ceramics, makes egg shell membrane-micropore ceramics composite adsorbing material.
The method of modifying of described micropore ceramics, its method is:
(1) gets first 80～100g micropore ceramics as raw material, utilize Ultrasonic Cleaning 2～4 times, behind 60～80 ℃ of lower oven dry 3～5h, be crushed to 100 orders;
(2) then get above-mentioned micropore ceramics 20～30g, put into container, add the cetrimonium bronmide solution of 30～40ml, stirring reaction 1～2h;
(3) mixture is put into baking oven (65～75 ℃), be dried to constant weight, make the modified micropore pottery.
The principle of the inventive method is: the egg shell membrane with huge specific area and good adsorption properties, be adsorbed on the micropore ceramics, and as the micropore ceramics of carrier, on it again load cetrimonium bronmide, can greatly strengthen the adsorption capacity to nitrate anion in the water.Therefore this composite by the combination of several materials, is mutually promoted, and has realized the effect of 1+1＞2, shows the adsorption capacity good to nitrate ion.
Concrete application process of the present invention is: get the composite adsorbing material 10g for preparing, the nitrate concentration of rendering to 200mL is in the sewage of 50mg/L, regulating the pH value is 6.5～7.5, leave standstill, adsorbed 2～4 hours, the concentration that records nitrate anion in the sewage all below 1.0mg/L, reaches " water environment quality standard " secondary standard.Concrete application process is very simple.
The beneficial effect of the inventive method is:
The composite adsorbing material of nitrate anion is a kind of novel method in the water of the present invention, on the one hand, has overcome the present chemical reduction method high energy consumption of commonly using, expensive shortcoming, so that no longer only rely on conventional method for the processing of nitrate anion in the sewage from now on; Sorbing material adsorption efficiency of the present invention is high on the other hand, material is simple, compared to the method for processing before nitrate anion in the water, have absorption more thoroughly, stable water outlet is up to standard, can not produce the advantage such as secondary pollution.
The specific embodiment
The technical solution used in the present invention is as follows:
Get first 80～100g micropore ceramics as raw material, utilize Ultrasonic Cleaning 2～4 times, behind 60～80 ℃ of lower oven dry 3～5h, be crushed to 100 orders; Then get above-mentioned micropore ceramics 20～30g, put into container, six alkyl trimethylamine solutions in the bromination of adding 30～40mL, stirring reaction 1～2h; Mixture is put into baking oven (65～75 ℃), in dry to constant weight, makes the modified micropore pottery:
Get common Fresh Egg eggshell 50～100g, with tweezers egg shell membrane is peeled from eggshell, join the 100mL mass fraction and be soak 2h in 15～20% the oxalic acid solution after, in 5～10% the NaOH that the 100mL mass fraction is, soak 1h, be dried to constant weight, grind into powder with putting into baking oven (50～60 ℃) after the distilled water washes clean; Get again above-mentioned egg shell membrane powder 10～15g, mix jointly placing constant-temperature table with micropore ceramics 40～50g after the modification, at 20～30 ℃, fully behind the vibration contact 3h, leave standstill 30min under the 200r/min condition; Get at last the mixed liquor after leaving standstill, with the physiological saline washing, wash-out does not stick to the egg shell membrane on the micropore ceramics, makes egg shell membrane-micropore ceramics composite adsorbing material.
Example 1
Get first the 80g micropore ceramics as raw material, utilize Ultrasonic Cleaning 2 times, behind 60 ℃ of lower oven dry 3h, be crushed to 100 orders; Then get above-mentioned micropore ceramics 20g, put into container, add the cetrimonium bronmide solution of 30ml, stirring reaction 1h; Mixture is put into baking oven (65 ℃), be dried to constant weight, make the modified micropore pottery;
Get common Fresh Egg eggshell 50g, with tweezers egg shell membrane is peeled from eggshell, join the 100mL mass fraction and be soak 2h in 15% the oxalic acid solution after, in 5% the NaOH that the 100mL mass fraction is, soak 1h, be dried to constant weight, grind into powder with putting into baking oven (50 ℃) after the distilled water washes clean; Get again above-mentioned egg shell membrane powder 10g, mix jointly placing constant-temperature table with micropore ceramics 40g after the modification, at 20 ℃, fully behind the vibration contact 3h, leave standstill 30min under the 200r/min condition; Get at last the mixed liquor after leaving standstill, with the physiological saline washing, wash-out does not stick to the egg shell membrane on the micropore ceramics, makes egg shell membrane-micropore ceramics composite adsorbing material.
Get the composite adsorbing material 10g in the example 1, the nitrate concentration of rendering to 200mL is in the sewage of 50mg/L, and regulating the pH value is 6.5, leave standstill, adsorbed 2 hours, the concentration that records nitrate anion in the sewage is 1.0mg/L, adsorption efficiency reaches 98%, reaches the surface water environment quality secondary standard.
Example 2
Get first the 90g micropore ceramics as raw material, utilize Ultrasonic Cleaning 3 times, behind 70 ℃ of lower oven dry 4h, be crushed to 100 orders; Then get above-mentioned micropore ceramics 25g, put into container, add the cetrimonium bronmide solution of 35ml, stirring reaction 1.5h; Mixture is put into baking oven (70 ℃), be dried to constant weight, make the modified micropore pottery;
Get common Fresh Egg eggshell 75g, with tweezers egg shell membrane is peeled from eggshell, join the 100mL mass fraction and be in 20% the oxalic acid solution and soak 2h jin, in 10% the NaOH that the 100mL mass fraction is, soak 1h, be dried to constant weight, grind into powder with putting into baking oven (55 ℃) after the distilled water washes clean; Get again above-mentioned egg shell membrane powder 15g, mix jointly placing constant-temperature table with micropore ceramics 45g after the modification, at 25 ℃, fully behind the vibration contact 3h, leave standstill 30min under the 200r/min condition; Get at last the mixed liquor after leaving standstill, with the physiological saline washing, wash-out does not stick to the egg shell membrane on the micropore ceramics, makes egg egg shell membrane-micropore ceramics composite adsorbing material.
Get the composite adsorbing material 10g in the example 2, the nitrate concentration of rendering to 200mL is in the sewage of 50mg/L, and regulating the pH value is 7.0, leave standstill, adsorbed 3 hours, the concentration that records nitrate anion in the sewage is 0.37mg/L, adsorption efficiency reaches 99.26%, reaches the surface water environment quality secondary standard.
Example 3
Get first the 100g micropore ceramics as raw material, utilize Ultrasonic Cleaning 4 times, behind 80 ℃ of lower oven dry 5h, be crushed to 100 orders; Then get above-mentioned micropore ceramics 30g, put into container, add the cetrimonium bronmide solution of 40mL, stirring reaction 2h; Mixture is put into baking oven (75 ℃), be dried to constant weight, make the modified micropore pottery;
Get common Fresh Egg eggshell 100g, with tweezers egg shell membrane is peeled from eggshell, join the 100mL mass fraction and be soak 2h in 20% the oxalic acid solution after, in 10% the NaOH that the 100mL mass fraction is, soak 1h, be dried to constant weight, the wood of pulverizing with putting into baking oven (60 ℃) after the distilled water washes clean; Get again above-mentioned egg shell membrane powder 15g, mix jointly placing constant-temperature table with micropore ceramics 50g after the modification, at 30 ℃, fully behind the vibration contact 3h, leave standstill 30min under the 200r/min condition; Get at last the mixed liquor after leaving standstill, with the physiological saline washing, wash-out does not stick to the egg shell membrane on the micropore ceramics, makes egg shell membrane-micropore ceramics composite adsorbing material.
Get the composite adsorbing material 10g in the example 3, the nitrate concentration of rendering to 200mL is in the sewage of 50mg/L, and regulating the pH value is 7.5, leaves standstill, and adsorbs 4 hours, does not detect and contains nitrate anion in the sewage, adsorption efficiency hundred 100%.Reach the surface water environment quality secondary standard.
Claims (3)
1. composite adsorbing material of removing nitrate anion in the water is characterized in that: micropore ceramics and the egg shell membrane of compound suction material after by modification is mixed with and forms.
2. preparation method who removes the composite adsorbing material of nitrate anion in the water is characterized in that the associated methods of described micropore ceramics and egg shell membrane is:
(1) gets first common Fresh Egg eggshell 50～100g, with tweezers egg shell membrane is peeled from the egg eggshell, join the 100mL mass fraction and be soak 2h in 15～20% the oxalic acid solution after, in 5～10% the NaOH that the 100mL mass fraction is, soak 1h, be dried to constant weight, grind into powder with putting into baking oven (50～60 ℃) after the distilled water washes clean:
(2) get again above-mentioned egg shell membrane powder 10～15g, mix jointly placing constant-temperature table with micropore ceramics 40～50g after the modification, at 20～30 ℃, fully behind the vibration contact 3h, leave standstill 30min under the 200r/min condition;
(3) get at last mixed liquor after leaving standstill, with the physiological saline washing, wash-out does not stick to the egg shell membrane on the micropore ceramics, makes egg shell membrane-micropore ceramics composite adsorbing material.
3. a kind of composite adsorbing material of removing nitrate anion in the water according to claim 2 and preparation method thereof is characterized in that the method for modifying of described micropore ceramics is:
(1) gets 80～100g micropore ceramics as raw material, utilize Ultrasonic Cleaning 2～4 times, behind 60～80 ℃ of lower oven dry 3～5h, be crushed to 100 orders;
(2) then get above-mentioned micropore ceramics 20～30g and put into container, add the cetrimonium bronmide solution of 30～40ml, stirring reaction 1～2h;
(3) mixture is put into baking oven (65～75 ℃), be dried to constant weight, make the modified micropore pottery.
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Cited By (2)
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| CN106943801A (en) * | 2017-03-24 | 2017-07-14 | 孙志廷 | A kind of waste modified activated carbon of egg shell is combined the preparation method of arsenic removal filter core |
| CN108557975A (en) * | 2018-03-30 | 2018-09-21 | 河南金盾环保设备安装工程有限公司 | A kind of sustained release sewage-treating agent and preparation method thereof |
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| JP2005262138A (en) * | 2004-03-19 | 2005-09-29 | Robotsuto Meeshiyon Kk | Decolorizing material of colored solution using eggshell membrane and decolorizing method |
| CN1239237C (en) * | 2002-12-24 | 2006-02-01 | 王旭生 | Preparing method for nanometer multi-microporous ceramic composite membrane for water treatment |
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| JP2005262138A (en) * | 2004-03-19 | 2005-09-29 | Robotsuto Meeshiyon Kk | Decolorizing material of colored solution using eggshell membrane and decolorizing method |
| US20090305883A1 (en) * | 2008-06-09 | 2009-12-10 | Alcoa Inc. | Defluoridation of water |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106943801A (en) * | 2017-03-24 | 2017-07-14 | 孙志廷 | A kind of waste modified activated carbon of egg shell is combined the preparation method of arsenic removal filter core |
| CN108557975A (en) * | 2018-03-30 | 2018-09-21 | 河南金盾环保设备安装工程有限公司 | A kind of sustained release sewage-treating agent and preparation method thereof |
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Application publication date: 20130116 |