CN102614841B - Method for removing arsenic from water body by using potassium permanganate (KMnO4) modified egg shells - Google Patents
Method for removing arsenic from water body by using potassium permanganate (KMnO4) modified egg shells Download PDFInfo
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- CN102614841B CN102614841B CN 201210112956 CN201210112956A CN102614841B CN 102614841 B CN102614841 B CN 102614841B CN 201210112956 CN201210112956 CN 201210112956 CN 201210112956 A CN201210112956 A CN 201210112956A CN 102614841 B CN102614841 B CN 102614841B
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- eggshell
- arsenic
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- egg shells
- potassium permanganate
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- 210000003278 egg shell Anatomy 0.000 title claims abstract description 94
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 39
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000012286 potassium permanganate Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000002351 wastewater Substances 0.000 claims abstract description 17
- 102000002322 Egg Proteins Human genes 0.000 claims description 83
- 108010000912 Egg Proteins Proteins 0.000 claims description 83
- 238000012986 modification Methods 0.000 claims description 46
- 230000004048 modification Effects 0.000 claims description 45
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- 239000002699 waste material Substances 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract 2
- 239000012528 membrane Substances 0.000 abstract 1
- 238000007873 sieving Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 235000012054 meals Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910018663 Mn O Inorganic materials 0.000 description 2
- 229910003176 Mn-O Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- -1 arsenate ions Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for removing arsenic from a water body by using potassium permanganate (KMnO4) modified egg shells. The method comprises the following steps of: preparing modified egg shells, namely adding 1.5 to 2.5g of pretreated egg shells into 100ml of 0.01 to 0.05mol/L KMnO4 solution, oscillating for 10 to 20 hours, and drying at the temperature of between 75 and 125 DEG C to obtain the modified egg shells; and removing the arsenic, namely adding 0.50 to 1.0g of modified egg shells into 100ml of 50ppb arsenic-containing wastewater, oscillating at normal temperature and the frequency of 135 to 145rpm for 5 to 24 hours, and adsorbing, wherein the pretreated egg shells are prepared by the steps of washing the recovered egg shells, removing membranes adhered to the inner walls of the egg shells, drying at the temperature of between 75 and 125 DEG C, grinding, and sieving with a 60-mesh screen. The method is simple and feasible and high in application value, waste is prepared from waste, and the arsenic adsorption capacity of the modified egg shells is rapidly increased.
Description
Technical field
The present invention relates to remove the method for arsenic in water body, particularly a kind of method of utilizing potassium permanganate modification eggshell to remove arsenic in water body.
Background technology
Contain protein in the eggshell, the surface has loose structure with negative electrical charge, can Liquidity limit, and such as gold, copper, iron etc., and the annual eggshell that produces of China is above 400 * 10
4T if these eggshells are directly discarded, not only to environment, and causes the waste of resource.At present, utilize the modification eggshell that the research of the adsorption capacity of heavy metal is carried out, as utilize egg shell-flyash to process respectively acidic fluorine-containing waste water, Acidic Cadmium-Containing Wastewater, acid lead waste water and acidic wastewater containing phosphorus, and process acidic copper-containing waste water etc. with egg shell.Yet, utilize potassium permanganate modification eggshell, improve the ability of its absorption toxic heavy metal, there is not yet report.
Summary of the invention
Technical problem to be solved by this invention is for the prior art deficiency, to provide a kind of method of utilizing potassium permanganate modification eggshell to remove arsenic in water body, it is good, with low cost that it has an effect of removing arsenic, and the source is abundant, simple possible, waste recycling has applications well and is worth.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of method of utilizing potassium permanganate modification eggshell to remove arsenic in water body, it comprises the following steps:
1). preparation modification eggshell: the eggshell that reclaims is cleaned, removal is bonded at the film on the eggshell inwall, in the time of 75-125 ℃, dry, grind, cross 60 mesh sieves, obtaining the preliminary treatment eggshell, is that gained preliminary treatment eggshell is added concentration is the KMnO of 0.01-0.05mol/L for the standard that adds 1.5-2.5g preliminary treatment eggshell in the liquor potassic permanganate of 0.01-0.05mol/L by 100ml concentration
4In the solution, behind vibration 10～20h, obtain the modification eggshell 75-125 ℃ of oven dry;
2). the arsenic removal process: be that the standard that adds 0.50-1.0g modification eggshell in the arsenic-containing waste water of 50ppb is added the modification eggshell by 100ml concentration in arsenic-containing waste water, and at normal temperatures with frequency 135-145rpm vibration absorption in 5-24 hour.
As everyone knows, the Main Ingredients and Appearance of eggshell is calcium carbonate CaCO
3, its wide material sources enter the water body non-secondary pollution, the early-stage Study demonstration, and the egg-shell meal surface has loose structure (as shown in Figure 1) with negative electrical charge, thereby has certain Cation adsorption ability, but its adsorbance is relatively less.As shown in Figure 1, through potassium permanganate KMnO
4Before the modification, the inner cavernous structure of eggshell is less, and some is also stopped up by organic substance, still, when eggshell through KMnO
4After solution modification was made the modification eggshell, not only as shown in Figure 2, the duct of originally being stopped up by organic substance disappeared under the oxidation of potassium permanganate, formed the CaCO in duct
3Because the dissolving of corrosiveness generating portion causes the duct to increase, and the aperture increase, so that the absorption affinity of modification eggshell strengthens; And eggshell is when soaking in liquor potassic permanganate, the large amount of organic matter that contains on the eggshell can be reduced potassium permanganate, the manganese dioxide that forms the dispersion of stratiform is attached to the surface of modification eggshell, by Fig. 3, the infrared scan comparison diagram as can be known before and after the eggshell modification of Fig. 4, after the eggshell modification, the N-H bond fission of unborn organic substance in the eggshell, oxidisability that potassium permanganate is described is with oxidation operation in the eggshell, it has not only further proved the result of Fig. 2 electron-microscope scanning gained, and increased the Mn-O key on its surface after the eggshell modification as can be known, this is that potassium permanganate itself is reduced into manganese dioxide and is attached on the eggshell, and has formed the peak of Mn-O key at wavelength 667cm place.Because at MnO
2There is a large amount of oh groups on the surface, and (OH), its easy and arsenate ions binding produces suction-operated, thereby is conducive to the Adsorption of arsenic.
Compared with prior art, the advantage of the invention is:
1, the present invention adopts potassium permanganate modification eggshell to remove arsenic in water body, because the modification eggshell after the potassium permanganate modification has preferably arsenic absorption affinity, its effect of removing arsenic strengthens greatly, and the arsenic adsorbance has reached 21 times of original unmodified egg-shell meal, is about 88.27%.
2, the inventive method is with low cost, and the source is abundant, simple possible, and waste recycling has applications well and is worth.
Description of drawings
Fig. 1 is egg-shell meal electron-microscope scanning figure before the potassium permanganate modification.
Fig. 2 is the egg-shell meal electron-microscope scanning figure after the potassium permanganate modification.
Fig. 3 is infrared scan comparison diagram before and after the eggshell modification.
Fig. 4 is that Fig. 3 wave number is at 400-1000cm
-1Interior partial enlarged drawing.
Fig. 5 is that potassium permanganate modification eggshell and unmodified eggshell are to arsenic adsorption rate temporal evolution situation map.
The specific embodiment
Embodiment 1:
1, the preliminary treatment of eggshell: eggshell is cleaned, removed the film that is bonded on the eggshell inwall, in the time of 75 ℃, dry, grind, cross 60 mesh sieves;
2, preparation modification eggshell: be that the preliminary treatment eggshell is added concentration is the KMnO of 0.01mol/L for the standard that adds 1.5g preliminary treatment eggshell in the liquor potassic permanganate of 0.01mol/L by 100ml concentration
4In the solution, behind the vibration 10h, obtain the modification eggshell 75 ℃ of oven dry;
3. arsenic removal process: be that the standard that adds 0.5g modification eggshell in the arsenic-containing waste water of 50ppb is added the modification eggshell by 100ml concentration in arsenic-containing waste water, and at normal temperatures with frequency 135rpm vibration absorption in 5 hours.
Embodiment 2:
1, the preliminary treatment of eggshell: eggshell is cleaned, removed the film that is bonded on the eggshell inwall, in the time of 100 ℃, dry, grind, cross 60 mesh sieves;
2, preparation modification eggshell: be that the preliminary treatment eggshell is added concentration is the KMnO of 0.025mol/L for the standard that adds 2g preliminary treatment eggshell in the liquor potassic permanganate of 0.025mol/L by 100ml concentration
4In the solution, behind the vibration 15h, obtain the modification eggshell 100 ℃ of oven dry;
3. arsenic removal process: be that the standard that adds 0.75g modification eggshell in the arsenic-containing waste water of 50ppb is added the modification eggshell by 100ml concentration in arsenic-containing waste water, and at normal temperatures with frequency 140rpm vibration absorption in 15 hours.
Embodiment 3:
1, the preliminary treatment of eggshell: eggshell is cleaned, removed the film that is bonded on the eggshell inwall, in the time of 125 ℃, dry, grind, cross 60 mesh sieves;
2, preparation modification eggshell: be that the preliminary treatment eggshell is added concentration is the KMnO of 0.05mol/L for the standard that adds 2.5g preliminary treatment eggshell in the liquor potassic permanganate of 0.05mol/L by 100ml concentration
4In the solution, behind the vibration 20h, obtain the modification eggshell 125 ℃ of oven dry;
3. arsenic removal process: be that the standard that adds 1.0g modification eggshell in the arsenic-containing waste water of 50ppb is added the modification eggshell by 100ml concentration in arsenic-containing waste water, and at normal temperatures with frequency 145rpm vibration absorption in 24 hours.
Adsorption experiment: take by weighing respectively the modification eggshell 0.50g that obtains among the embodiment 1-3 and add in the arsenic-containing waste water of 100ml 50ppb, vibrate respectively 0.5,1,5,10,15,24, filter behind the 48h, measure the content of arsenic in the supernatant, obtain the result as shown in Figure 5, as shown in Figure 5, the modification eggshell is along with the growth of duration of oscillation, the removal of arsenic takes the lead in increasing, and behind vibration 24h, adsorption rate reaches 88.27%, then tend towards stability, namely 24h post-modification eggshell reaches adsorption equilibrium to the absorption of arsenic.Under the identical condition, the eggshell of non-modified only has 4.02% to the removal efficient of arsenic in the water.This has increased about 21 times the adsorption capacity of arsenic with regard to showing the modification eggshell.
Claims (1)
1. a method of utilizing potassium permanganate modification eggshell to remove arsenic in water body is characterized in that comprising the following steps:
1). preparation modification eggshell: the eggshell that reclaims is cleaned, removal is bonded at the film on the eggshell inwall, in the time of 75-125 ℃, dry, grind, cross 60 mesh sieves, obtaining the preliminary treatment eggshell, is that gained preliminary treatment eggshell is added concentration is the KMnO of 0.01-0.05mol/L for the standard that adds 1.5-2.5g preliminary treatment eggshell in the liquor potassic permanganate of 0.01-0.05mol/L by 100ml concentration
4In the solution, behind vibration 10～20h, obtain the modification eggshell 75-125 ℃ of oven dry;
2). the arsenic removal process: be that the standard that adds 0.50-1.0g modification eggshell in the arsenic-containing waste water of 50ppb is added the modification eggshell by 100ml concentration in arsenic-containing waste water, and at normal temperatures with frequency 135-145rpm vibration absorption in 5-24 hour.
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| CN 201210112956 CN102614841B (en) | 2012-04-17 | 2012-04-17 | Method for removing arsenic from water body by using potassium permanganate (KMnO4) modified egg shells |
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| CN 201210112956 CN102614841B (en) | 2012-04-17 | 2012-04-17 | Method for removing arsenic from water body by using potassium permanganate (KMnO4) modified egg shells |
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| CN102963954B (en) * | 2012-12-10 | 2013-11-06 | 湖南农业大学 | Method for removing cadmium in water by using potassium permanganate and calcium nitrate modified cotton |
| CN104772105A (en) * | 2014-01-15 | 2015-07-15 | 中国科学院大学 | Preparation of MnO2 loaded fly ash adsorbent and application of adsorbent in removal of water body As (III) |
| CN106540649B (en) * | 2016-12-07 | 2019-02-22 | 福州大学 | A kind of green syt of the manganese calcium nano adsorber constructed by egg shell and its application |
| CN111569818A (en) * | 2020-05-06 | 2020-08-25 | 三峡大学 | Drinking water defluorinating agent and preparation method and application thereof |
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| CN1239252C (en) * | 2003-07-04 | 2006-02-01 | 王睿 | Preparation method of heavy metal ion adsorbing agent |
| JP2005255737A (en) * | 2004-03-09 | 2005-09-22 | Sumitomo Osaka Cement Co Ltd | Method for producing heavy metal adsorbent from waste and heavy metal adsorbent obtained by the method |
| CN102190343B (en) * | 2010-03-03 | 2012-11-28 | 南京信息工程大学 | Method for adsorbing phosphate in sewage by using eggshells |
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