CN101412572A - In-situ covering method for heavy metal in nano agustite immobilized sediment - Google Patents
In-situ covering method for heavy metal in nano agustite immobilized sediment Download PDFInfo
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- CN101412572A CN101412572A CNA2008101531040A CN200810153104A CN101412572A CN 101412572 A CN101412572 A CN 101412572A CN A2008101531040 A CNA2008101531040 A CN A2008101531040A CN 200810153104 A CN200810153104 A CN 200810153104A CN 101412572 A CN101412572 A CN 101412572A
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Abstract
The invention discloses an in-situ covering method for heavy metal in nano phosphorite fixed sediment, which comprises the following steps: preparing nano hydroxylapatite; preparing an in-situ fixing material, that is, adopting one or more than one material of the nano hydroxylapatite, nano fluorapatite or nano chlorapatite; and carrying out in-situ covering for polluted rivers or lakes. The method also comprises the step of using an in-situ covering material mixed by one or mixture of more than one of unpolluted sediment, earth or soil, wherein specific usage amount of the in-situ covering material is 10 to 490 centimeters of covering thickness. The total covering thickness of the in-situ fixing material and the in-situ covering material is between 0.05 and 500 centimeters. The in-situ covering method is used for restoring the sediments polluted by organic substances in the rivers or the lakes, can effectively prevent pollutants such as the heavy metal in the sediments from entering water body, has remarkable function of improving water quality, has the functions of fixing the heavy metal in the sediments, reducing biological effectiveness, and the like, and has the advantages of good effect, no secondary pollution, and wide application range.
Description
Technical field
The present invention relates to a kind of to the sedimental restorative procedure of heavy metal contamination.Particularly relate to a kind of by adding heavy metal in the nano-apatite tectum immobilized sediment, reduce its bioavailability, reduce simultaneously that heavy metal discharges to water body in the settling, influence the in-situ covering method of heavy metal in the nano agustite immobilized sediment of human health.
Background technology
Water body deposit pollutes, it is a worldwide important environmental problem, its pollutent deposits in the layer deposition thing and enrichment gradually mainly by atmospheric precipitation, discharge of wastewater, soil erosion, rainwater leaching and wash away and enter water body at last, makes bed mud be subjected to severe contamination.The pollution of water body deposit is an important factor that influences the water body environment quality; this is to have quite a few usually because of the pollutent that enters into water body to store in settling by effects such as absorption or precipitations; in case water body environment changes; be deposited on the nitrogen phosphorus nutrition element in the bed mud; heavy metal and hardly degraded organic substance can discharge again and enter water body; influence the water quality of overlying water; settling just becomes the secondary pollution source like this; can directly or indirectly cause the evil effect to bottom-dwelling or the biological intoxicating that produces of overlying water; and by biomagnification; processes such as food chain amplification further influence terrestrial life and human health.
Over nearly 20 years, bed mud heavy metal contamination is subject to people's attention day by day.Chinese scholar has been carried out investigation and research in various degree to more domestic important rivers, lake heavy metal contamination, as the Changjiang river, the Yellow River, Haihe River, Xiang River, canal, Nansi Lake, Taihu Lake, all river mouths, Bohai Rim, Shandong Xiaoqinghe River etc., in addition, Jing Mahe, mountain, mouth of a river mining area Kang Jiaxi, the 200 prescription marsh wetlands etc. that also have Suzhou River, the Xuzhou in Shanghai.The evaluation result of various places shows, heavy metal content is apparently higher than local soil background in the bed mud, partial rivers or lake, especially the water body of municipal effluent, industrial sewage, the influence of mining industry waste water, its bed mud heavy metal contamination is serious, its content has surpassed " soil environment quality standard ", part index number even surpassed " pollution substance control criterion in the agricultural mud ".
At present, from governing measure, reparation is broadly divided into dystopy processing and in-situ treatment two classes to sediment pollution both at home and abroad, with respect to the dystopy treatment technology, the expense of in-situ treatment method is then cheaper, engineering construction is also simple relatively, is therefore becoming the dominant direction that settling is repaired gradually.And traditional original position to cover generally be to lay materials such as the fine sand that polluted, clay, bed mud in contaminated deposit surface, between bottom-dwelling and water body, form physical barrier at contaminated settling, thereby can slow down even stop the release of pollutent in water body.But these materials are heavy metal effectively fixedly, just postpones it and spreads to aqueous phase.Since the reported first such as Suzuki of Japan in 1981 since the artificial-synthetic hydroxyapatite can remove lead in the aqueous solution, the heavy metal contamination of phosphorated material repairing and treating, cause a plurality of field scholars' such as geology, environment, chemistry and agricultural extensive interest, be considered to one of effective ways of field repair heavy metal contamination.China's phosphate rock resource is abundant, and the advantage that makes full use of China's phosphate rock resource is is effectively prevented and treated the serious heavy metal pollution problem of China and had feasibility and realistic meaning.
Summary of the invention
Technical problem to be solved by this invention is, the in-situ covering method of heavy metal in the nano agustite immobilized sediment of a kind of effective, non-secondary pollution, applied range is provided.
The technical solution adopted in the present invention is: the in-situ covering method of heavy metal in a kind of nano agustite immobilized sediment comprises the steps: (1) preparation nanometer hydroxyapatite; (2) configuration anchored in place material, promptly nano-apatite adopts one or more mixing in nanometer hydroxyapatite, nanometer fluorapatite or the nanometer chlorapatite material to use;
(3) contaminated river or lake are carried out the original position covering.
Also include the original position covering material that is used by one or more mixing in unpolluted settling, soil or the sand, concrete consumption is that cladding thickness is 10-490 centimetre.
The described preparation nanometer hydroxyapatite of step (1) is: adopt saturated aqua calcis, phosphoric acid, in room temperature, the pH value is 9, under the 6 hours reaction times condition, employing volumetry altogether prepares nano-grade hydroxy apatite, and the ratio of calcium and phosphorus of described saturated aqua calcis and phosphoric acid solution is 1.67.
In employing nanometer hydroxyapatite described in the step (2), nanometer fluorapatite or the nanometer chlorapatite material one or more mix use, and concrete consumption is: every square metre of 0.5-50 kilogram.
Contaminated river is carried out original position to be covered, be with the anchored in place material and covering material directly broadcasts sowing or the contaminated settling that is laid on, or the compound back of anchored in place material and covering material material is filled in the sack of good water permeability, then on the bedding settling.
Described with the anchored in place material and covering material directly broadcasts sowing or the contaminated settling that is laid on, be successively to lay anchored in place material and original position covering material from bottom to top, or will lay after two kinds of material mixing.
Described anchored in place material addition is 0.05-10 centimetre a thickness, or every square metre of 0.5-50 kilogram.
It is 0.05-500 centimetre that anchored in place material and covering material are laid total thickness.
The in-situ covering method of heavy metal in the described nano agustite immobilized sediment, be used for repairing the river or the lake in the settling that is subjected to Organic pollutants.
The in-situ covering method of heavy metal in the nano agustite immobilized sediment of the present invention, utilize the bigger specific surface area of nano-apatite, to the strong response capacity of heavy metal and to the reactionlessness of other materials, can realize efficient quick and durable repairing heavy metal pollution settling.When the heavy metal that discharges when contaminated settling is about to move to water body, this nano material is the heavy metal that discharges of immobilized sediment in time, and this nano material transforms into remaining attitude heavy metal harmless or that bioavailability is extremely low by precipitation or surface complexation interaction energy with the exchangeable species in the settling, organism ADSORPTION STATE, carbonate ADSORPTION STATE heavy metal simultaneously.Can prevent effectively in the settling that pollutent such as heavy metal enters water body, water quality is improved significantly, and to heavy metal in the settling play fixing, reduce effect such as biological effectiveness.Effective, non-secondary pollution, applied range.
Description of drawings
Fig. 1 is that the present invention repairs back overlying water repairing effect curve;
Fig. 2 is the biological effectiveness that the present invention repairs heavy metal (Pb) in the settling of back;
Fig. 3 is the form distribution that the present invention repairs heavy metal (Pb) in the settling of back.
Embodiment
Below in conjunction with embodiment the in-situ covering method of heavy metal in the nano agustite immobilized sediment of the present invention is made a detailed description.
The in-situ covering method of heavy metal comprises the steps: in the nano agustite immobilized sediment of the present invention
(1) preparation nanometer hydroxyapatite;
Adopt saturated aqua calcis, phosphoric acid, in room temperature, the pH value is 9, and under the 6 hours reaction times condition, adopting altogether, volumetry prepares nano-grade hydroxy apatite, described saturated aqua calcis (Ca (OH)
2Supernatant liquor) and the ratio of calcium and phosphorus of phosphoric acid solution be 1.67.
(2) configuration anchored in place material, promptly nano-apatite adopts nanometer hydroxyapatite (Ca
5(PO
4)
3(OH)), nanometer fluorapatite (Ca
5(PO
4)
3F) or nanometer chlorapatite (Ca
5(PO
4)
3Cl) one or more in the material mix use; Concrete consumption is: every square metre of 0.5-50 kilogram.
Impact the increase repairing effect in order effectively to reduce the river, can also add and use the original position covering material, be that one or more mixing in unpolluted settling, soil or the sand are used, concrete consumption is that cladding thickness is 10-490 centimetre, cover the anchored in place material above, or adopt the amount and the use of anchored in place material mixing of 10-490 centimetre of thickness.
(3) contaminated river or lake are carried out the original position covering.
Method of the present invention be used for repairing the river or the lake in the settling that is subjected to Organic pollutants.Contaminated river or lake are carried out the original position covering, be with the anchored in place material and covering material directly broadcasts sowing or the contaminated settling that is laid on, or the compound back of anchored in place material and covering material material is filled in the sack of good water permeability, then on the bedding settling.
Described with the anchored in place material and covering material directly broadcasts sowing or the contaminated settling that is laid on, be successively to lay anchored in place material and original position covering material from bottom to top, described anchored in place material addition is 0.05-10 centimetre a thickness, or every square metre of 0.5-50 kilogram, can change can be arranged according to the difference of contaminated degree of settling and water conservancy operational condition.It is 0.05-500 centimetre that anchored in place material and covering material are laid total thickness.
Or adopt and to lay after two kinds of material mixing.
Concrete covering can be adopted a kind of in the following manner:
(1) anchored in place material and covering material are adopted mechanical means such as truck, lifting machine directly in water, topple over, by obducent action of gravity natural subsidence will be sediment covered firmly.
(2) carry anchored in place material and covering material with barge and in the overlay area, slowly move, open the barge false bottom, spreading anchored in place material and covering material.
(3) by the pipe on the barge anchored in place material and covering material are injected into water body lower floor.
Example 1:
1. adopt Ca (OH)
2Supernatant liquor and phosphoric acid solution (both ratio of calcium and phosphorus are 1.67), in room temperature, the pH value is 9, under the 6 hours reaction times condition, adopting altogether, volumetry prepares nano-grade hydroxy apatite;
2. directly adopt nanometer hydroxyapatite (Ca
5(PO
4)
3(OH)) be nano-apatite, lay the anchored in place material, laying depth is 5 centimetres;
3. select for use more unpolluted soil be laid on the anchored in place material above, 200 centimetres of laying depths.
Example 2:
1. adopt Ca (OH)
2Supernatant liquor and phosphoric acid solution (both ratio of calcium and phosphorus are 1.67), in room temperature, the pH value is 9, under the 6 hours reaction times condition, adopting altogether, volumetry prepares nano-grade hydroxy apatite;
2. adopt nanometer hydroxyapatite (Ca
5(PO
4)
3(OH)) with nanometer fluorapatite (Ca
5(PO
4)
3F) each 50%, be mixed with the anchored in place material, i.e. nano-apatite
3. lay the anchored in place material, laying depth is 5 centimetres;
4. select for use more unpolluted soil be laid on the anchored in place material above, 200 centimetres of laying depths.
Be to use below before the present invention and after experiment:
1, settling Pb contamination.Get not comtaminated settling and put into brown sample bottle, add the lead nitrate of 2.0mM (414.47mg/L) and the SODIUMNITRATE mixing solutions of 0.02mM (1.70mg/L), settling, aqueous solution ratio are 1:6Kg/L, place impeller (1rpm, room temperature) on, stand-by behind the molecular balance 7d.
2, cover experiment
Contaminated settling is paved into 5cm thickness in the stratiform simulator, the relative add-on of spreading is that 0%, 1.0%, 3.16%, 5.5% and 10.0% (thickness is roughly 0cm respectively on Marine sediments, 0.05cm, 0.2cm, 0.3cm, 0.5cm) nanometer hydroxyapatite, left standstill 3,7,14 days, it is to be measured to get sample segment.
3, coverage effect assessment
3.1 supernatant liquor is measured.Add the certain amount of nano hydroxyapatite in settling Pb contamination equilibrium system, place on the impeller (1rpm, room temperature), centrifugal (2000rpm, 20min), supernatant liquor is crossed the content of measuring Pb behind the 0.45 μ m filter membrane with mixture after reaction.
3.2 the biological effectiveness of Pb test in the settling.After above-mentioned residue after centrifugal places and handles 24h in the lyophilizer, be ground to uniform particles, take by weighing 1.2000 ± 0.0003g then to the transparent sample bottle, add 12mL0.05M disodium EDTA (EDTA) solution, place on the reciprocating type shaking table of level (150rpm, 25.0 ± 3.0 ℃), behind the vibration 1h, mixture is centrifugal, measure the Pb content in the filtrate behind the filtering membrane.
3.3 the form distribution test of Pb in the settling.Take by weighing solid 1.0000 ± 0.0003g after the above-mentioned grinding in the transparent sample bottle, heavy metal to various forms in the settling extracts continuously, place then on the reciprocating type shaking table of level, centrifugal after the oscillatory reaction balance, to be measured behind the filtering membrane, add the 10mL deionized water again and clean in centrifugal residue, each step is measured the Pb content in the extracting solution all through after vibration-centrifugal-filtration-cleaning.
Facts have proved:, can reduce the extremely approaching blank level (as shown in Figure 1) of Pb content in the contamination overlying water by adding nanometer hydroxyapatite; Nanometer hydroxyapatite can effectively reduce the biological effectiveness (as shown in Figure 2) of Pb in the settling; Nanometer hydroxyapatite can increase remaining attitude Pb content in the settling, reduces exchangeable species Pb content, can obviously reduce the transfer ability (as shown in Figure 3) of Pb in the settling.
Claims (9)
1. the in-situ covering method of heavy metal in the nano agustite immobilized sediment is characterized in that, comprises the steps:
(1) preparation nanometer hydroxyapatite;
(2) configuration anchored in place material, promptly nano-apatite adopts one or more mixing in nanometer hydroxyapatite, nanometer fluorapatite or the nanometer chlorapatite material to use;
(3) contaminated river or lake are carried out the original position covering.
2. the in-situ covering method of heavy metal in the nano agustite immobilized sediment according to claim 1, it is characterized in that, also include the original position covering material that is used by one or more mixing in unpolluted settling, soil or the sand, concrete consumption is that cladding thickness is 10-490 centimetre.
3. the in-situ covering method of heavy metal in the nano agustite immobilized sediment according to claim 1, it is characterized in that, the described preparation nanometer hydroxyapatite of step (1) is: adopt saturated aqua calcis, phosphoric acid, in room temperature, the pH value is 9, under the 6 hours reaction times condition, employing volumetry altogether prepares nano-grade hydroxy apatite, and the ratio of calcium and phosphorus of described saturated aqua calcis and phosphoric acid solution is 1.67.
4. the in-situ covering method of heavy metal in the nano agustite immobilized sediment according to claim 1, it is characterized in that, in employing nanometer hydroxyapatite described in the step (2), nanometer fluorapatite or the nanometer chlorapatite material one or more mix use, and concrete consumption is: every square metre of 0.5-50 kilogram.
5. the in-situ covering method of heavy metal in the nano agustite immobilized sediment according to claim 1 and 2, it is characterized in that, contaminated river is carried out original position to be covered, be with the anchored in place material and covering material directly broadcasts sowing or the contaminated settling that is laid on, or the compound back of anchored in place material and covering material material is filled in the sack of good water permeability, then on the bedding settling.
6. the in-situ covering method of heavy metal in the nano agustite immobilized sediment according to claim 5, it is characterized in that, described with the anchored in place material and covering material directly broadcasts sowing or the contaminated settling that is laid on, be successively to lay anchored in place material and original position covering material from bottom to top, or will lay after two kinds of material mixing.
7. the in-situ covering method of heavy metal is characterized in that in the nano agustite immobilized sediment according to claim 5, and described anchored in place material addition is 0.05-10 centimetre a thickness, or every square metre of 0.5-50 kilogram.
8. the in-situ covering method of heavy metal is characterized in that in the nano agustite immobilized sediment according to claim 5, and it is 0.05-500 centimetre that anchored in place material and covering material are laid total thickness.
9. the in-situ covering method of heavy metal is characterized in that in the nano agustite immobilized sediment according to claim 1, be used for repairing the river or the lake in the settling that is subjected to Organic pollutants.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101531040A CN101412572A (en) | 2008-11-17 | 2008-11-17 | In-situ covering method for heavy metal in nano agustite immobilized sediment |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260097A (en) * | 2010-05-25 | 2011-11-30 | 张永锋 | New energy power generation and biological fertilizer |
| CN102335674A (en) * | 2010-07-27 | 2012-02-01 | 周静 | Method for restoring soil polluted by heavy metals Cu and Cd in apatite field |
| CN102965116A (en) * | 2012-11-14 | 2013-03-13 | 浙江省环境保护科学设计研究院 | Heavy metal stabilizing agent and method for treating heavy metal contaminated soil by using same |
| CN103613257A (en) * | 2013-12-05 | 2014-03-05 | 中国科学院东北地理与农业生态研究所 | Active covering method for in-situ remediation of sediments |
| CN103771674A (en) * | 2014-02-17 | 2014-05-07 | 河海大学 | Method for in-situ remediation of polluted bed mud |
| CN104529101A (en) * | 2014-11-28 | 2015-04-22 | 北京交通大学 | City sludge heavy metal passivation method by using hydroxyapatite as passivating agent |
| CN104861740A (en) * | 2015-03-23 | 2015-08-26 | 湖南大学 | Modified nanometer chlorapatite and preparation method thereof |
| CN105368460A (en) * | 2015-12-08 | 2016-03-02 | 江苏盖亚环境工程有限公司 | Lead metal soil pollution nanometer repairing agent and preparation method thereof |
| CN105536739A (en) * | 2016-01-29 | 2016-05-04 | 上海理工大学 | Heavy metal adsorption mineralizing agent for synchronously restoring water body and bottom mud of water body and preparation method of heavy metal adsorption mineralizing agent |
| CN106673384A (en) * | 2017-01-06 | 2017-05-17 | 山东建筑大学 | Water body heavy metal polluted sediment in-situ covering and repairing method |
| CN114516709A (en) * | 2022-02-21 | 2022-05-20 | 中国水利水电第六工程局有限公司 | Active mixed covering material and using method and application thereof |
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2008
- 2008-11-17 CN CNA2008101531040A patent/CN101412572A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260097A (en) * | 2010-05-25 | 2011-11-30 | 张永锋 | New energy power generation and biological fertilizer |
| CN102335674A (en) * | 2010-07-27 | 2012-02-01 | 周静 | Method for restoring soil polluted by heavy metals Cu and Cd in apatite field |
| CN102965116A (en) * | 2012-11-14 | 2013-03-13 | 浙江省环境保护科学设计研究院 | Heavy metal stabilizing agent and method for treating heavy metal contaminated soil by using same |
| CN103613257A (en) * | 2013-12-05 | 2014-03-05 | 中国科学院东北地理与农业生态研究所 | Active covering method for in-situ remediation of sediments |
| CN103771674B (en) * | 2014-02-17 | 2015-07-29 | 河海大学 | A kind of in-situ remediation method of polluted bed mud |
| CN103771674A (en) * | 2014-02-17 | 2014-05-07 | 河海大学 | Method for in-situ remediation of polluted bed mud |
| CN104529101A (en) * | 2014-11-28 | 2015-04-22 | 北京交通大学 | City sludge heavy metal passivation method by using hydroxyapatite as passivating agent |
| CN104861740A (en) * | 2015-03-23 | 2015-08-26 | 湖南大学 | Modified nanometer chlorapatite and preparation method thereof |
| CN104861740B (en) * | 2015-03-23 | 2017-06-16 | 湖南大学 | Modified Nano chlorapatite and preparation method thereof |
| CN105368460A (en) * | 2015-12-08 | 2016-03-02 | 江苏盖亚环境工程有限公司 | Lead metal soil pollution nanometer repairing agent and preparation method thereof |
| CN105536739A (en) * | 2016-01-29 | 2016-05-04 | 上海理工大学 | Heavy metal adsorption mineralizing agent for synchronously restoring water body and bottom mud of water body and preparation method of heavy metal adsorption mineralizing agent |
| CN106673384A (en) * | 2017-01-06 | 2017-05-17 | 山东建筑大学 | Water body heavy metal polluted sediment in-situ covering and repairing method |
| CN106673384B (en) * | 2017-01-06 | 2019-07-09 | 山东建筑大学 | A kind of heavy metal pollution of water body sediment in-situ covering restorative procedure |
| CN114516709A (en) * | 2022-02-21 | 2022-05-20 | 中国水利水电第六工程局有限公司 | Active mixed covering material and using method and application thereof |
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Open date: 20090422 |