CN103433275B - Fulvic acid-potassium chloride combined eluant, and preparation method and application thereof - Google Patents
Fulvic acid-potassium chloride combined eluant, and preparation method and application thereof Download PDFInfo
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- CN103433275B CN103433275B CN201310373513.2A CN201310373513A CN103433275B CN 103433275 B CN103433275 B CN 103433275B CN 201310373513 A CN201310373513 A CN 201310373513A CN 103433275 B CN103433275 B CN 103433275B
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Abstract
The invention discloses a fulvic acid-potassium chloride combined eluant, and a preparation method and application thereof, relating to the technical field of restoration of heavy metal pollution in soil. According to the invention, humic acids with different qualities for restoring heavy metal cadmium polluted soil are dissolved in a 0.1m/L potassium chloride solution, a 0.1m/L sodium hydroxide solution is utilized to regulate the pH value to 11 or so to prepare a 0.05-1.00% humic acid solution, centrifugation is performed, and the separated solution is a fulvic acid-potassium chloride mixed solution; and the fulvic acid-potassium chloride mixed solution can be used as a combined eluant to elute the cadmium polluted soil. The chemical eluant used in the invention has the advantages of simple formula, obvious effect, strong operability, low application cost, high elution rate and high removal effect for cadmium ions in soil. The test indicates that the elution rate is optimal when the concentration of the eluate is 0.05%, the pH value is 4, the volume ratio of the eluant to the cadmium polluted soil is 10:1 and the elution time is 2 hours; and the eluate can not generate secondary pollution to the soil, and has an obvious supplementation action on potassium lost in the elution process.
Description
Technical field
The invention discloses a kind of fulvic acid and potassium chloride combines eluent and preparation method thereof and applies, relate to the recovery technique field that heavy metal in soil pollutes, is the eluent that pollutes of rehabilitating soil cadmium (Cd) and application specifically.
Background technology
Heavy metal pollution of soil is one of serious environmental problems of facing of the current whole world.Improvement at present for Cadmium Pollution in Soils adopts plant restoration method more.But because recommended heavy metal accumulation or super enriching plant often have, biomass is low, repairing efficiency long, be subject to the features such as climatic effect, and thus reparation benefit is low.
Soil washing belongs to heavy metal chemical repair method, is namely to utilize chemistry or biological eluent to strengthen the animal migration of heavy metal in soil, thus is effectively removed from soil by heavy metal.In scientific research and practice, the normal eluent used comprises inorganic eluent, artificial chelating agent, biosurfactant etc.But research shows strong acid eluent meeting spoiled soil structure in lessivation, and the biocoene poisoned in soil causes soil again to utilize; EDTA, EDDS and its biological degradability of surfactant poor, production cost is high, easily causes secondary pollution (Dermont, et al., 2007).And reparation object mainly concentrates on mine, smeltery, the drip washing (Moutsatsou, et al., 2006) of the serious pollution soil and water heavy metal pollutions such as municipal sludge.
Humic acid is the polymeric set compound be made up of multiple functional group, and extensively exist with soil environment, current research focus mostly in discussion humic acid to water body environment in the Adsorption and desorption characteristics of heavy metal or the miscellaneous function in phytoremediation, and to component each in humic acid especially fulvic acid and other agent combination, the ELUTION METHOD to Cadmium Pollution in Soils rarely has report, and present eluent does not consider the loss of eluent to soil potassium nutrient, in soil, most of heavy metal is combined with solid phase the drip washing effect of eluent heavy metal is restricted in addition, elution efficiency is not high.
Summary of the invention
The object of the invention is to the deficiency overcoming prior art existence, provide a kind of fulvic acid and potassium chloride to combine eluent and preparation method thereof, and remove the application of Cadmium Pollution in Soils.
In the present invention, fulvic acid and potassium chloride combine eluent and are made up of fulvic acid and potassium chloride.
Fulvic acid of the present invention and potassium chloride combine eluent preparation method, and its preparation method is as follows:
A. humic acid is dissolved in the Klorvess Liquid of 0.1m/L, and regulates pH ≈ 11 to make 0.05-1.00%(weight ratio with the sodium hydroxide solution of 0.1m/L) humic acid solution;
B. the pH=4.0 of the humic acid solution of regulating step a preparation, produces after precipitation centrifugal until solution, gets its clear liquid, and obtained fulvic acid and potassium chloride combine eluent.
Fulvic acid of the present invention and potassium chloride combine the application of eluent, specifically with this eluent, cadmium pollution soil is repaired, the combination eluent of above-mentioned concentration is added in cadmium pollution soil, described eluent and the volume ratio of cadmium pollution soil are 10:1, at room temperature carry out the rear centrifugal 15min of vibration, gained is precipitated as the soil after drip washing.
Fulvic acid of the present invention and potassium chloride combine the application of eluent, when eluent concentration be 0.05%, the volume ratio of pH=4, eluent and cadmium pollution soil is 10:1, the drip washing time is 2h time washout rate best.
Compared with prior art, the present invention has following beneficial effect:
1. the present invention's chemical leaching used agent prescription is simple, Be very effective, application cost are low, washout rate is high, have obvious removal effect to the cadmium ion existed in soil.
2. the present invention's chemical leaching method used is for cadmium pollution soil, and can to the eluent processing time, and the parameters such as concentration adjust.Shown by test: when eluent concentration be 0.05%, the volume ratio of pH=4, eluent and cadmium pollution soil be 10:1 and the drip washing time is 2h time washout rate reach more than 80%, thus show the outstanding drip washing effect of this eluent to cadmium pollution soil.
3. this combination eluent has obvious supplementary function to the soil potassium lost in lessivation.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail
The drip washing of embodiment 1 soil heavy metal cadmium
First humic acid different quality being used for remediating heavy metal cadmium pollution soil is dissolved in the Klorvess Liquid of 0.1m/L, and regulate pH to 11 to make the humic acid solution that concentration is respectively 0.05%, 0.10%, 0.20%, 0.50%, 1.00% by the sodium hydroxide solution of 0.1m/L, be separated with the pH to 4.0 of the nitric acid adjustment solution of 0.1m/L subsequently, the combination eluent of obtained fulvic acid and 0.1m/L potassium chloride.Choosing cadmium content is that the contaminated soil of 18.76mg/kg adds eluent according to liquid-solid volume ratio 10:1.At room temperature vibrate, hunting speed is 200 revs/min.Subsequently eluate to be transferred in centrifuge tube with the centrifugation 15 minutes of 4000 revs/min, get its supernatant liquid filtering and collect, and utilizing atomic absorption spectrophotometry light instrument degree to measure the content (accompanying drawing 1) of Cd in leacheate.As can be seen from accompanying drawing 1, when the drip washing time is 2h when concentration is 0.05%, 98% is reached to cadmium pollution soil washout rate.
Embodiment 2
In order to explore combination eluent to the impact of soil potassium, choosing in embodiment 1 and combining the soil after eluent drip washing with fulvic acid and potassium chloride, and choosing only with the soil after single fulvic acid drip washing in contrast simultaneously, measuring the content of potassium in soil respectively.Fulvic acid in the present embodiment is obtained by the humic acid solution separation of 0.05%, choose the contaminated soil that cadmium content is 18.76mg/kg, according to eluent concentration be 0.05%, the volume ratio of pH=4, eluent and cadmium pollution soil is 10:1, the drip washing time is the soil that 2h obtains, and chooses in embodiment 1
0.05% fulvic acid and potassium chloride combine eluent, when eluent concentration be 0.05%, the volume ratio of pH=4, eluent and cadmium pollution soil is 10:1, the drip washing time is 2h time soil.Can find out combination eluent drip washing from accompanying drawing 2 after, the potassium content of soil is significantly higher than single fulvic acid washed off soil, thus shows this combination eluent and have obvious supplementary function to the soil potassium lost in lessivation.
The Soil leaching rate computing formula related in example of the present invention and parameter are defined as follows:
(1) the content of beary metal M(mg kg that washes out of eluent
-1) computing formula
In formula:
M---eluent washes out
the content of heavy metal in soil (mg kg
-1);
Heavy metal mass concentration (the mg L that C---flame photometer records
-1)
The volume of V---constant volume in volumetric flask (ml);
D---to the multiple of raw sample solution dilution;
M---pedotheque quality (g)
(2) clearance (%) computing formula of eluent heavy metal
In formula:
The clearance (%) of R---eluent heavy metal;
Content of beary metal (mg kg in the soil that M---eluent washes out
-1);
M is complete---content of beary metal (the mg kg that soil is whole
-1)
Accompanying drawing explanation
Fig. 1 is that variable concentrations humic acid and 0.1m/L potassium chloride combine the washout rate figure of eluent to cadmium;
Fig. 2 is different eluent process soil potassium content figure.
Claims (3)
1. fulvic acid and potassium chloride combine an eluent preparation method, and its preparation method is as follows:
A. humic acid is dissolved in the Klorvess Liquid of 0.1m/L, and regulates pH ≈ 11 to make the humic acid solution that weight ratio is 0.05-1.00% with the sodium hydroxide solution of 0.1m/L;
B. the pH=4.0 of the humic acid solution of regulating step a preparation, produces after precipitation centrifugal until solution, gets its clear liquid, and obtained fulvic acid and potassium chloride combine eluent.
2. the fulvic acid that obtains of preparation method described in claim 1 and potassium chloride combine an application for eluent, and it is characterized in that: the combination eluent adding above-mentioned concentration in cadmium pollution soil, described eluent and the volume ratio of cadmium pollution soil are 10:1.
3. fulvic acid according to claim 2 and potassium chloride combine the application of eluent, it is characterized in that: eluent concentration is 0.05%, the volume ratio of pH=4, eluent and cadmium pollution soil is 10:1, when the drip washing time is 2h.
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| CN103706629B (en) * | 2013-12-20 | 2017-01-25 | 四川农业大学 | Method for removing cadmium in contaminated soil through watermelon peel leaching |
| CN103817147B (en) * | 2014-02-17 | 2016-04-27 | 四川农业大学 | A kind of method utilizing the potassium chloride leaching liquor drip washing of edible fungi residues or schlempe to remove Cadium In Polluted Soil |
| CN107057710A (en) * | 2017-03-15 | 2017-08-18 | 中国科学院烟台海岸带研究所 | A kind of heavy metal-polluted soil eluent, preparation method, application method and method for treating waste liquid |
| CN109290362A (en) * | 2018-11-12 | 2019-02-01 | 湖南农业大学 | A kind of method of quick reduction soil full cadmium and effective cadmium content |
| CN109777429B (en) * | 2019-02-18 | 2020-03-24 | 浙江省农业科学院 | Humic acid source soil heavy metal effective state regulating agent and application thereof |
| CN109762568A (en) * | 2019-03-08 | 2019-05-17 | 河南沐天农业科技有限公司 | A kind of preparation method and applications of fulvic acid biological bacteria modifying agent |
| CN113083873A (en) * | 2021-03-23 | 2021-07-09 | 华南理工大学 | Mineral fractionation soluble organic matter material, preparation method thereof and application thereof in heavy metal passivation |
| CN115338249B (en) * | 2022-08-19 | 2023-04-07 | 生态环境部南京环境科学研究所 | Optimization method for restoring arsenic-cadmium polluted soil by leaching humic acid based on D-optimal design |
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| CN102049412A (en) * | 2009-11-05 | 2011-05-11 | 南开大学 | Biological compound preparation for repairing soil heavy metal pollution |
| CN102550603B (en) * | 2010-12-29 | 2014-03-05 | 北京市松浦经贸发展公司 | Extraction method of mineral concentrate for environmental restoration and application thereof |
| CN102319729B (en) * | 2011-07-30 | 2013-01-16 | 台州职业技术学院 | New method for combined remediation of compound contaminated soil |
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