CN101293254B - Method for eluting and renovating soil with heavy metal-organic matter combined pollution - Google Patents
Method for eluting and renovating soil with heavy metal-organic matter combined pollution Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 33
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- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 27
- 239000006228 supernatant Substances 0.000 claims abstract description 21
- 239000003480 eluent Substances 0.000 claims abstract description 20
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
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Abstract
The invention a method for restoring the soil with combined pollution of heavy metal-organic matter by leaching; the steps are as follows: the contents of polycyclic aromatic hydrocarbon and heavy metal as well as the basic physicochemical properties of the soil are analyzed; lactic ester is diluted to 5-20 weight percent according to the contents of organic matter and polycyclic aromatic hydrocarbon in the soil, then organic ligand of ethylenediamine is added according to the content of heavy metal in the soil, and the pH value is adjusted to neuter, thus an eluent is prepared; based on the dry weight of the soil, the eluent and the soil are added according to the proportion of 10:1 to 5:1 for leaching the soil for 24 hours, and then the soil and supernatant fluid are separated; the supernatant fluid is firstly adsorbed by organic adsorption resin, then passes through cation exchange resin, and the treated eluent can be recycled. The method has the following characteristics and advantages that: (1) the eluent can restore the soil with combined pollution of heavy metal-organic matter at the same time, and the environmental risk is small; (2) after the eluent is utilized circularly, the using amount of the eluent is reduced by, thus lowering the cost of restoration.
Description
Technical field
The present invention relates to a kind of ELUTION METHOD of rehabilitating soil combined pollution, the field is administered in the soil pollution that belongs in the environmental protection.
Background technology
Combined pollution when inorganic and organic pollution coexists is the direction and the emphasis of current combined pollution research.Research at present mainly concentrates on the combined pollution of organic chelating, agricultural chemicals, petroleum hydrocarbon and aromatic compounds and heavy metal.Heavy metal and polycyclic aromatic hydrocarbon are the important pollutants of two classes in the soil environment, often while or priority enter soil environment and form combined pollution, for a long time, both at home and abroad the microbial ecological toxicological effect and the reclamation activities of combined pollution between the independent pollution of heavy metal and polycyclic aromatic hydrocarbon and the different heavy metal have been carried out more research.Only at the single type pollutant, the restorative procedure of combined contamination soil rarely has report to present restorative procedure mostly.The combined pollution of existing foreign study is repaired simultaneously and is often needed to adopt the technology more than 2 or 2 to make up mutually, and this has improved the cost of repairing greatly, and negative effect is bigger.Up to the present, domestic soil remediation also all is confined to research at a kind of pollution type.
Heavy-metal contaminated soil also contains organic pollution usually, as benzene, and toluene, ethylbenzene, dimethylbenzene (BTEX) and polycyclic aromatic hydrocarbon.According to the investigation result of USEPA1997, there is 41% pollution preferentially to control and contains heavy metal and multiring aromatic hydrocarbon substance in the register simultaneously.The heavy metal and the PAHs pollution of administering simultaneously in the soil are more and more paid close attention to.At present, physics, chemistry, biology and various combination technique have been used to repairing heavy metal in soil-organic compound contaminated.Utilize the complexing and the solubilising power of organic ligand to come repairing heavy metal in soil and organic matter contaminated soil drip washing technology also to be used more.The advantage of this method is to have a high extraction, various agent in advance as: acid, chelating agent, oxidant and surfactant are widely used in the drip washing technology.Surfactant is owing to its high solubilising is used to repair in the research.But some surfactants are residual in soil easily, and to the deep subsoil migration, therefore may pollute underground water.Chelating agent as citric acid, NTA and EDTA, is the extractant that comparatively effectively extracts heavy metal in soil.Therefore EDTA causes second environmental pollution probably because its high complexing heavy metal ability has been widely used in still, because EDTA is difficult to by biodegradation, is easy to hold in environment and stays in the soil drip washing reparation.Therefore the selective extraction ability is strong, and the less eluent of environmental risk has become the focus of drip washing recovery technique.
In recent years, [S, S]-ethylenediaminedisuccinic acid (EDDS) owing to have the character of stronger complexing metal and easily biological-degradable, more and more is used as the substitute of EDTA.EDDS 7 to 11 days after soil drip washing begin degraded, and its degradation half life is 4.18 to 5.60 days.Discover that near neutral acidity scope, EDDS has higher extraction heavy metal in soil ability than EDTA.EDDS becomes effectively, safety and eco-friendly organic ligand are widely used in soil drip washing and the phytoremediation inductive technology.
The lactic acid ester material has easily biological-degradable and nontoxic characteristic, is widely used in food additives, biochemistry, medicine, the cosmetics manufacturing industry, also is used as solvent simultaneously and uses.It is " green solvent " that ethyl lactate is become, have high-solvency, can 100% degraded, easy characteristics such as circular regeneration, non-corrosiveness, non-carcinogenic, and in industrial production, use morely, easily obtain, cheap.Discover that the ligand solution that adds ethyl lactate and ethanol has better eluting power than simple part to the heavy metal in the soil, therefore in the technology of traditional part elution method remediating heavy metal, add a certain amount of ethyl lactate, in improving leacheate organic ligand to heavy metal mating reaction and desorption ability in, make it possess solvability simultaneously, just can reach the purpose that soil organic matter-heavy-metal composite pollution is repaired simultaneously organic pollution.
The soil elution method has all been obtained effect preferably at repairing heavy metal in soil and the organic matter field of polluting, but this technology need consume a large amount of leacheates usually, and this method just changes pollutant in the leacheate over to some degree.
Summary of the invention
1. invent the technical problem that will solve:
At spininess in the drip washing repairing polluted soil technology to the deficiency of single pollutant drip washing, the invention provides a kind of method of eluting and renovating soil with heavy metal-organic matter combined pollution, can be used for remediating heavy metal and organic material contaminated soil simultaneously, be used for solving the problem that the leacheate use amount is big, rehabilitation cost is high that the soil leaching repairing method exists.
2. technical scheme
A kind of method of eluting and renovating soil with heavy metal-organic matter combined pollution, its step comprises:
(1) analyzes polycyclic aromatic hydrocarbon and content of beary metal and soil basic physical and chemical in the soil;
(2) be 5%～20% according to the soil organism and polycyclic aromatic hydrocarbon content diluted lactic acid ester to percentage by weight, the content according to heavy metal in soil adds the ethylenediamines organic ligand then, regulates pH to neutral, is mixed with eluent;
(3) according to the soil dry weight, according to eluent: soil=added eluent washed off soil 24h in 10: 1～5: 1, separate soil and supernatant;
(4) supernatant is at first adsorbed by organic polymeric adsorbent, by cationic ion-exchange resin, the eluent after the processing can be recycling once more then.
Above-mentioned ethylenediamines organic ligand and heavy metal in soil content mol ratio are 1～3.
For the pouring fluid in the lessivation, technology by the absorption of resin two step reaches the recycling purpose of leacheate: will drench with organic polymeric adsorbent at first that organic pollution absorbs in the fluid, to drench in the fluid to be got off with cationic ion-exchange resin then by part chelated metal Copper Ion Exchange, leacheate after the resin treatment can be recycling once more, thereby further reach the use amount that reduces whole leacheate, reduce rehabilitation cost.The resin that adsorbs in the step (4) is NDA-150, and cationic ion-exchange resin is 001 * 7 storng-acid cation exchange resin.Replenish 2%～4% of ethyl lactate consumption in the resin treatment process.
3. beneficial effect
The method of a kind of eluting and renovating soil with heavy metal-organic matter combined pollution of the present invention, comparing with other heavy-metal contaminated soil restorative procedures has following characteristics and advantage: 1. leacheate repairing heavy metal in soil-organic compound contaminated soil simultaneously, and environmental risk is little; 2. leacheate has reduced the drip washing consumption after recycling, has reduced rehabilitation cost.
Description of drawings
Fig. 1 is that ethyl lactate-EDDS-aqueous systems is repaired the design sketch of Cu-PAHs combined pollution simultaneously; Wherein:
A be ethyl lactate-EDDS-water to polycyclic aromatic hydrocarbon-cuprum compound polluted extraction effect,
B is that ethanol-EDDS-water is to polycyclic aromatic hydrocarbon-cuprum compound polluted extraction effect;
Fig. 2 is the figure as a result of Cu morphological analysis in the soil before and after ethyl lactate-part-water wash liquid drip washing of using among the present invention;
Fig. 3 is the design sketch with the leacheate cycling elution PAHs of NDA-150 resin treatment;
Fig. 4 is the loss late figure as a result of leacheate ethyl lactate after different disposal, wherein:
A is through the NDA-150 resin treatment; B is for regulating pH after the NDA-150 resin treatment;
C is after the NDA-150 resin treatment, regulates pH, again through 001 * 7 resin treatment;
Fig. 5 is the recycling design sketch after the solution ethyl lactate loss problem.
The specific embodiment
Pedotheque is from Tang Shan mining area, Nanjing soil.Remove rubble, lose foreign material such as leaf, natural air drying in air is crossed the 2mm aperture sieve, and is standby.With a certain amount of phenanthrene of acetone solution and pyrene, slowly add in a certain amount of pedotheque then and mix thoroughly.The aging two week backs stand-by (Roy et al., 1997) of the brown wide-mouth bottle of packing into after air-dry.Final luxuriant and rich with fragrance concentration is 79.3mgkg
-1The concentration of pyrene is 95.8mg kg
-1Physicochemical property sees Table 1:
Table 1 soil basic physical and chemical
Embodiment 1:
The mining area pedotheque 1g that gets respectively in 2.5 has in the glass centrifuge tube of Teflon lid in 22ml, adding variable concentrations ethyl lactate to percentage by weight in another container is 5%～20%, and EDDS (EDDS/Cu mol ratio=2) solution, regulate drip washing system pH to neutral, be mixed with eluent, according to the soil dry weight, according to eluent: soil=added eluent washed off soil 24h in 10: 1～5: 1, separate soil and supernatant; 25 ± 1 ℃ of 24h that vibrate down, centrifugal after the balance, get supernatant liquor HPLC and analyze luxuriant and rich with fragrance and pyrene content, Cu in the atomic absorption detecting extract
2+Concentration, three every group are parallel, and research ethyl lactate-EDDS-water (ethanol-EDDS-water) is to the extraction effect of polycyclic aromatic hydrocarbon in the combined contamination soil and Cu.Supernatant is at first adsorbed by organic polymeric adsorbent, and by the cationic ion-exchange resin resin, the eluent after the processing can be recycling once more then.
What Fig. 1 showed is that solubilizer-part-aqueous systems is polluted the effect of repairing simultaneously to Cu and PAHs in the soil of mining area.The result shows that the mixing leacheate of ethyl lactate and EDDS has extraction effect preferably to Cu in the soil and PAHs.Along with the addition increase of ethyl lactate or ethanol, the extraction efficiency of Cu and PAHs all improves.The existence of Cu does not exert an influence to the extraction efficiency of PAHs, and when combined pollution was repaired, the average washout rate of Cu was 41.54%, and the result who pollutes soil with independent reparation mining area copper is more consistent.Along with the increase of ethyl lactate in the eluent and ethanol content, the washout rate of polycyclic aromatic hydrocarbon significantly increases.20% ethyl lactate is respectively 69.69% and 39.87%, 20% ethanol to the washout rate of luxuriant and rich with fragrance and pyrene the washout rate of luxuriant and rich with fragrance and pyrene is respectively 37.72% and 15.45%, and the extraction effect of phenanthrene is better than pyrene, and also the result with independent reparation polycyclic aromatic hydrocarbon is more consistent for this.
Embodiment 2:
The basic handling method is with embodiment 1, and treating capacity wherein is different with amount of reagent.
The BCR of European Union continuous extraction is adopted in morphological analysis, is divided into acid and can extracts attitude, oxide-bonded attitude, organic matter in conjunction with attitude, four kinds of forms of residual form.
First attitude (exchangeable species and carbonate are in conjunction with attitude) is (B1): get respectively 0.5g repair before and after soil sample, place 50ml polyethylene centrifuge tube, add 20ml 0.1mol/L HAc, the 16h that vibrates under the room temperature under the 3000rpm centrifugal 20 minutes, gets supernatant liquor, add the 0.2ml red fuming nitric acid (RFNA), measure.
Second attitude (Fe-Mn oxidation is in conjunction with attitude) is (B2): add 20ml 0.1mol/L NH in the upper level solid phase
2OHHCI, the 16h that vibrates under the room temperature, under the 3000rpm centrifugal 20 minutes, get supernatant liquor, add the 0.2ml red fuming nitric acid (RFNA), measure.
Elicit illness state (organic matter is in conjunction with attitude) is (B3): add 5ml 30%H in the upper level solid phase
2O
2, place 25 ℃ of water-bath 1h, place 85 ℃ of water-bath 1h again, add 5ml 30%H
2O
2Place 85 ℃ of water-bath 1h to do, in residue, add 25ml 1mol/L NH then near
4Ac (pH2.0HNO
3), the 16h that vibrates under the room temperature, under the 3000rpm centrifugal 20 minutes, get supernatant liquor, add the 0.2ml red fuming nitric acid (RFNA), measure.
The 4th attitude (residual form) perchloric acid-chloroazotic acid is cleared up, and adds 10ml chloroazotic acid (7ml nitric acid+3ml hydrochloric acid) in higher level's soil sample and heat 4-6h in 85 ℃ of water-baths, turns greyish white until soil sample, shifts, and is filtered in the 25ml volumetric flask constant volume mensuration with the middling speed quantitative filter paper.
The result of Fig. 2 shows that four kinds of form content are followed successively by residual form (36.19%)＞combination attitude (31.65%)＞exchangeable species (20.59%)＞oxide-bonded attitude (11.54%) in the preceding soil of extraction.Wherein the copper biological effectiveness of exchangeable species and oxide-bonded attitude is higher, is easily utilized by plant absorbing.Four kinds of form content are followed successively by residual form (28.88%)＞combination attitude (20.10%)＞exchangeable species (5.51%)＞oxide-bonded attitude (2.56%) in ethyl lactate-EDDS-aqueous systems extraction back soil.The Cu that the drip washing system is extracted is mainly from exchangeable species, oxide-bonded attitude and combination attitude.Extract back three kinds of form copper content and reduced 73.2%, 77.6% and 36.5% respectively.Similarly, ethanol-EDDS-aqueous systems obtains similar conclusion after extracting.Therefore extract the higher exchangeable species of biological effectiveness in the soil of back and the copper of oxide-bonded attitude and be extracted substantially, thereby reduced the plant utilizability, reduced environmental risk.
Compare with dystopy elution method repairing polluted soil method commonly used both at home and abroad at present, ethyl lactate-EDDS-glassware for drinking water has the advantage of heavy metal-polycyclic aromatic hydrocarbon combined pollution in the while rehabilitating soil, the remediation efficiency height, and the drip washing system has good biodegradability, toxicity is less, the ecological security height has important scientific value and wide application prospect.
Embodiment 3:
Get 1g soup mountain copper and pollute soil in 22mlCorex glass centrifuge tube, add 10ml leacheate (Tu Shui was than 1: 10 for EDDS/Cu=2, ethyl lactate 20%), use NaNO
3The ionic strength of regulation system is 0.01M, NaOH and HCI regulation system pH=7.Constant temperature vibration 12h.4000r/min leaves heart 10min, gets supernatant atomic absorption detecting copper content.Get 0.5g NDA-150 type resin in leachate, vibration 0.5h.Leachate after the resin treatment filters, and treats that cycling elution is used for the second time.Consider cause in the resin adsorption process the loss of leacheate, cycling elution is got 0.8g soup mountain copper and is polluted in the native 22mlCorex glass centrifuge tube for the second time, add resin processed leacheate (Tu Shui is than 1: 10, ionic strength 0.01M, pH=7).Constant temperature vibration 12h, 4000r/min leaves heart 10min, gets supernatant atomic absorption detecting copper content.Get 0.5g NDA-150 type resin in leachate, vibration 0.5h.After leachate after the resin treatment filters, treat that cycling elution is used for the third time.Get 0.5g soup mountain copper and pollute soil in 22mlCorex glass centrifuge tube, add resin processed leacheate (Tu Shui is than 1: 50, ionic strength 0.01M, pH=7).Constant temperature vibration 12h, 4000r/min leaves heart 10min, gets the content that supernatant is measured luxuriant and rich with fragrance and pyrene.
Behind the independent washed off soil polycyclic aromatic hydrocarbon of leacheate (Tu Shui was than 1: 10 for EDDS/Cu=2, ethyl lactate 20%), recycling after screening definite NDA-150 resin treatment that polycyclic aromatic hydrocarbon is had than the strong selectivity adsorption capacity, obtained cyclic utilization rate preferably.Recycling 2 times efficient is that 88%, 3 time efficient is 81%, sees Fig. 3.
Embodiment 4:
Get 1g soup mountain copper and pollute soil in 22mlCorex glass centrifuge tube, add 10ml leacheate (Tu Shui was than 1: 5 for EDDS/Cu=2, ethyl lactate 20%), use NaNO
3The ionic strength of regulation system is 0.01M, NaOH and HCl regulation system pH=7.Constant temperature vibration 12h.4000r/min leaves heart 10min, gets supernatant atomic absorption detecting copper content.Get 0.5g NDA-150 type resin in leachate, vibration 0.5h.Leachate after the resin treatment filters, and regulates leacheate pH=2, gets 0.5g001 * 7 resin adsorption again and handles, and recalls to pH after the processing for neutral, treats that cycling elution is used for the second time.Consider cause in the resin adsorption process the loss of leacheate, for the second time cycling elution is got 0.8g soup mountain copper and is polluted in the native 22mlCorex glass centrifuge tube, adding leacheate vibrates in oscillator, get supernatant after centrifugal and measure Cu content, use NDA-150 and 001 * 7 resin adsorption treatment pouring fluid respectively equally.After leachate after the resin treatment filters, treat that cycling elution is used for the third time.Get 0.5g soup mountain copper and pollute soil in 22mlCorex glass centrifuge tube, add resin processed leacheate.Constant temperature vibration 12h, 4000r/min leaves heart 10min, gets the content that supernatant is measured copper, phenanthrene and pyrene.
Leacheate (EDDS/Cu=2, ethyl lactate 20%, Tu Shui was than 1: 10) behind drip washing heavy metal-polycyclic aromatic hydrocarbon combined pollution, leacheate is recycling after NDA-150 resin and 001 * 7 resin treatment, drip washing effect to heavy metal Cu is followed successively by 41%, 32%, 31%, and decline trend is arranged; Drip washing effect to polycyclic aromatic hydrocarbon is then lower, and luxuriant and rich with fragrance elution efficiency is respectively 65%, 54%, 41% three times; Three elution efficiencies of pyrene are followed successively by 37%, 30%, 23%, and are bigger with the recycling difference of independent drip washing.
Embodiment 5:
Get 1g soup mountain copper and pollute soil in 22mlCorex glass centrifuge tube, adding 10ml leacheate (EDDS/Cu=3, the ethyl lactate percentage by weight is 5%, Tu Shui was than 1: 8), NaN0 used
3The ionic strength of regulation system is 0.01M, NaOH and HCl regulation system pH=7.Constant temperature vibration 12h.4000r/min leaves heart 10min, gets supernatant and measures luxuriant and rich with fragrance content.Get 0.5g NDA-150 type resin in leachate, vibration 0.5h.Leachate after the resin treatment filters, and regulates leacheate pH=2, gets 0.5g001 * 7 resin adsorption again and handles, and recalls to pH after the processing for neutral, treats that cycling elution is used for the second time.Consider cause in the resin adsorption process the loss of leacheate, for the second time cycling elution is got 0.8g soup mountain copper and is polluted in the native 22mlCorex glass centrifuge tube, add leacheate, add 2% and 4% ethyl lactate more respectively, in oscillator, vibrate, get supernatant after centrifugal and measure luxuriant and rich with fragrance content, use NDA-150 and 001 * 7 resin adsorption treatment pouring fluid respectively equally.After leachate after the resin treatment filters, treat that cycling elution is used for the third time.Get 0.5g soup mountain copper and pollute soil in 22mlCorex glass centrifuge tube, add and add 2% and 4% ethyl lactate behind the resin processed leacheate more respectively.Constant temperature vibration 12h, 4000r/min leaves heart 10min, gets supernatant and measures luxuriant and rich with fragrance content.
Consider the ethyl lactate loss, method by replenishing a certain amount of ethyl lactate before circulating is with leacheate cycling elution three times, for the first time the efficient of drip washing phenanthrene is 64%, and resin treatment replenishes behind 2% ethyl lactate for the second time that the efficient of cycling elution is 61.3%, and cycling elution is 61.7% for the third time; And the twice cycling elution rate behind 4% ethyl lactate of replenishing to have reached respectively be 68.6% and 75.1%, be higher than 65% of first drip washing.Therefore, the method for the hydrolysising loss of ethyl lactate is can solve the elution efficiency that the ethyl lactate minimizing causes in the resin adsorption process to descend by replenishing in a small amount, thereby makes that the cycling elution technology is pratical and feasible.
Claims (4)
1. the method for an eluting and renovating soil with heavy metal-organic matter combined pollution, its step comprises:
(1) analyzes polycyclic aromatic hydrocarbon and content of beary metal and soil basic physical and chemical in the soil;
(2) be 5%～20% according to the soil organism and polycyclic aromatic hydrocarbon content diluted lactic acid ester to percentage by weight, the content according to heavy metal in soil adds the ethylenediamines organic ligand then, regulates pH to neutral, is mixed with eluent;
(3) according to the soil dry weight, according to eluent: soil=added eluent washed off soil 24h in 10: 1～5: 1, separate soil and supernatant;
(4) supernatant is at first adsorbed by organic polymeric adsorbent, by cationic ion-exchange resin, the eluent after the processing can be recycling once more then.
2. the method for a kind of eluting and renovating soil with heavy metal-organic matter combined pollution according to claim 1 is characterized in that ethylenediamines organic ligand and heavy metal in soil content mol ratio are 1～3.
3. the method for eluting and renovating soil with heavy metal-organic matter combined pollution according to claim 1, the resin that adsorbs in the step (4) is NDA-150, cationic ion-exchange resin is 001 * 7 storng-acid cation exchange resin.
4. according to the method for claim 3 described eluting and renovating soil with heavy metal-organic matter combined pollution, it is characterized in that replenishing in the resin treatment process 2%～4% of ethyl lactate consumption.
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| CN109092881A (en) * | 2018-07-25 | 2018-12-28 | 上海松沅环境修复技术有限公司 | A kind of polycyclic aromatic hydrocarbon-heavy-metal contaminated soil elution device and repair system |
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