CN105154093A - Stabilizer for treating lead contaminated soil and application thereof - Google Patents
Stabilizer for treating lead contaminated soil and application thereof Download PDFInfo
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- CN105154093A CN105154093A CN201510437497.8A CN201510437497A CN105154093A CN 105154093 A CN105154093 A CN 105154093A CN 201510437497 A CN201510437497 A CN 201510437497A CN 105154093 A CN105154093 A CN 105154093A
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Abstract
The invention discloses a stabilizer for treating lead contaminated soil and application thereof. The stabilizer contains the ingredients in parts by weight: 1 part of organic sulfide, 0.4-2.5 parts of soluble phosphate and 0.5-3.5 parts of quick lime, wherein the organic sulfide is dithiocarboxylate. The stabilizer, which is prepared through proportionally mixing the organic sulfide, soluble phosphate and the quick lime, has a very good effect on treatment on the lead contaminated soil, and particularly, aiming at soil with relatively high lead content, the treated soil can reach standards by only once treatment; and moreover, the stabilizer is low in cost and better in treatment effect.
Description
Technical field
The present invention relates to a kind of stablizer for administering lead pollution of soil and application thereof, belonging to heavy-metal contaminated soil and administering field.
Background technology
At present, about 5,000,000 tons of lead are discharged in the whole world every year on average.Between past 50 years, the lead be discharged in global environment about has 7.83 × 10
5ton, wherein major part enters soil, causes countries in the world soil appearance heavy metal contamination in various degree.In 320 emphasis zone of pollution in the very fast area of the Economic developments such as China 24 province (city) outskirts of a town, sewage irrigation district, industrial and minerals, the agricultural output that heavy metal content exceeds standard and area account for pollutent and to exceed standard more than 80% of agricultural-food total amount and the total area, and wherein lead is one of the most serious vertical distribution.According to statistics, plumbous in China In The Suburbs of Large And Medium Cities vegetables, grain, fruit, meat and livestock product exceeding standard rate is respectively 38.6%, 28.0%, 27.6%, 41.9% and 71.1%.For Shenyang City, exposure plumbous in environment is general, and soil full lead content scope in urban district is 26 ~ 2910mg/kg, and pollution level is higher.In the lead pollution of soil of place, Chongqing, lead content scope is 10000 ~ 60000mg/kg, pollutes quite serious.
The recovery technique of lead pollution of soil can be divided into two large classes: physical chemistry recovery technique and bioremediation technology.Physical chemistry recovery technique can be divided into again isolation embedding techniques, solidification stabilization technique, chemical agent stabilization technique and electric repairing technique etc.Bioremediation technology can be divided into microorganism remediation technology and phytoremediation technology etc. again.At present, the reparation for lead pollution of soil mainly concentrates on chemical agent stabilization method.This method has the features such as cost is lower, remediation efficiency is higher, simple to operate.First this technology obtains investigation and application in some industrially developed country, and last decade is developed rapidly.
The medicament that chemical agent stabilization method is conventional comprises organic sequestering agent and inorganic chelator.The sequestering power of organic sequestering agent heavy metal is far away higher than inorganic chelator, organic chelated agent molecule and heavy metal generation faster sequestration react, generate stable heavy metal complex, be embedded in firmly in ped, there is very strong antiacid leaching ability, its shortcoming is that price is high, is not suitable for using in soil in a large number.Existing lead pollution of soil stabilization treatment uses inorganic chelator, as phosphoric acid salt more.The lead phosphate class precipitation of insoluble can be formed add phosphoric acid salt in lead pollution of soil after, this kind of precipitation water-soluble extremely low, thus the Available Lead that can effectively reduce in soil, its shortcoming is that solubleness is limited, fully can not react with Lead In Soil, medicament utilization ratio is not high, cause medicament to increase and waste, and the change of environment easily causes the leaching again of heavy metal.CN201410672066 mentions, and not only efficiency is low to add separately phosphate solution stabilization treatment lead pollution of soil, and it is partially long to expend the cycle.Application number be 201210107906.4 Chinese invention patent application disclose a heavy metal species ambient cure agent and use the method for heavy metal in its curing heavy metal pollutent.The heavy phosphates wherein formed after solidification exists with insoluble or sl. sol. compound form, and after potential of hydrogen condition changes, heavy metal ion is easily anti-molten.Except organic sequestering agent and inorganic chelator stabilization method, also have some modification methods for heavy-metal contaminated soil.CN201310477113 discloses with solid bamboo shoot shell base charcoal as soil improvement agent is for the modification method of heavy metal lead pollution soil.This modification method is conducive to improveing soil acidity and improving the adsorptive capacity of lead ion, but the lead concentration of the defined that can not ensure that the leaching concentration of Lead In Soil reaches " consumer waste filling and embedding pollutant catabolic gene standard " is lower than the standard of 0.25mg/L.And charcoal preparation process needs to dry and pulverizes and 400 DEG C of high temperature pyrolysis, preparation process is complicated and energy consumption is comparatively large, inapplicable to large-area severe lead pollution of soil or solid waste.In addition, by the restriction of chemical reaction equilibrium mechanism, the lead pollution of soil stabilization effect of one or more kind phosphoric acid salt single to serious pollution is limited, and a large amount of uses the secondary pollution that also can cause soil.In sum, current various lead pollution of soil stablizer to the reparation of severe lead pollution of soil have validity difference or utilization ratio is low or high in cost of production weak point.
Summary of the invention
The object of the invention is to overcome existing stablizer and have validity difference or utilization ratio is low or high in cost of production is not enough, provide that a kind of validity is good, utilization ratio is high, moderate cost, the simple stablizer of production.This stablizer effectively can reduce leaching concentration plumbous in lead pollution of soil, makes plumbous leaching concentration be reduced to below 0.25mg/L.
Technical scheme of the present invention is, provides a kind of stablizer for administering lead pollution of soil, and by weight, comprise 1 part of organic sulfide, 0.4 ~ 2.5 part of soluble phosphate and 0.5 ~ 3.5 part of unslaked lime, described organic sulfide is dithionate.
Further, described organic sulfide is dimethyl dithiocarbamate, N,N-Diethyldithiocarbamic Acid, ethyl dithiocarbonate, dithiocarbonic acid acetic acid disodium salt or its combination.
Further, soluble phosphate is the potassium of phosphoric acid, sodium, ammonium salt or its combination.Can be phosphoric acid salt, can be monohydric phosphate, dihydrogen phosphate.
The present invention provides a kind of application of the stablizer for administering lead pollution of soil further, adds aforementioned stable agent 5 ~ 20 weight part, stir in every 100 weight part lead pollution of soil, keeps water content 30 ~ 40%, maintenance 3 ~ 5 days.
The effect that this stablizer is used for lead pollution of soil stabilization treatment comprises two aspects: on the one hand, single calcium phosphate precipitation mechanism is limited, easily reach stabilization reactions saturated, limited to the stabilising effect of severe lead pollution of soil, the pH value of lead pollution of soil maintains between 8 ~ 10 by adding of appropriate unslaked lime, this will be conducive to soluble phosphate can form di lead with lead ion, thus realizes stable plumbous object.In addition, unslaked lime is met water heat release and is promoted phosphatic dissolving, increases the content of Soil Phosphorus acid ion, and can improve speed of reaction, lead ion stabilization reactions process is completed in the short period of time.On the other hand, organic sulfide composition and lead ion can form covalent type inner complex, have very high stability, and changing adaptable to environment pH, is the important supplement to phosphate-stabilized lead pollution of soil.The inner complex that organic sulfide is formed with lead is more stable than di lead, plumbous the depositing at organic sulfide of di of therefore reacting generation can be converted into chelating lead compound in case, and promotes that the chemical reaction equilibrium of phosphoric acid salt and lead ion moves to the direction generating di lead further.Dithionic acid the root (-CS of organic sulfide
2 -) two Sauerstoffatoms namely in carboxylate radical are replaced by sulphur, this structure can with lead ion stoichiometrically 2:1 react and generate stable complex compound.
Lead pollution of soil of the present invention is stabilizing agent specially used when disposing for lead pollution of soil, define machine sulfide and soluble phosphate addition according to acid extractable lead content in the soil that solid waste Leaching leaching method is measured, the addition of organic sulfide is 1.2 ~ 2.0 times of the metering of soil acid extractable lead content theoretical molar; Soluble phosphate is 3.0 ~ 5.5 times of the metering of soil acid extractable lead content theoretical molar; Mix with certain proportion unslaked lime before using, the soil moisture can be made to raise, improve phosphatic solubleness and chemical reaction rate.Add this stablizer in mass ratio in lead pollution of soil, stir, then add the abundant moistening mixture of a certain amount of water, the water content keeping mixture is 30% ~ 40%, maintenance 3 ~ 5 days.
The invention has the beneficial effects as follows, the improvement of stablizer to lead pollution of soil organic sulfide, soluble phosphate and unslaked lime being mixed in proportion composition has extraordinary effect, and particularly for the soil that lead content is higher, only need once administer can be up to standard; In addition, this kind of stablizer with low cost, regulation effect is better.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated: the application Lead contamination of the present invention in this concrete case study on implementation is repaired stablizer and significantly can be reduced Leaching concentration plumbous in lead pollution of soil, reaches the requirement of lead concentration limit value in the determined reparation target of contaminated soil remediation engineering.
Embodiment 1: it is that after repairing, soil meets the requirement of " household refuse landfill sites Environmental capacity standard " (GB16889-2008) that the lead determined in the lead pollution of soil recovery project of somewhere, Chongqing repairs target value.Collection in worksite lead pollution of soil sample, lead content is 68909mg/kg, and in the leach liquor prepared by " solid waste Leaching leaching method hac buffer method " (HJ/T300-2007), lead concentration is 808.8mg/L (corresponding acid extractable lead content is 16176mg/kg).Stabilization treatment is carried out to this lead pollution of soil, takes 100g lead pollution of soil, add the stablizer of mass ratio 20% (i.e. 20g) wherein, the component of stablizer and ratio are, Sodium dimethyldithiocarbamate 40min 4.4g, tertiary sodium phosphate 4.4g, unslaked lime 11.2g.Wherein the addition of Sodium dimethyldithiocarbamate 40min is 1.97 times (4.4% of soil quality) of theoretical molar metering, the addition of tertiary sodium phosphate is 5.15 times (4.4% of soil quality) of theoretical molar metering, the addition of unslaked lime is 11.2% of soil quality, then appropriate water-wet soil is added, the water content keeping mixture is 35%, maintenance 3 days.Concentration plumbous in the soil extract prepared by HJ/T300 after stabilization is 0.09mg/L, can meet the requirement of " household refuse landfill sites Environmental capacity standard " (GB16889-2008) middle lead concentration lower than 0.25mg/L.
In embodiment 1, Sodium dimethyldithiocarbamate 40min with plumbous reaction equation is:
2(CH
3)
2NCS
2Na+Pb
2+＝[(CH
3)
2NCS
2]
2Pb+2Na
+
Tertiary sodium phosphate with plumbous reaction equation is:
2Na
3PO
4+3Pb
2+＝Pb
3(PO
4)
2+6Na
+
Theoretical molar metering and excessive multiple calculation result are as table 1:
The metering of table 1 theoretical molar and excessive multiple calculate
Embodiment 2: the lead determined in Certain District, Hunan lead pollution of soil recovery project is repaired target value and met III class standard requirement in " groundwater quality standard " (GB/T14848-93) for repairing rear soil.Collection in worksite lead pollution of soil sample, lead content is 8100mg/kg, and in the leach liquor prepared by " solid waste Leaching leaching method sulfonitric method " (HJ/T299-2007), lead concentration is 225.6mg/L (corresponding acid extractable lead content 4512mg/kg).Stabilization treatment is carried out to this lead pollution of soil, takes 100g lead pollution of soil, add the stablizer of mass ratio 5% (i.e. 5g) wherein, the component of stablizer and ratio are, Sodium dimethyldithiocarbamate 40min 0.94g, SODIUM PHOSPHATE, MONOBASIC 0.70g, unslaked lime 3.36g.Wherein the addition of Sodium dimethyldithiocarbamate 40min is 1.51 times (0.94% of soil quality) of theoretical molar metering, the addition of SODIUM PHOSPHATE, MONOBASIC is 4.01 times (0.70% of soil quality) of theoretical molar metering, the addition of unslaked lime is 3.36% of soil quality, then appropriate water-wet soil is added, the water content keeping mixture is 30%, maintenance 5 days.Concentration plumbous in the soil extract prepared by HJ/T299-2007 after stabilization is 0.03mg/L, can meet the requirement of III ekalead concentration limit 0.05mg/L in " groundwater quality standard " (GB/T14848-93).
Embodiment 3: it is that after repairing, soil meets the requirement of " household refuse landfill sites Environmental capacity standard " (GB16889-2008) lead concentration lower than 0.25mg/L that the lead determined in certain place lead pollution of soil recovery project repairs target value.Collection in worksite lead pollution of soil sample, lead content is 18630mg/kg, and in the leach liquor prepared by " solid waste Leaching leaching method hac buffer method " (HJ/T300-2007), lead concentration is 507.6mg/L (corresponding acid extractable lead content is 10152mg/kg).The stablizer of 3 kinds of different ingredients is adopted to carry out stabilization treatment effect comparison to this lead pollution of soil.
(1) comparative example 1, takes 1 part of 100g lead pollution of soil, add wherein soil quality than 10% the dipotassium hydrogen phosphate of (i.e. 10g), wherein the addition of dipotassium hydrogen phosphate is 17.4 times that theoretical molar is measured.
(2) comparative example 2, take 1 part of 100g lead pollution of soil, add wherein soil quality than 10% the Sodium dimethyldithiocarbamate 40min of (i.e. 10g), wherein the addition of Sodium dimethyldithiocarbamate 40min is 7.14 times that theoretical molar is measured.
(3) embodiment 3, add wherein soil quality than 10% the stablizer of (i.e. 10g), the component of stablizer and ratio be, Sodium dimethyldithiocarbamate 40min 2.5g, dipotassium hydrogen phosphate 2.5g, unslaked lime 5.0g.Wherein the addition of Sodium dimethyldithiocarbamate 40min is 1.78 times (2.5% of soil quality) of theoretical molar metering, the addition of dipotassium hydrogen phosphate is 4.39 times (2.5% of soil quality) of theoretical molar metering, and the addition of unslaked lime is 5.0% of soil quality.Mixture after above-mentioned employing three kinds of different stabilizers process is all by adding appropriate water, the water content keeping mixture is 35%, curing time is 4 days, then prepares the leach liquor of mixture by HJ/T300, and Steep cencentration detected result and effect analysis are as table 2:
Table 2 three kinds of different ingredients stabilizer treatment lead pollution of soil effects
The lead pollution of soil effect comparison identical according to above-mentioned 3 kinds of different ingredients stabilizer treatments is analyzed, independent interpolation excess phosphoric acid salt pair soil carries out stabilization can not meet the requirement of " household refuse landfill sites Environmental capacity standard " (GB16889-2008) middle lead concentration lower than 0.25mg/L, during stablizer described in embodiment 3 all can meet " household refuse landfill sites Environmental capacity standard " (GB16889-2008), lead concentration is lower than the requirement of 0.25mg/L, treatment effect is better than comparative example 2, and the processing costs of embodiment 3 saves 59% than the processing costs of comparative example 2.
Claims (4)
1. for administering a stablizer for lead pollution of soil, it is characterized in that, by weight, comprise 1 part of organic sulfide, 0.4 ~ 2.5 part of soluble phosphate and 0.5 ~ 3.5 part of unslaked lime, described organic sulfide is dithionate.
2. stablizer as claimed in claim 1, is characterized in that, described organic sulfide is dimethyl dithiocarbamate, N,N-Diethyldithiocarbamic Acid, ethyl dithiocarbonate, dithiocarbonic acid acetic acid disodium salt or its combination.
3. stablizer as claimed in claim 1, is characterized in that, soluble phosphate is the potassium of phosphoric acid, sodium, ammonium salt or its combination.
4. for administering an application for the stablizer of lead pollution of soil, it is characterized in that, adding stablizer 5 ~ 20 weight part described in any one of claims 1 to 3 in every 100 weight part lead pollution of soil, stirring, keep water content 30 ~ 40%, maintenance 3 ~ 5 days.
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Cited By (9)
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| CN105820821A (en) * | 2016-05-18 | 2016-08-03 | 北京建筑材料科学研究总院有限公司 | Lead-zinc combined contaminated soil immobilizing agent and preparation method thereof |
| CN105967470A (en) * | 2016-05-12 | 2016-09-28 | 江西洁地环境治理生态科技有限公司 | Cadmium copper lead polluted bottom mud curing agent and curing method thereof |
| CN107418591A (en) * | 2017-08-09 | 2017-12-01 | 成都德菲环境工程有限公司 | The reparation medicament and restorative procedure of a kind of cadmium pollution soil |
| CN109207157A (en) * | 2018-11-05 | 2019-01-15 | 湖南泰谷生态工程有限公司 | A kind of chelating heavy metal soil conditioner and preparation method thereof |
| CN109201722A (en) * | 2017-07-04 | 2019-01-15 | 江西盖亚环保科技有限公司 | A method of strengthening Pb, As, Cu, Cd, Zn heavy-metal contaminated soil regulation effect |
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| CN110105958A (en) * | 2019-06-14 | 2019-08-09 | 许昌学院 | A kind of the mine soil reparation reagent and its application method of heavy metal lead pollution |
| CN110184069A (en) * | 2018-02-22 | 2019-08-30 | Snf加拿大有限公司 | The method for repairing the agricultural land soil by heavy metal pollution |
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| CN105820821A (en) * | 2016-05-18 | 2016-08-03 | 北京建筑材料科学研究总院有限公司 | Lead-zinc combined contaminated soil immobilizing agent and preparation method thereof |
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| CN110184069A (en) * | 2018-02-22 | 2019-08-30 | Snf加拿大有限公司 | The method for repairing the agricultural land soil by heavy metal pollution |
| CN109207157A (en) * | 2018-11-05 | 2019-01-15 | 湖南泰谷生态工程有限公司 | A kind of chelating heavy metal soil conditioner and preparation method thereof |
| CN109207157B (en) * | 2018-11-05 | 2021-05-25 | 湖南泰谷生态工程有限公司 | Heavy metal chelated soil conditioner and preparation method thereof |
| CN109913223A (en) * | 2019-03-29 | 2019-06-21 | 武汉强丰新特科技有限公司 | A kind of soil-repairing agent and its application method |
| CN109943345A (en) * | 2019-04-17 | 2019-06-28 | 湖南清之源环保科技有限公司 | Reparation medicament and its preparation method and application for handling heavy-metal contaminated soil |
| CN110105958A (en) * | 2019-06-14 | 2019-08-09 | 许昌学院 | A kind of the mine soil reparation reagent and its application method of heavy metal lead pollution |
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Application publication date: 20151216 |