CN104624630A - Passivant for in-situ remediation of polluted farmland and application method of passivant - Google Patents
Passivant for in-situ remediation of polluted farmland and application method of passivant Download PDFInfo
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- CN104624630A CN104624630A CN201510016334.2A CN201510016334A CN104624630A CN 104624630 A CN104624630 A CN 104624630A CN 201510016334 A CN201510016334 A CN 201510016334A CN 104624630 A CN104624630 A CN 104624630A
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Abstract
The invention provides a passivant for in-situ remediation of a polluted farmland and an application method of the passivant and belongs to the technical field of farmland soil remediation management. The passivant is characterized by taking a pelelith as a carrier; the passivant is modified by thiosulfate, and phosphate and oxalic acid are used for adjusting the pH; the oxidation-reduction property of an iron salt is adjusted to prepare a micro-powder mixing reagent; and the biological effectiveness of mercury in the polluted farmland is reduced through the effects of chelating, oxidizing/reducing, precipitating, adsorbing and the like. A stabilizing agent is composed of the following components in mass ratio: the pelelith to thiosulfate to the total amount of phosphate and oxalic acid to the iron salt is 1 to (0.2-0.3) to (0.1-0.2) to (0.02-0.05); the pH of the reagent is 7.2-8.0 and the adding amount is 0.1%-0.5% of the mass of remediated soil; and the reagent can be applied with a fertilizer. The passivant has a simple synthetic process; and the content of the mercury in crops can be reduced and the activity of the farmland soil is kept.
Description
Technical field
The invention belongs to soil remediation Treatment process field, particularly a kind of passivator of in-situ immobilization mercury pollution farmland and using method.
Background technology
Mercury and mercuric compounds has very strong neurotoxicity and teratogenesis, and build-up effect and genetoxic significantly, can enter human body by forms such as breathing, skin contact and food chains, cause high risks to human health.Soil Mercury Pollution is the important component part of mercury pollution problem, and especially farmland mercury pollution directly has influence on and wants Food Security, and in the Wanshan Mountain, China Guizhou, regional representation obtains particularly evident.
For the repairing and treating of mercury pollution; all the time lack can scale application technology; stabilization technology is the comparatively ripe and economically viable method of one comparatively speaking; but stabilizing agent (i.e. passivator) type conventional is at present single; replicability is poor; as sulfide, phosphate etc., all there is the problems such as addition is large, reagent is unstable, long-term effect is poor.
If publication number is in the patent of invention of CN103639194A, propose to be that mercury contaminated soil is repaired in raw material passivation with sodium bentonite, but the mercury of only Absorbable organic halogens more than 65%, have strict demand to moisture content in soil, and the cycle is three months.
Publication number is in the patent of invention of CN102703090A, proposition hydroxyapatite, sodium alginate, calcium hydroxide carry out composite passivator of preparing and repair mercury contaminated soil in vegetable garden, but this reagent pH value is high, only reaches 50% to available mercury coefficient of stabilization, cannot promotion and application on a large scale.
Publication number is in the patent of invention of CN102873086A, proposes, by water-soluble salt compounded of iodine, sulfate, nitrate and thiosulfate preparation extract, repair, but this technical costs to be high in the mode extracted, and technical sophistication, cannot carry out scale application.
Publication number is in the patent of invention of CN101491811, proposes to strengthen gill fungus bacterium and repairs, but due to mushroom uptake limited, cultivation cycle is long, there is many unfavorable factors.
Publication number is in the patent of invention of CN104032138A, proposes to repair with thiosulfate solution, but needs to carry out drenching leaching early stage, complex process, and directly uses thiosulfate to there is the risk of mercury migration in course of reaction.
Publication number is in the patent of invention of CN103834409A, and propose bentonite and the composite passivated reagent of diammonium hydrogen phosphate, addition, up to 9%, cannot realize using in agricultural land soil.
Therefore, for the innovation of passivator be the core of this technology.
Summary of the invention
The present invention is the deficiency overcoming above-mentioned passivator, proposing a kind of passivator and using method of in-situ immobilization mercury pollution farmland, take pelelith as carrier, by thiosulfate modification, be aided with phosphate and oxalic acid carries out pH adjustment, and regulate oxidation/reduction by molysite.
The passivator in a kind of in-situ immobilization mercury pollution farmland of the present invention and using method, it is characterized in that each constituent mass ratio of passivator is, pelelith: thiosulfate: phosphate and total oxalate: molysite=1: (0.2 ~ 0.3): (0.1 ~ 0.2): (0.02 ~ 0.05).
The passivator in a kind of in-situ immobilization mercury pollution farmland of the present invention and using method, it is characterized in that phosphate and oxalic acid mass ratio are determined with pH, reagent preparation pH is 7.2 ~ 8.0.
The passivator in a kind of in-situ immobilization mercury pollution farmland of the present invention and using method, it is characterized in that passivator preparation method is: pelelith pulverizes and sieves 100 orders, add thiosulfate in proportion, add suitable quantity of water (can stir) and be heated to more than 50 DEG C, after stirring reaction 30min, add molysite, continue to stir 10min, be cooled to normal temperature, outfit phosphate and oxalic acid mixture add, fully air-dry pulverizing after mixing, and sieve 60 orders.
The passivator in a kind of in-situ immobilization mercury pollution farmland of the present invention and using method, it is characterized in that this passivator addition is 0.1% ~ 0.5% of rehabilitating soil amount, can add or mix with fertilizer before fertilising and add, directly turn over and enter in the 30cm soil of top layer, farmland, reaction time should be greater than one week.
This passivator synthesis technique is simple, can at reduction crop mercury content simultaneously, keep agricultural land soil active.
The passivator in a kind of in-situ immobilization mercury pollution of the present invention farmland and using method, its dominant mechanism is chelating, oxidation/reduction, precipitation, suction-operated, pelelith skeleton is wherein had to be carrier, by its surface modification functional group, nonvalent mercury is adsorbed, complexing, carry sulfo-sulfide and be decomposed to form sulfide, can form stable mercuric sulphide with mercury ion, the mercury ion conversion of the adjustable labile state of molysite is carried out chelatropic reaction with phosphate radical, oxalate etc. and is formed the extremely low residual form mercury of biological effectiveness; Simultaneously because the alkalescent of reagent can neutralizing acid contact scar soil (mercury pollution farmland property all on the weak side), the mineralogical character of pelelith can play cushioning effect for extreme soda acid external condition for guarantee reagent.Consider the positive charge on pelelith surface, can carry biomembrane richness, be conducive to the growth of crops.
With conventional passivation Reagent evaluation ratio, the passivator that the present invention proposes, has no side effect, with strong points, addition is few, fast and reliable, and agricultural land soil can be kept active simultaneously.The present invention is applicable to the stabilisation of mercury pollution agricultural land soil, but is not limited only to this, is applicable to other soil simultaneously, as mine tailing, slag, bed mud, flying dust etc. and mercury combined pollution situation.
Detailed description of the invention
Passivator take pelelith as carrier, by thiosulfate modification, is aided with phosphate and oxalic acid carries out pH adjustment, and regulates oxidation/reduction by molysite.Pelelith pulverizes and sieves 100 orders, add thiosulfate in proportion, add suitable quantity of water (can stir) and be heated to more than 50 DEG C, molysite is added after stirring reaction 30min, continue to stir 10min, be cooled to normal temperature, outfit phosphate and oxalic acid mixture add, air-dry pulverizing after abundant mixing, sieve 60 orders.。
Its specific embodiment has:
Embodiment 1: get milled 100 mesh sieve pelelith 2kg, mixing adds sodium thiosulfate 0.4kg, and add water 5L, is heated to 50 DEG C, adds 0.04kg Fe after stirring 30min
2o
3, continue to stir 10min, be cooled to normal temperature.Add after getting sodium dihydrogen phosphate 0.3kg, oxalic acid 0.1kg mixing, stir 5min, fully after mixing, air-dry 60 orders that sieve are for subsequent use, and passivator pH is 8.0.Test site is certain mercury pollution farmland, and Hg content is 117.4mg/kg, and region, experimental plot is 10m
2, blank and add each half of reagent, addition is that the farmland 30cm that turns over tests the 0.1%2.4kg of soil amount, and rice cultivation, gets Duplicate Samples and detect after maturation.
Table 1 mercury contaminated soil treatment effect mg/kg
| Project | Blank | Add | Standard is limit |
| Rice | 0.089±0.003 | 0.014±0.002 | 0.02 |
Note: standard limited value is with reference to GB2762-2005 " pollutants in food limitation "
Embodiment 2: get milled 100 mesh sieve pelelith 4kg, mixing adds sodium thiosulfate 1kg, and add water 10L, is heated to 50 DEG C, adds 0.12kg Fe (OH) after stirring 30min
3, continue to stir 10min, be cooled to normal temperature.Add after getting sodium dihydrogen phosphate 0.4kg, oxalic acid 0.4kg mixing, stir 5min, fully after mixing, air-dry 60 orders that sieve are for subsequent use, and passivator pH is 7.5.Test site is certain mercury pollution farmland, and Hg content is 182.3mg/kg, and region, experimental plot is 10m
2, blank and add each half of reagent, addition is that the agriculture 30cm that turns over tests the 0.2%4.8kg of soil amount, and rice cultivation, gets Duplicate Samples and detect after maturation.
Table 2 mercury contaminated soil treatment effect mg/kg
| Project | Blank | Add | Standard is limit |
| Rice | 0.119±0.005 | 0.015±0.003 | 0.02 |
Note: standard limited value is with reference to GB2762-2005 " pollutants in food limitation "
Embodiment 3: get milled 100 mesh sieve pelelith 6kg, mixing adds sodium thiosulfate 1.2kg, and add water 15L, is heated to 50 DEG C, adds 0.3kg Fe after stirring 30min
2sO
47H
2o, continues to stir 10min, is cooled to normal temperature.Add after getting sodium dihydrogen phosphate 0.9kg, oxalic acid 0.3kg mixing, stir 5min, fully after mixing, air-dry 60 orders that sieve are for subsequent use, and passivator pH is 7.8.Test site is certain mercury pollution farmland, and Hg content is 182.3mg/kg, and region, experimental plot is 10m
2, blank and add each half of reagent, addition is that the farmland 30cm that turns over tests the 0.3%7.2kg of soil amount, and plantation pakchoi, gets Duplicate Samples and detect after maturation.
Table 3 mercury contaminated soil treatment effect mg/kg
| Project | Blank | Add | Standard is limit |
| Pakchoi | 0.073±0.003 | 0.005±0.001 | 0.01 |
Note: standard limited value is with reference to GB2762-2005 " pollutants in food limitation "
Embodiment 4: get milled 100 mesh sieve pelelith 10kg, mixing adds sodium thiosulfate 3kg, and add water 25L, is heated to 50 DEG C, adds 0.4kg Fe after stirring 30min
2sO
47H
2o, continues to stir 10min, is cooled to normal temperature.Add after getting sodium dihydrogen phosphate 1kg, oxalic acid 1kg mixing, stir 5min, fully after mixing, air-dry 60 orders that sieve are for subsequent use, and passivator pH is 7.2.Test site is certain mercury pollution farmland, and Hg content is 243.8mg/kg, and region, experimental plot is 10m
2, blank and add each half of reagent, addition is that the farmland 30cm that turns over tests the 0.5%12kg of soil amount, and plantation pakchoi, gets Duplicate Samples and detect after maturation.
Table 4 mercury contaminated soil treatment effect mg/kg
| Project | Blank | Add | Standard is limit |
| Pakchoi | 0.132±0.002 | 0.006±0.002 | 0.01 |
Note: standard limited value is with reference to GB2762-2005 " pollutants in food limitation ".
Claims (5)
1. the passivator in in-situ immobilization mercury pollution farmland and a using method, it is characterized in that, passivator take pelelith as carrier, by thiosulfate modification, is aided with phosphate and oxalic acid carries out pH adjustment, and regulates oxidation/reduction by molysite.
2. the passivator in a kind of in-situ immobilization mercury pollution farmland as claimed in claim 1 and using method, it is characterized in that each constituent mass ratio of passivator is, pelelith: thiosulfate: phosphate and total oxalate: molysite=1: (0.2 ~ 0.3): (0.1 ~ 0.2): (0.02 ~ 0.05).
3. the passivator in a kind of in-situ immobilization mercury pollution farmland as claimed in claim 1 and using method, it is characterized in that phosphate and oxalic acid mass ratio are determined with pH, reagent preparation pH is 7.2 ~ 8.0.
4. the passivator in a kind of in-situ immobilization mercury pollution farmland as claimed in claim 1 and using method, is characterized in that passivator preparation method is:
Pelelith pulverizes and sieves 100 orders, adds thiosulfate in proportion, adds suitable quantity of water, be heated to more than 50 DEG C, add molysite after stirring reaction 30min, continue to stir 10min, be cooled to normal temperature, outfit phosphate and oxalic acid mixture add, fully air-dry pulverizing after mixing, and sieve 60 orders.
5. the passivator in a kind of in-situ immobilization mercury pollution farmland as claimed in claim 1 and using method, it is characterized in that this passivator addition is 0.1% ~ 0.5% of rehabilitating soil amount, can add or mix with fertilizer before fertilising and add, reaction time should be greater than one week.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105414166A (en) * | 2015-12-31 | 2016-03-23 | 陕西清扬环境科技有限公司 | Repair method for mercury-polluted soil |
| CN106281337A (en) * | 2016-08-05 | 2017-01-04 | 中国地质大学（北京） | One utilizes potassium-enriched rock to prepare farmland soil heavy metals Cd passivator and preparation method thereof |
| CN106281332A (en) * | 2016-07-27 | 2017-01-04 | 武汉都市环保工程技术股份有限公司 | Mercury contaminated soil reparation passivator and mercury contaminated soil restorative procedure and application |
| CN107350284A (en) * | 2017-08-16 | 2017-11-17 | 航天凯天环保科技股份有限公司 | A kind of efficient restorative procedure of mercury contaminated soil |
| CN109265244A (en) * | 2018-10-24 | 2019-01-25 | 安文彬 | A kind of sterile soil conditioner and preparation method thereof containing a large amount of micro- mine elements |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107350284B (en) * | 2017-08-16 | 2020-02-04 | 航天凯天环保科技股份有限公司 | Efficient remediation method for mercury-contaminated soil |
| CN109265244A (en) * | 2018-10-24 | 2019-01-25 | 安文彬 | A kind of sterile soil conditioner and preparation method thereof containing a large amount of micro- mine elements |
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Application publication date: 20150520 |