CN103740372A - Fixing agent for repairing arsenic-polluted soil, and preparation and application method thereof - Google Patents
Fixing agent for repairing arsenic-polluted soil, and preparation and application method thereof Download PDFInfo
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- CN103740372A CN103740372A CN201410006537.9A CN201410006537A CN103740372A CN 103740372 A CN103740372 A CN 103740372A CN 201410006537 A CN201410006537 A CN 201410006537A CN 103740372 A CN103740372 A CN 103740372A
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Abstract
The invention discloses a fixing agent for repairing arsenic-polluted soil, and preparation and an application method thereof. The preparation of a chemical fixing agent comprises the following steps: 1) preparing a solution by using ferrous sulfate as a raw material, slowly adding an oxidant to the solution while stirring, collecting sediments after reacting for a period of time; 2) adding a sodium hydroxide solution to the collected sediments; filtering after reacting for 6-24 hours; and baking residues at 40-70 DEG C, grinding and sieving by a 100-mesh sieve, so as to obtain the chemical fixing agent. After the chemical fixing agent is added to the arsenic-polluted soil, the fixed rates of water-soluble arsenic and effective-state arsenic respectively reach 99.5% and 72.81%; the pH value of the soil does not need to be adjusted when the chemical fixing agent is in use, the physicochemical property of the soil is not destroyed, and the repaired soil is still applicable to plant growth.
Description
Technical field
The invention belongs to As polluted soil and administer field, in particular to a kind of fixing agent and methods for making and using same thereof of repairing As polluted soil.
Background technology
Mining, all can cause the arsenic pollution problem of soil containing the discharge of arsenic three industrial wastes etc.Arsenic in soil pollution can cause crop production reduction, causes agricultural product security problem simultaneously, and the arsenic in soil may or directly contact the health of human body is worked the mischief by food chain, tap water.China is in the urgent need to As polluted soil recovery technique at present.
Soil pollution has the features such as persistence, refractory reason, and how administering safely and effectively at present As polluted soil has become study hotspot.The improvement method of contaminated soil has drip-rinsing process, electrochemical process, Vitrification, fixing/stabilising method, phytoremediation, microorganism reparation etc.Wherein chemistry fixedly belongs to one of effective ways of administering As polluted soil.
Application number is that 200510136982 patent discloses a kind of method for the treatment of As polluted soil, described method can make arsenic compound (organic form or three or pentavalent inorganic form) not dissolve, thereby their leaching degree is reduced to below edatope standard value.Described method is comprised of the following step: As polluted soil heats at 200～700 ℃, and then the soil after heating mixes with calcium cpd and water again.Described method also can be comprised of the following step: As polluted soil mixes with calcium cpd, and then mixed soil heats at 200～700 ℃, and the soil after heating mixes with water again.Not only energy consumption is large and spoiled soil structure and fertility for the method.
Application number is that 200910272496.7 patent discloses a kind of chemical fixing material that is applicable to the arsenic in fixing soil and uses thereof, the mine tailing that the settling that chemical fixing material prepared by this invention can effectively pollute As polluted soil, arsenic and arsenic pollute etc. carries out the fixing processing of arsenic, reduce its biological effectiveness, suppress absorption and the accumulation of farm crop to arsenic.But this invention, take the sharp state type of nanometer titanium dioxide, nm-class rutile-type TiO 2, zeroth order iron powder as solid material, is prepared more complicated, and raw materials cost is higher, is not suitable for large-area applying.
Application number is that 201010204184.5 patent discloses a kind of method for the treatment of As polluted soil, and the method is to add iron salt solutions in As polluted soil, and iron salt solutions is reacted with the arsenic in soil, forms the arsenate FeAsO of iron
3or FeAsO
4.And, then add and also contaminated soil is carried out to fragmentation, pH regulator before iron salt solutions and measure in As polluted soil the steps such as arsenic content.Iron salt solutions can cause detrimentally affect to the physico-chemical property of soil, especially serious on soil pH value impact, still needs unslaked lime to carry out pH regulator, and it is convenient not to make to use.
Therefore, need to provide a kind of and can overcome medicament prior art deficiency, simply efficient, novel improvement As polluted soil.
Summary of the invention
Object of the present invention aims to provide a kind of environmental friendliness, and expense is low, not chemical fixatives and the methods for making and using same thereof of the cost-effective reparation As polluted soil of spoiled soil physico-chemical property.
A preparation method who repairs the fixing agent of As polluted soil, comprises the following steps:
(1) copperas solution that preparation ferrous ion concentration is 0.04-1.2mol/L;
(2) to the solution of step (1), add oxygenant while stirring, after reaction 6-24h, filter, collect residue;
(3) residue of step (2) is joined in the NaOH solution of 7<pH<9 of 30-70 ℃, after reaction 6-24h, filter, dry residue obtainedly, grind, obtain chemical fixatives.
Oxygenant described in step (2) is one or more in hydrogen peroxide, Potcrate, clorox, and the mol ratio of oxygenant and Fe2+ is 1:1-2.
While filtering in step (2), in the acid of 1.5-3, clean residue with pH, then clean with pure water.
Described in step (3), residue is 40-70 ℃ of oven dry.
Described in step (3), residue ground 100 mesh sieves.
Repairing a fixing agent for As polluted soil, is to be prepared from by described method.
The application method of the fixing agent of described reparation As polluted soil, As polluted soil adds described fixing agent, then adds tap water, and quality is soil than scope: fixing agent: water=100:(3-6): (30-60), be stirred to evenly at least 7 days treatment times.
The present invention has following advantage:
1. the main production raw material of fixing agent of the present invention is ferrous sulfate, and raw material sources are extensive, with low cost.The production operation of fixing agent is simple and convenient, is beneficial to scale operation.
2. the main production raw material of fixing agent of the present invention is the oxygenants such as ferrous sulfate and hydrogen peroxide, clorox.The fixing agent of preparation is mainly comprised of chemical elements such as iron, oxygen, hydrogen and sulphur, and these chemical elements are the main components of soil itself.Therefore, fixing agent prepared by the present invention is applied to the heavy metal of contaminated soil and fixes, and can not cause soil secondary pollution problem.
3. fixing agent of the present invention, has huge specific surface area and contains the groups such as great amount of hydroxy group, sulfate radical, and it has stronger absorption and co-precipitation to arsenate or arsenous anion ion.(Asia) arsenate can not only carry out ligand exchange with fixing agent surface hydroxyl, may can also form stable inner-sphere complex with sulfate groups, thereby strengthen the fixed effect of arsenic.
4. compare with conventional molysite (ferric sulfate, iron(ic) chloride and bodied ferric sulfate etc.) As retention, fixing agent of the present invention can not cause soil severe acidification problem in application process, the reparation later stage does not need to regulate soil pH value, can not break and change Soil structure, is more conducive to cultivate crop.
Accompanying drawing explanation
Fig. 1 is the XRD figure of chemical fixatives of the present invention;
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of chemical fixatives of the present invention;
Fig. 3 is the infrared spectrogram (FT-IR) of chemical fixatives of the present invention;
Fig. 4 be chemical fixatives of the present invention when different usage quantity to As polluted soil in the fixed effect figure of As;
Fig. 5 is chemical fixatives of the present invention and the ferric sulfate fixed effect comparison diagram to As in As polluted soil respectively.
Embodiment
Below in conjunction with the drawings and specific embodiments, be intended to the present invention to be described in further details, and unrestricted the present invention.
Preparation the present invention repairs As polluted soil fixing agent:
(1) copperas solution that preparation ferrous ion concentration is 0.04-1.2mol/L;
(2) limit is stirred and to above-mentioned solution, is added oxidant hydrogen peroxide, oxygenant and Fe
2+mol ratio be 1:1-2; Reaction 6-24h, then cleans residue 2-3 time with pH in the acid of 1.5-3 left and right during suction filtration, then cleans 2-3 time collection residue with pure water.
(3) above-mentioned residue is dissolved in 30-70 ℃ of 7<pH<9NaOH solution, after reaction 6-24h, suction filtration, 40-70 ℃ of oven dry is residue obtained, grinds 100 mesh sieves, obtains chemical fixatives.
In this example, in each Erlenmeyer flask, take 10g As polluted soil, add the fixing agent of embodiment 1 of the mass ratio 4% of preparing under condition of different temperatures in polluted soil, according to native quality, than 2:1, add tap water, be stirred to evenly.Sampling afterwards in standing 7～14 days, measures water-soluble state As and available state As(sodium bicarbonate extraction agent state in soil) content.After testing, in soil after fixing agent reparation prepared by lesser temps, the content of water-soluble state As and sodium bicarbonate lixiviate state As is reduced to 0.98mg/kg and 156.28mg/kg by original 27.11mg/kg and 312.49mg/kg respectively, the fixed rate of water-soluble state is 96.38%, and the fixed rate of sodium bicarbonate lixiviate state is 49.99%; In soil after fixing agent reparation prepared by comparatively high temps, the content of water-soluble state As and sodium bicarbonate lixiviate state As is reduced to 0.12mg/kg and 84.97mg/kg by original 27.11mg/kg and 312.49mg/kg respectively, the fixed rate of water-soluble state is 99.57%, and the fixed rate of sodium bicarbonate lixiviate state is 72.81%.
Embodiment 3
Experiment is picked up from Hunan Province's crossdrift with soil, after air-dry, impurity elimination and grinding, crosses 20 order nylon mesh.In this example, take 10g As polluted soil in each Erlenmeyer flask, chemical fixatives is added in contaminated soil with mass ratio 1%, 2%, 4%, 4.5%, 5%, 6%, 8%, 10% respectively, according to native quality, than 2:1, adds tap water, is stirred to evenly.Sampling afterwards in standing 7～14 days, measures water-soluble state As and available state As(sodium bicarbonate extraction agent state in soil) content.After testing, when fixing agent addition is 4%, in soil, the content of water-soluble state As and sodium bicarbonate lixiviate state As is reduced to 0.94mg/kg and 104.86mg/kg by original 33.17mg/kg and 226.78mg/kg respectively, the fixed rate of water-soluble state is 97.17%, and the fixed rate of sodium bicarbonate lixiviate state is 53.76%.
Claims (7)
1. a preparation method who repairs the fixing agent of As polluted soil, is characterized in that, comprises the following steps:
(1) copperas solution that preparation ferrous ion concentration is 0.04-1.2mol/L;
(2) to the solution of step (1), add oxygenant while stirring, after reaction 6-24h, filter, collect residue;
(3) residue of step (2) is joined in the NaOH solution of 7<pH<9 of 30-70 ℃, after reaction 6-24h, filter, dry residue obtainedly, grind, obtain chemical fixatives.
2. preparation method according to claim 1, is characterized in that: oxygenant described in step (2) is one or more in hydrogen peroxide, Potcrate, clorox, oxygenant and Fe
2+mol ratio be 1:1-2.
3. preparation method according to claim 1, is characterized in that: while filtering in step (2), clean residue with pH in the acid of 1.5-3, then clean with pure water.
4. preparation method according to claim 1, is characterized in that: described in step (3), residue is 40-70 ℃ of oven dry.
5. preparation method according to claim 1, is characterized in that: described in step (3), residue ground 100 mesh sieves.
6. a fixing agent of repairing As polluted soil, is characterized in that, is to be prepared from by the method described in claim 1-5 any one.
7. the application method of the fixing agent of reparation As polluted soil claimed in claim 6, it is characterized in that, As polluted soil adds described fixing agent, add again tap water, quality is soil than scope: fixing agent: water=100:(3-6): (30-60), be stirred to evenly at least 7 days treatment times.
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Cited By (9)
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| CN104263949A (en) * | 2014-08-01 | 2015-01-07 | 中国电建集团中南勘测设计研究院有限公司 | Method for stably treating arsenic caustic sludge |
| CN105032910A (en) * | 2015-06-12 | 2015-11-11 | 湖南大学 | Composite eluting agent for repairing arsenic contaminated soil and application method thereof |
| CN105542776A (en) * | 2015-12-18 | 2016-05-04 | 北京高能时代环境技术股份有限公司 | Stabilizing agent for harmless treatment of arsenic-contaminated soil |
| CN106075800A (en) * | 2016-06-03 | 2016-11-09 | 中南大学 | A kind of ferric arsenate/goethitum material utilizing arsenic containing solution preparation to have nucleocapsid structure realizes the method for solid arsenic |
| CN107254313A (en) * | 2017-06-29 | 2017-10-17 | 中南大学 | As polluted soil passivator and preparation method, the method for administering As polluted soil |
| CN109777427A (en) * | 2019-01-16 | 2019-05-21 | 深圳市铁汉生态环境股份有限公司 | A kind of medicament and its application for As polluted soil and arsenic-containing waste residue reparation |
| CN109777425A (en) * | 2019-01-22 | 2019-05-21 | 袁艺宁 | A kind of preparation method and applications of phosphorus ferric sulfate polymer |
| CN110079323A (en) * | 2019-04-30 | 2019-08-02 | 湖南省和清环境科技有限公司 | A kind of arsenic, nickel combined pollution place soil remediation stabilizer and its processing method |
| CN111676018A (en) * | 2020-06-08 | 2020-09-18 | 北京高能时代环境技术股份有限公司 | In-situ remediation medicament for contaminated site and construction method |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104263949A (en) * | 2014-08-01 | 2015-01-07 | 中国电建集团中南勘测设计研究院有限公司 | Method for stably treating arsenic caustic sludge |
| CN105032910A (en) * | 2015-06-12 | 2015-11-11 | 湖南大学 | Composite eluting agent for repairing arsenic contaminated soil and application method thereof |
| CN105542776A (en) * | 2015-12-18 | 2016-05-04 | 北京高能时代环境技术股份有限公司 | Stabilizing agent for harmless treatment of arsenic-contaminated soil |
| CN106075800A (en) * | 2016-06-03 | 2016-11-09 | 中南大学 | A kind of ferric arsenate/goethitum material utilizing arsenic containing solution preparation to have nucleocapsid structure realizes the method for solid arsenic |
| CN106075800B (en) * | 2016-06-03 | 2019-01-15 | 中南大学 | A method of using arsenic containing solution preparation there is ferric arsenate/goethite material of core-shell structure to realize solid arsenic |
| CN107254313A (en) * | 2017-06-29 | 2017-10-17 | 中南大学 | As polluted soil passivator and preparation method, the method for administering As polluted soil |
| CN109777427A (en) * | 2019-01-16 | 2019-05-21 | 深圳市铁汉生态环境股份有限公司 | A kind of medicament and its application for As polluted soil and arsenic-containing waste residue reparation |
| CN109777425A (en) * | 2019-01-22 | 2019-05-21 | 袁艺宁 | A kind of preparation method and applications of phosphorus ferric sulfate polymer |
| CN109777425B (en) * | 2019-01-22 | 2021-06-04 | 袁艺宁 | Preparation method and application of iron phosphosulfate polymer |
| CN110079323A (en) * | 2019-04-30 | 2019-08-02 | 湖南省和清环境科技有限公司 | A kind of arsenic, nickel combined pollution place soil remediation stabilizer and its processing method |
| CN111676018A (en) * | 2020-06-08 | 2020-09-18 | 北京高能时代环境技术股份有限公司 | In-situ remediation medicament for contaminated site and construction method |
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Application publication date: 20140423 |