CN106281331A - A kind of manufacture method of ferrum system heavy metal-polluted soil immobilization material - Google Patents
A kind of manufacture method of ferrum system heavy metal-polluted soil immobilization material Download PDFInfo
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- CN106281331A CN106281331A CN201510251997.2A CN201510251997A CN106281331A CN 106281331 A CN106281331 A CN 106281331A CN 201510251997 A CN201510251997 A CN 201510251997A CN 106281331 A CN106281331 A CN 106281331A
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Abstract
The present invention relates to the manufacture method of a kind of ferrum system heavy metal-polluted soil immobilization material, the manufacture method of a kind of simple, fast and efficient ferrum system immobilization of heavy metals material.The ferrum system heavy metal-polluted soil immobilization material of stable performance can be produced by simple step and device.The mechanism of the method be trivalent iron salt aqueous solution under the effect of metallic iron system reducing agent, part iron salt is reduced to ferrous salt, forms a certain proportion of iron salt and ferrous salt immobilization of heavy metals material.This material and heavy metal effect form magnetic ferrite precipitation, reduce heavy metal toxicity in soil.The advantage of this material is that heavy metal-polluted soil immobilization process is the most effective, with low cost, environment will not be caused secondary pollution.Lead (Pb), hydrargyrum (Hg), cadmium (Cd), chromium (Cr), nickel (Ni), copper (Cu), zinc (Zn), silver (Ag), manganese and the anions and canons such as metalloid arsenic (As), selenium (Se) all there is good immobilization treatment effect simultaneously.
Description
Technical field
The present invention relates to the manufacture method of a kind of ferrum system efficient immobilization material of heavy metal-polluted soil, prepare efficient immobilization of heavy metals material by simple step and device, anion, cationic heavy metal can be processed simultaneously.Can be widely used for the insoluble of various heavy-metal contaminated soil or immobilization processes, reduce its bio-toxicity.
Background technology
Soil pollution refers to that the material with physiological-toxicity or excessive plant nutrient enter soil and cause soil property to deteriorate and the phenomenon of physiological function of plants imbalance, and including agriculture plantation pollution, brownfield site pollutes and mining soil pollutes.Though soil has certain self-purification capacity, but it is once contaminated, the most contaminated by heavy metals, is difficult to recover.In a very long time in past, soil contamination problem never obtains enough attention, until occurring and the exposure of sudden environment public accident of serious soil pollution events such as " cadmium rice " in recent years " poison Rhizoma Zingiberis Recens " " cancer village " " arseniasiss ", Soil Pollution Control is just made really to cause the attention of the public.
Soil pollution situation is abnormal severe.China's soil pollution is in the situation increasingly aggravated at present, and prevention and control situation is the severeest.China's soil pollution area distribution is wider; " whole nation Soil Pollution Investigation publication " announced on April 17th, 2014 according to Environmental Protection Department and Ministry of Land and Resources; the point position exceeding standard rate that whole nation soil is total at present is 16.1%; and arable soil point position exceeding standard rate is more up to 19.4%; wherein slight, slight, moderate and serious pollution point ratio are respectively 13.7%, 2.8%, 1.8% and 1.1%; whole nation grain acreage is 20.27 hundred million mu at present; thus speculating, having arable soil area to be repaired is 3.9 hundred million mu.Result of study shows the heavy metal of different occurrence patterns, and its dirt reason activity and toxicity are the most variant.Wherein with water-soluble state and the activity of exchangeable species, toxicity maximum, the activity of residual form is minimum.
Soil Pollution Control technology is immature.Corresponding with severe soil pollution situation, the still aobvious weakness of the Soil Pollution Control technology of China.Owing to contaminated soil area is big, pollution level is deep mixed, and natural conditions are complicated and changeable, high to Soil Pollution Control technology and technological requirement.Existing Soil Pollution Control technology is immature, and physics administering method spends huge, and chemical repair method becomes the Main way of following remediation contaminated soil development.At present conventional method has: the medicament heavy metal drip washing extraction process such as the curing materials soil improvements such as cement process, acid, organic immobilization and or the complexed-precipitation method such as inorganic fixing agent.Organic heavy metal fixing agent is mainly aminodithioformic acid alkali metal salt, as: diethylamine aminodithioformic acid potassium, piperazine pair-aminodithioformic acid potassium, diethyl triamine-aminodithioformic acid potassium, trientine-aminodithioformic acid potassium, tetraethyl amylamine-aminodithioformic acid potassium, penta hexamine-aminodithioformic acid potassium etc..These organic chelated class immobilization of heavy metals agent, have good complexation immobilization effect to cation heavy metals such as lead, hydrargyrum, cadmiums, but to the anion such as arsenic, selenium without complexing power, immobilization effect are poor.
Additionally, inorganic heavy metal fixing agent, such as: the ferrum system immobilization of heavy metals agent that phosphoric acid, phosphate and bodied ferric sulfate, ferrous sulfate, ferrous chloride, iron chloride are formed by combining is to lead, Cr VI, arsenic, selenium immobilization simultaneously.The especially ferrous immobilization of heavy metals material combined according to a certain percentage with ferrum, but ferrous unstable, the most oxidized and reduce immobilization of heavy metals effect.
Summary of the invention
For the problems referred to above, the immobilization of heavy metals material that the present invention manufactures, it is simply that a certain proportion of ferrous salt and the mixed aqueous solution of trivalent iron salt.Without the powder body sold on the markets such as ferrous sulfate or aqueous solution, use simple step and device, stable ferrum system immobilization of heavy metals material can be produced at short notice.
The present invention solves above-mentioned technical problem and employed technical scheme comprise that the manufacture method that have employed a kind of ferrum system heavy metal-polluted soil immobilization material:
The present invention is directly to mix bodied ferric sulfate with metallic iron system reducing agent to contact, a ferric iron part in polyaluminum sulfate water solution is reduced to bivalence ferrous iron aqueous solution, produces bivalence ferrous iron aqueous solution and the ferrum system immobilization of heavy metals material of the trivalent iron salt aqueous solution common combination not being reduced.
Ferrous ratio (the Fe with full ferrum in the ferrum system heavy metal-polluted soil immobilization material that the present invention prepares2+/ (Fe2++ Fe3+)) be 0.2～0.8, optimal ratio be 0.2～0.4.The ferrous ratio with full ferrum less than 0.2 or is higher than 0.8, then this ferrum system heavy metal-polluted soil immobilization material can not react with heavy metal and generate ferrite precipitation, thus reduces the effect processing heavy metal.
Beneficial effects of the present invention:
1, the ferrum system immobilization of heavy metals material that this method manufactures is without using the most oxidized unstable perferrite solution, the most do not use the ferrous sulfate pressed powder being dissolved in water slow, but use simple step and device, produce stable immobilization of heavy metals material in the short time.
2, the reducing agent that the present invention uses is the metallic iron system reducing agents such as metallic iron, can increase so manufacturing ferrous iron concentration and full concentration of iron in the ferrum system immobilization of heavy metals agent obtained.
3, the ferrum system immobilization of heavy metals material that this method manufactures can have good immobilization treatment effect to lead (Pb), hydrargyrum (Hg), cadmium (Cd), trivalent chromium (Cr), nickel (Ni), copper (Cu), zinc (Zn), the silver anion such as the cation such as (Ag), manganese (Mn) and Cr VI, metalloid arsenic (As), selenium (Se) simultaneously.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.Described embodiment and result thereof are merely to illustrate the present invention, and should be also without limitation on the present invention described in detail in claims.
The manufacture method of the ferrum system immobilization of heavy metals material of the present invention is to add metallic iron system reducing agent in polyaluminum sulfate water solution, both are allowed to be fully contacted mixing, ferric iron in bodied ferric sulfate is reduced to bivalence ferrous iron aqueous solution, this ferrous iron aqueous solution forms a certain proportion of ferrous salt and trivalent iron salt aqueous solution with new bodied ferric sulfate aqueous solution, manufactures and obtains ferrum system immobilization of heavy metals material.
Such as: polyaluminum sulfate water solution adds metallic iron system reducing agent, it is bivalence ferrous iron aqueous solution by the ferric iron back in polyaluminum sulfate water solution, the bivalence ferrous iron aqueous solution prepared transports scene, at the scene, ferrous aqueous solution is mixed into ferrous salt and trivalent iron salt aqueous solution by a certain percentage with new polyaluminum sulfate water solution, manufactures and obtain ferrum system immobilization of heavy metals material.
This manufacture method because not using instability, the most oxidized ferrous aqueous solution, so without the storage management equipment of ferrous aqueous solution, and do not use pressed powder ferrous iron raw material to need not dissolution time, improve the efficiency and product stability manufactured.And the reduction reaction of this manufacture method is very fast, can complete in the shortest time, comparing traditional method time is greatly shortened.Reducing agent is metallic iron system reducing agent, and manufacturing ferrous iron concentration and full concentration of iron in the ferrum system immobilization of heavy metals agent obtained can increase.
(1) polyaluminum sulfate water solution
Polyaluminum sulfate water solution is the raw material that on market, comparison solution is bought.In order to promote that metallic iron system reducing agent dissolves and prevents ferric ion from hydrolyzing, preferably in bodied ferric sulfate aqueous solution, add sulphuric acid or dilute sulfuric acid carries out acidity adjustment.Ferrum 1 weight portion in metallic iron system reducing agent, 100% sulphuric acid needs 0.5 ~ 5.0 weight portion, preferably 1.5 ~ 2.5 weight portions.
(2) metallic iron system reducing agent
Metallic iron system reducing agent refers to the metallic iron based materials such as ferrum oxide and alloyed iron such as soft net and the cast iron of reduced iron powder, electrolytic iron powder and other granules.Metallic iron clock iron-holder is more than 90%, and lead, arsenic, selenium, antimony and chromium containing ratio are below 1%, and the containing ratio such as carbon, manganese, nickel is below 10%, if containing insoluble matter, then needs to increase filtering technique.When metallic iron reducing agent dissolves slow, then dissolving and reduce and carry out simultaneously, dissolved, ferric ion is also terminated by reduction simultaneously, and stirring can accelerate dissolving and reduction process.Metallic iron system reducing agent is preferably used the mean diameter powdery metal ferrum at 2mm.If particle diameter is more than 2mm, then metallic iron easily settles, and stirs insufficient, reduction treatment time lengthening, and product quality can not be guaranteed.
Manufacture:
(1) groove is manufactured
This manufacture method uses medicament to manufacture the manufacture device of groove, and this manufacture groove is acidproof, is the steel groove by the included polyethylene of polyethylene groove sold on market and fiber composite material groove etc., built with mechanical stirring device.First in manufacturing groove, add polyaluminum sulfate water solution and metallic iron system reducing agent, be sufficiently stirred for contact, dissolve and reduction reaction occurs, by ferric iron Restore All in polyaluminum sulfate water solution.Add new polyaluminum sulfate water solution, mix homogeneously, obtain the amount of ferrous and full iron substance than the mixed solution for 0.2-1.0.
(2) packed layer
This manufacture method is to be filled in packed layer with by metallic iron system reducing agent, and wherein ferrum system reducing agent is mainly ferrum oxide, alloyed iron and other cheap ferrum system reducing agents.The height of packed layer is 0.5m ~ 2m, in packed layer, the mean diameter of ferrum system reducing agent is 2mm ~ 20mm powder, 20mm ~ 50 mm is block, it is also possible to be thick 1mm ~ 10mm, the amorphous tabular of wide a length of 10mm ~ 50mm, the scrap iron material sold on market time all right and discarded steel, the particle diameter iron powder less than 2mm, because granule is too thin, is difficult to when polyaluminum sulfate water solution passes through contact with reducing agent uniformly, affect reduction effect, cause reduction not exclusively.Polyaluminum sulfate water solution passes through the mode of packed layer and contacts mixing with reducing agent, prepares bivalence ferrous iron aqueous solution.When polyaluminum sulfate water solution is by packed layer, directly contact with iron material surface in filling bed, and redox reaction occurs on surface, obtain bivalence perferrite solution.This structure needs periodically from the upper supplementary ferrum system reducing agent of packed layer.
Embodiment 1
At 1m3Included polyvinyl resin steel construction groove in load iron content 11% bodied ferric sulfate 1000Kg, under stirring, be simultaneously introduced the dilute sulfuric acid 120Kg of reproducibility iron powder 60Kg and 75%.In bodied ferric sulfate, ferric ion is completely reduced and obtains perferrite solution for bivalence ferrous ion.The pH1.5 of this perferrite solution, owing to a part of reproducibility iron powder is converted into ferrous iron, so the concentration of ferrous ion increases to 13.9% after tested, the ferric ion concentration not being reduced is only 0.01%, and total concentration of iron is 14.0%.Composition according to table 1 rejoins polyaluminum sulfate water solution, and the ferrum system heavy metal obtaining the present invention processes material.
Table 1
Embodiment 2
Block reduced iron, long 5 ~ 150mm, generous 5 ~ 10mm, purity more than 99%.Take 15 ~ 20Kg, load in packed column, fill the packed layer of high 0.8 ~ 1.2m diameter 0.5m.Bodied ferric sulfate aqueous solution is imported from the top of packed layer, the iron content of bodied ferric sulfate is 11%, under natural gravity effect, polyaluminum sulfate water solution passes through metallic iron system reducing agent packed layer, during by packed layer, polyaluminum sulfate water solution contacts with metallic iron reducing agent, it is ferrous that a part of ferric iron is reduced to bivalence, suitable adds dilute sulfuric acid in polyaluminum sulfate water solution, help speed up reduction process, the amount of metal reduced iron reduces, so constantly to add metal reduced iron, keeps packed layer height.The bottom of packed column obtains the ferrum system heavy metal of the present invention and processes material.Control dilute sulfuric acid consumption and can regulate the composition of the ferrum system heavy metal process material ultimately generated, be shown in Table 2.
Table 2
Embodiment 3
Lead-contaminated soil: according to Tessier continuous extraction, with soluble state heavy metal, pH7 in deionized water extraction soil, 25 DEG C, adds water than 100:1 according to water and soil earth, shakes 2 hours, and 6000r/min is centrifuged 20min and takes the supernatant, then with the MgC1 of 1mol/L2Solution extraction exchangeable species heavy metal, pH7,25 DEG C, according to MgC12Solution and soil add MgC1 than 100:12Solution, shakes 2 hours, and 6000r/min is centrifuged 20min and takes the supernatant.Measuring soluble state (water-soluble state and exchangeable species) lead concentration is 32.1mg/Kg.
The ferrum system immobilization of heavy metals that embodiment 1 and 2 prepares is processed material and is used for processing lead-contaminated soil, after room temperature stands 24 hours, measure soluble state lead concentration, result such as table 3.
Comparative example 1
The same method of embodiment 3, the ferrum system immobilization of heavy metals replacing the present invention with bodied ferric sulfate processes material, the results are shown in Table 3.
Comparative example 2
The same method of embodiment 3, the ferrum system immobilization of heavy metals replacing the present invention with ferrous sulfate processes material, the results are shown in Table 3.
Table 3
Claims (7)
1. a manufacture method for ferrum system heavy metal-polluted soil immobilization material, is characterized in that trivalent iron salt aqueous solution contacts mixing with reducing agent, an iron salt part is reduced to ferrous salt, thus builds the mixture-metal immobilization aqueous solution of bivalence ferrous salt and trivalent iron salt.
The manufacture method of a kind of ferrum system the most as claimed in claim 1 heavy metal-polluted soil immobilization material, it is characterized in that there are two kinds of manufacturing process: (1) is after manufacturing in groove trivalent iron salt is reduced into bivalence ferrous salt completely, then the method adding new three-iron iron salt mixing；(2) being to be filled in packed layer by metallic iron system reducing agent, trivalent iron salt aqueous solution mixes with reducing agent uniform contact by the way of filling bed, thus part ferric iron back becomes bivalence ferrous.
3. the manufacture method of a kind of ferrum system heavy metal-polluted soil immobilization material as described in claim 1 and 2, it is characterised in that trivalent iron salt refers to iron chloride, iron sulfate, bodied ferric sulfate, ferric nitrate, iron phosphate etc..
4. the manufacture method of a kind of ferrum system heavy metal-polluted soil immobilization material as described in claim 1 and 2, it is characterised in that reducing agent is that performance reduction effect manufacture is tapped a blast furnace in acid condition is heavy metal-polluted soil immobilization material.
5. the manufacture method of a kind of ferrum system heavy metal-polluted soil immobilization material as described in claim 1,2 and 3, it is characterised in that acid regulator has the mineral acids such as sulphuric acid, hydrochloric acid, nitric acid, and acetic acid, formic acid, citric acid organic acid.
6. the manufacture method of a kind of ferrum system heavy metal-polluted soil immobilization material as described in claim 1 and 2, it is characterised in that reducing agent is metallic iron reducing agent, refer specifically to reduced iron divide, iron block.
The manufacture method of a kind of ferrum system the most as claimed in claim 1 heavy metal-polluted soil immobilization material, it is characterised in that the ferrous and ratio (Fe of full ferrum in prepared ferrum system heavy metal-polluted soil immobilization material2+/ (Fe2++ Fe3+)) it is 0.2～0.8.
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| CN111253943A (en) * | 2020-03-09 | 2020-06-09 | 四川宜可环保技术有限公司 | Passivation repairing agent for cadmium-polluted soil and preparation method and repairing method thereof |
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