CN104759463A - Organic-polluted soil restoration method - Google Patents
Organic-polluted soil restoration method Download PDFInfo
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- CN104759463A CN104759463A CN201510031481.7A CN201510031481A CN104759463A CN 104759463 A CN104759463 A CN 104759463A CN 201510031481 A CN201510031481 A CN 201510031481A CN 104759463 A CN104759463 A CN 104759463A
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Abstract
The invention relates to an organic-polluted soil restoration method. Excavated polluted soil is divided into two types of soil, the first type of the soil contains non-aqueous phase liquid and the second type of the soil does not contain non-aqueous phase liquid. The method comprises the following steps of carrying out crushing and screening on the polluted soil containing non-aqueous phase liquid by a crushing-screening combined device, simultaneously, carrying out flushing pre-treatment by a surfactant, uniformly spreading and stacking all the polluted soil subjected to crushing and screening in an enclosed greenhouse, heating the polluted soil to a temperature of 80-100 DEG C by a geothermal system at the lower part of the polluted soil, keeping the temperature of the heated polluted soil in a range of 80-100 DEG C for 2-4h, then spraying a first oxidizing agent to the polluted soil by a spraying system in the enclosed greenhouse, then carrying out heating treatment on the polluted soil to a temperature of 60-80 DEG C and keeping the temperature for 6-10h.
Description
Technical field
The present invention relates to a kind of organic material contaminated soil restorative procedure, especially quick the and efficient restorative procedure of organic material contaminated soil.
Background technology
At present, for the soil containing volatile organic matter pollutant (VOCs) and total petroleum hydrocarbon (TPH), recovery technique both domestic and external comparatively ripe (as chemical oxidation, gas phase extracting, biological compost, normal temperature parsing etc.), its repairing effect also can be guaranteed; For the soil containing multiring aromatic hydrocarbon (PAHs) pollutant, mainly contain four kinds of recovery techniques: microbial degradation, light degradation, high-temperature heat treatment and chemical oxidation.Research finds, PAHs more than 4 rings, because of its poorly water-soluble, makes it be difficult to be degraded by microorganisms.In addition microbial degradation needs longer Deal with Time, high to the control overflow of temperature, and the workload in early stage is large, and the duration of engineering can be very long; For photooxidation technology, also only rest on theoretical research stage at present, domestic also without practical application example; For high-temperature heat treatment technology (as high-temperature hot desorption), use both at home and abroad comparatively extensive, can remove thoroughly PAHs all kinds of in soil, but this technology cost of disposal is high, and equipment debugging, run also relative complex; For chemical oxidation, this technology maturation, dispose the cycle short, cost is also lower.Be widely used at present in the reparation by VOCs, TPH and part PAHs (below 5 rings) contaminated soil.And for the contaminated soil containing 5 rings and the above PAHs of 5 rings, chemical oxidation techniques repairing effect is not good.
Therefore, need to find and a kind ofly not only have good removal effect to VOCs, TPH of containing in contaminated soil and part PAHs (below 5 rings), also to there is better removal effect to the other types PAHs contained (5 rings and 5 rings more than), and the restorative procedure that operating cost is lower, equipment operating simple, Deal with Time is shorter.
CN201320426278 discloses the treatment system of a kind of normal temperature desorb associating chemical oxidation repairing organic polluted soil.Described system comprises room temperature desorption workshop, and moveable-type soil turns over polishing apparatus, volatilization gas collection tubes apparatus, blast pipe, exhaust gas processing device and portable photo-ionization detector.Wherein, described room temperature desorption workshop is built-in with moveable-type soil and turns over polishing apparatus, described soil turns over polishing apparatus and comprises soil turner, liquid filling, water pump, flexible pipe, flowmeter, manual control valve and jet pipe, for spraying liquor potassic permanganate, throws process while turn over soil; Turn over the volatilization gas that throwing process produces to be collected by gas-collecting pipe, gas-collecting pipe is connected with exhaust gas processing device by blast pipe.The volatile harmful material of 9 one-tenth can be removed.
Summary of the invention
The present invention seeks to, consider the factors such as contaminated site present situation, rehabilitation cost, reparation duration, recovery technique maturity and following land development scheme (as business lives land used, industrial land or agricultural land), propose a kind of quick and efficient restorative procedure to organic material contaminated soil.
Technical scheme of the present invention: a kind of organic material contaminated soil restorative procedure, the contaminated soil excavated is divided into two classes, one class is the contaminated soil containing nonaqueous phase liquid (Non-aqueous phase liquid), and another kind of is not containing the contaminated soil of nonaqueous phase liquid; While carrying out crushing and screening containing the contaminated soil of nonaqueous phase liquid on crushing and screening equipment integrating, carry out surfactant (Surfactant, as: neopelex, Tween 80) rinse pretreatment, surfactant waste liquor stream after having processed through collecting-tank, eventually through water processing establishment rear discharge up to standard; Contaminated soil not containing nonaqueous phase liquid directly carries out crushing and screening on crushing and screening equipment integrating; Contaminated soil after all crushing and screenings complete evenly tiles stacking in airtight booth, and utilizes the geothermal system of contaminated soil bottom to heat described contaminated soil, heating-up temperature to 80 ~ 100 DEG C; When the contaminated soil after heating arrives preset temperature range, and after maintaining 2 ~ 4 hours, by the spray system in airtight booth, contaminated soil is carried out to the spray work of the first oxidant, after spray work completes, contaminated soil is heated again, heating-up temperature to 60 ~ 80 DEG C, and maintain 6 ~ 10 hours, detect contaminated soil and whether reach repairing standard; The organic exhaust gas produced in described contaminated soil heating and spray process and steam, intermittent extracting is carried out, the rear discharge up to standard of the tail gas absorbing system eventually through airtight booth outside by SVE (extracting of the Soil vapor extraction gas phase) system in airtight booth.
Further, after first oxidizer treatment completes, as contaminated soil does not reach repairing standard, by the spray system in airtight booth, contaminated soil is carried out to the spray work of the second oxidant again, after spray work completes, contaminated soil is heated again, heating-up temperature to 60 ~ 80 DEG C, and maintain 18 ~ 24 hours, until contaminated soil reaches repairing standard.
Further, first oxidant adopts Fenton reagent to process, the auxiliary mode adopting applying electric field, and the mode applying electric field arranges uniform parallel graphite cake on a vertical plane, adjoining graphite plate applies the voltage assisted oxidation of opposed polarity, and voltage range is 5 ~ 25V.Especially electric-field intensity is at 30-50V/m.
During process, the moisture content of contaminated soil maintains more than 30%.
Further, the second oxidant adopts permanganate or persulfate.
Further, dosage of surfactant need be carried out calculating according to pollutant kind in soil nonaqueous phase liquid and pollution concentration and be determined, the concentration that surfactant adopts is 40 ~ 80mM.
Further, what adopt geothermal system to heat described contaminated soil is temperature after Resistant heating, and the inventive method is lower than the temperature of open firing, and this technical maturity is reliable.
Further, the first oxidant Fenton reagent, its concrete used in amounts is carried out calculating according to pollutant in soil kind and pollution concentration and is determined, the concentration that the first oxidant Fenton reagent adopts is 3 ~ 8%; Second oxidant permanganate or persulfate, its concrete used in amounts is carried out calculating according to pollutant in soil kind and pollution concentration and is determined, the concentration that the second oxidant permanganate or persulfate adopt is 1 ~ 3%.
Further, airtight booth is half buried design, is steel plate structure bottom booth, booth surrounding except one side leaves plug-type large outdoors, its excess-three face canopy wall is cement structures, and booth ceiling is telescopic folding structure.
Further, contaminated soil is stacked in the steel plate tiling adopting 20mm thick, and the insulating barrier between steel plate and space, ground evenly lays resistance wire, and the underground heat formed after Resistant heating is delivered on steel plate uniformly, realizes heating described soil.
Beneficial effect of the present invention: plan Low Temperature Heat Treatment for contaminated soil and chemical oxidation organically combines, the present invention proposes the method for a kind of quick and efficient restorative procedure to organic material contaminated soil for high volatility and poor (boiling point higher, low saturated vapor pressure pollutant) organic material contaminated soil K cryogenic treatment, namely in airtight booth, contaminated soil is heated (as underground heat), completes the disposal of organic material contaminated soil at a certain temperature.The present invention effectively can process VOCs, TPH and the part PAHs (below 5 rings) of all categories contained in soil.For part PAHs (5 rings and 5 rings more than), also there is good disposal ability.Due to part PAHs (5 rings and 5 rings more than), this kind of boiling point substance is higher, volatility is also poor, therefore on the basis of chemical oxidation, (and simultaneously heat even be oxidized under added electric field condition) is heated to soil, promotes decomposition and the volatilization of organic pollutant in soil.The present invention is directed to contaminated soil, adopt original place dystopy chemical oxidation, the recovery technique of Low Temperature Heat Treatment and the coupling of electrochemistry householder method disposes.Recovery technique of the present invention is simple, be convenient to management, and rehabilitation cost is low, it is more ripe to repair the sub-technology of duration short, each reparation; Can according to factors such as following land development schemes, lower by a kind of cost of optimization of the present invention, the duration is shorter, the method for renovation of better effects if.
Accompanying drawing explanation
Fig. 1 is the structural representation of airtight booth process.
Fig. 2 is Fig. 1 airtight booth planar structure schematic diagram.
Detailed description of the invention
The present invention relates to and adopt the mode of original place dystopy to dispose to the contaminated soil in place, after building waste cleans out within the scope of Polluted area, the excavation of contaminated soil can be carried out, clear and repair.Concrete steps are as follows:
The contaminated soil excavated is divided into two classes, and a class is the contaminated soil containing nonaqueous phase liquid (Non-aqueous phase liquid), and another kind of is not containing the contaminated soil of nonaqueous phase liquid; While carrying out crushing and screening containing the contaminated soil of nonaqueous phase liquid on crushing and screening equipment integrating, carry out surfactant (Surfactant, as: neopelex, Tween 80) rinse pretreatment, surfactant waste liquor stream after having processed through collecting-tank, eventually through water processing establishment rear discharge up to standard; Contaminated soil not containing nonaqueous phase liquid directly carries out crushing and screening on crushing and screening equipment integrating; Contaminated soil after all crushing and screenings complete evenly tiles stacking in airtight booth, and utilizes the geothermal system of contaminated soil bottom to heat described contaminated soil, heating-up temperature to 80 ~ 100 DEG C; When the contaminated soil after heating arrives preset temperature range, and after maintaining 2 ~ 4 hours, by the spray system in airtight booth, contaminated soil is carried out to the spray work of the first oxidant, after spray work completes, contaminated soil is heated again, heating-up temperature to 60 ~ 80 DEG C, and maintain 6 ~ 10 hours, detect contaminated soil and whether reach repairing standard; After first oxidizer treatment completes, as contaminated soil does not reach repairing standard, by the spray system in airtight booth, contaminated soil is carried out to the spray work of the second oxidant again, after spray work completes, contaminated soil is heated again, heating-up temperature to 60 ~ 80 DEG C, and maintain 18 ~ 24 hours, until contaminated soil reaches repairing standard.Repaired qualified after soil carry out backfilling or recycling according to the demand of owner.The mode applying electric field arranges uniform parallel graphite cake on a vertical plane, and adjoining graphite plate applies the voltage assisted oxidation of opposed polarity, and voltage range is 5 ~ 25V.The spacing of especially electric-field intensity: 40-50cm, applying voltage is 15-20V.
In described contaminated soil heating and temperaturel maintenance process, spray system in airtight booth is according to the moisture evaporation situation of booth internal contamination mound, to pollution mound spray hot water (hot water temperature is 80 DEG C), the moisture content of pollution mound is made to maintain more than 30%.
The organic exhaust gas produced in described contaminated soil heating and spray process and steam, intermittent extracting is carried out, the rear discharge up to standard of the tail gas absorbing system eventually through airtight booth outside by SVE (extracting of the Soil vapor extraction gas phase) system in airtight booth.Meanwhile in SVE system and the waste active carbon of replacing in tail gas absorber entrust process.
The showering technological process of contaminated soil original place:
Contaminated soil original place showering comprises contaminated soil excavation and two stages of contaminated soil remediation.According to renovation technique flow process, needed for this, capital equipment comprises: airtight greenhouse system 1, geothermal system 4, tail gas absorbing system 2, spray system 3, discharge of wastewater groove 5, backacter, dumper, bull-dozer, immersible pump, Geoprobe rig, crushing and screening and surfactant flushing integration apparatus, water tower and self-checking equipment etc.
Because the contaminated soil 6 in place all adopts the mode of original place dystopy to dispose, therefore, in place, Polluted Soil stockyard, Polluted Soil disposal area and final disposal mound field must be set in rational position.
Some airtight booths are arranged for contaminated soil disposal area.Each disposal unit, when carrying out organic material contaminated soil process, according to stacking the kind of pollutant in soil and pollution level, determines the time that the addition of the interpolation number of times of medicament every day, each medicament and every day heats soil and stirring number of times.
It is highly 0.75m that contaminated soil is stacked, the construction period of each contaminated soil disposal unit be 6 days (comprise Deal with Time 3 days, excavation, shortly to refute, transition times 3 days).
Contaminated soil lab scale:
1) first in the former contaminated soil fetched, 1 group of contrast pedotheque (numbering: DZ-1) send third party laboratory to carry out detection and analyze, thus determine the initial concentration of pollutant in soil is gathered.Pedotheque analysis indexes comprises pH, water content, VOCs, PAHs, TPH etc.
2) the former contaminated soil fetched manually is carried out pretreatment, further by the rubble in contaminated soil mixing and removal soil and foreign material.
3) pretreatment complete after contaminated soil, equal portions load large pallet, often coil 4 kilograms, amount to 3 dish (i.e. 3 groups of pedotheques, numbering: CL-1, CL-2, CL-3 correspondence three kinds of processing methods);
4) by after the pallet covering and heat insulating cotton of loading contaminated soil, be placed on electric hot plate and be heated to 90 DEG C, maintain 3 hours.
5) open the heat-preservation cotton above pallet, in three pallets, spray the Fenton reagent containing 5% hydrogen peroxide, until pallet internal contamination soil soaks completely with watering can.
6) apply to three pallets with electric field, the mode applying electric field arranges uniform parallel graphite cake on a vertical plane, and adjoining graphite plate applies the voltage assisted oxidation of opposed polarity, and voltage is 15V.
7) by after the pallet covering and heat insulating cotton of loading contaminated soil, be placed on electric hot plate and be heated to 90 DEG C, maintain 8 hours.During this period, according to contaminated soil moisture loss situation, spray the hot water of 90 DEG C in good time to the contaminated soil in three pallets, make the moisture content of contaminated soil maintain more than 30%.
8) heat-preservation cotton above pallet is opened, pure water sprayed, in the pallet being numbered CL-2, sprays the potassium permanganate of 2% concentration, spray in the pallet being numbered CL-3 the sodium peroxydisulfate solution of 2% concentration with watering can, until three pallet internal contamination soil soak completely respectively to the pallet being numbered CL-1.
9) by after the pallet covering and heat insulating cotton of loading contaminated soil, be placed on electric hot plate and be heated to 70 DEG C, maintain 20 hours.During this period, according to contaminated soil moisture loss situation, spray the hot water of 70 DEG C in good time to the contaminated soil in three pallets, make the moisture content of contaminated soil maintain more than 30%.
10), after above-mentioned steps completes, the soil after disposing in three pallets is carried out laboratory censorship analysis.
11) lab analysis index is: pH, water content, VOCs, PAHs, TPH.
Process conditions 1 (CL-1): Low Temperature Heat Treatment+Fenton reagent oxidation (electrolytic oxidation)
Process conditions 2 (CL-2): Low Temperature Heat Treatment+Fenton reagent oxidation (electrolytic oxidation)+potassium permanganate oxidation
Process conditions 3 (CL-3): Low Temperature Heat Treatment+Fenton reagent oxidation (electrolytic oxidation)+persulfate oxidation
Laboratory detection result shows, for lab scale contaminated soil, the comprehensive treatment effect of condition 2 (Low Temperature Heat Treatment+Fenton reagent oxidation (electrolytic oxidation)+potassium permanganate oxidation) is best, the comprehensive treatment effect of condition 3 (Low Temperature Heat Treatment+Fenton reagent oxidation (electrolytic oxidation)+persulfate oxidation) takes second place, and the comprehensive treatment effect of condition 1 (Low Temperature Heat Treatment+Fenton reagent oxidation (electrolytic oxidation)) is the poorest.Electrolytic oxidation all applies 16V voltage (interelectrode distance is 40cm).
In these three kinds of process conditions, for 10 kinds of VOCs involved in the test of this lab scale, all have and well dispose effect, in soil, the clearance of VOCs reaches 100%.This shows, condition 1 (Low Temperature Heat Treatment+Fenton reagent oxidation (electrolytic oxidation)) can meet the processing demands containing VOCs contaminated soil.But condition 1 is for the removal effect of PAHs and TPH in soil not good (as table 1, Fig. 1, Fig. 2), wherein to PAHs clearance below 11 kind of 5 ring involved in this contaminated soil between 54% ~ 95%, to 4 kind of 5 ring involved in this contaminated soil and the above PAHs clearance of 5 rings between 2% ~ 10%, be 71% to the clearance of total petroleum hydrocarbon in this contaminated soil.
For the deficiency that condition 1 technique exists, condition 1 technique is optimized, formation condition 2 and condition 3 technique.As can be seen from the testing result of condition 2 technique we, this technique has good clearance (clearance is between 76% ~ 100%) to PAHs below 11 kind of 5 ring involved in this contaminated soil, and moreover this technique also has good clearance (clearance is 45% ~ 80%) to 4 kind of 5 ring involved in this contaminated soil and the above PAHs of 5 rings.Meanwhile condition 2 technique to the clearance of TPH in contaminated soil also up to 92%; As can be seen from the testing result of condition 3 technique we, this technique has good clearance (clearance is between 58% ~ 100%) to PAHs below 11 kind of 5 ring involved in this contaminated soil, and moreover this technique also has good clearance (clearance is 25% ~ 97%) to 4 kind of 5 ring involved in this contaminated soil and the above PAHs of 5 rings.Meanwhile condition 2 technique to the clearance of TPH in contaminated soil also up to 87%.By finding out that the comprehensive treatment effect of condition 2 is better than condition 3 to condition 2 and condition 3 technological experiment testing result.But from condition 3 engineer testing testing result, we find out, this technique will apparently higher than condition 2 to the clearance of a few PAHs.If the clearance of benzo in soil [α] pyrene is up to 97%, the clearance of fluorenes is up to 99%, and these two kinds of organic pollutants are respectively 80% and 89% by the clearance of condition 2.
Table 1 pollutant type and the processing method table of comparisons
Claims (9)
1. an organic material contaminated soil restorative procedure, is characterized in that the contaminated soil excavated to be divided into two classes, and a class is the contaminated soil containing nonaqueous phase liquid, and another kind of is not containing the contaminated soil of nonaqueous phase liquid; While carrying out crushing and screening containing the contaminated soil of nonaqueous phase liquid on crushing and screening equipment integrating, carry out with surfactant flushing pretreatment, the surfactant waste liquor stream after having processed through collecting-tank, eventually through water processing establishment rear discharge up to standard; Contaminated soil not containing nonaqueous phase liquid directly carries out crushing and screening on crushing and screening equipment integrating; Contaminated soil after all crushing and screenings complete evenly tiles stacking in airtight booth, and utilizes the geothermal system of contaminated soil bottom to heat described contaminated soil, heating-up temperature to 80 ~ 100 DEG C; When the contaminated soil after heating arrives preset temperature range, and after maintaining 2 ~ 4 hours, by the spray system in airtight booth, contaminated soil is carried out to the spray work of the first oxidant, after spray work completes, contaminated soil is heated again, heating-up temperature to 60 ~ 80 DEG C, and maintain 6 ~ 10 hours, detect contaminated soil and whether reach repairing standard; The organic exhaust gas produced in described contaminated soil heating and spray process and steam, carry out intermittent extracting by the gas phase extraction system in airtight booth, the rear discharge up to standard of the tail gas absorbing system eventually through airtight booth outside.
2. organic material contaminated soil restorative procedure according to claim 1, after it is characterized in that the first oxidizer treatment completes, as contaminated soil does not reach repairing standard, by the spray system in airtight booth, contaminated soil is carried out to the spray work of the second oxidant again, after spray work completes, contaminated soil is heated again, heating-up temperature to 60 ~ 80 DEG C, and maintain 18 ~ 24 hours, until contaminated soil reaches repairing standard.
3. organic material contaminated soil restorative procedure according to claim 1, it is characterized in that the first oxidant adopts Fenton reagent to process, the auxiliary mode adopting applying electric field, the mode applying electric field arranges uniform parallel graphite cake on a vertical plane, adjoining graphite plate applies the voltage assisted oxidation of opposed polarity, and voltage range is 5 ~ 25V.
4. organic material contaminated soil restorative procedure according to claim 1, is characterized in that the second oxidant adopts permanganate or persulfate.
5. according to the organic material contaminated soil restorative procedure one of Claims 1-4 Suo Shu, it is characterized in that the first oxidant Fenton reagent, its concrete used in amounts is carried out calculating according to pollutant in soil kind and pollution concentration and is determined, the concentration that the first oxidant Fenton reagent adopts is 3 ~ 8%; Second oxidant permanganate or persulfate, its concrete used in amounts is carried out calculating according to pollutant in soil kind and pollution concentration and is determined, the concentration that the second oxidant permanganate or persulfate adopt is 1 ~ 3%.
6. according to the organic material contaminated soil restorative procedure one of Claims 1-4 Suo Shu, it is characterized in that dosage of surfactant need be carried out calculating according to pollutant kind in soil nonaqueous phase liquid and pollution concentration and be determined, the concentration that surfactant adopts is 40 ~ 80mM.
7., according to the organic material contaminated soil restorative procedure one of Claims 1-4 Suo Shu, it is characterized in that the geothermal system adopted is the temperature of Resistant heating.
8. according to the organic material contaminated soil restorative procedure one of Claims 1-4 Suo Shu, it is characterized in that airtight booth is half buried design, is steel plate structure bottom booth, booth surrounding except one side leaves plug-type large outdoors, its excess-three face canopy wall is cement structures, and booth ceiling is telescopic folding structure.
9. according to the organic material contaminated soil restorative procedure one of Claims 1-4 Suo Shu, it is characterized in that adopting the thick steel plate of 20mm to the stacking contaminated soil that tiles, insulating barrier between steel plate and space, ground evenly lays resistance wire, the underground heat formed after Resistant heating is delivered on steel plate uniformly, realizes heating described soil.
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