CN104056848B - A kind of solidification processing method of petroleum hydrocarbon mild or moderate Polluted Soil - Google Patents
A kind of solidification processing method of petroleum hydrocarbon mild or moderate Polluted Soil Download PDFInfo
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- CN104056848B CN104056848B CN201310096388.5A CN201310096388A CN104056848B CN 104056848 B CN104056848 B CN 104056848B CN 201310096388 A CN201310096388 A CN 201310096388A CN 104056848 B CN104056848 B CN 104056848B
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- 238000003672 processing method Methods 0.000 title description 4
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- LVDRREOUMKACNJ-BKMJKUGQSA-N N-[(2R,3S)-2-(4-chlorophenyl)-1-(1,4-dimethyl-2-oxoquinolin-7-yl)-6-oxopiperidin-3-yl]-2-methylpropane-1-sulfonamide Chemical compound CC(C)CS(=O)(=O)N[C@H]1CCC(=O)N([C@@H]1c1ccc(Cl)cc1)c1ccc2c(C)cc(=O)n(C)c2c1 LVDRREOUMKACNJ-BKMJKUGQSA-N 0.000 claims 1
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Abstract
The invention provides a kind of petroleum hydrocarbon Polluted Soil mixed curing agent, comprise lime 30-50% and the cement quasi-chelate compound 70-50% of independent packaging, wherein said cement quasi-chelate compound comprises cement 40%, atlapulgite 50% and Na
2s10%, also provides the method with this mixed curing agent, petroleum hydrocarbon Polluted Soil being cured to process.The inventive method is relatively simple and efficient, and the solidification process carried out petroleum hydrocarbon Polluted Soil can meet the demand of extensive soil remediation, and the innoxious solidification being especially applicable to a large amount of building site processes.
Description
Technical field
The present invention relates to field of environment protection, be specifically related to soil remediation, more specifically relate to the processing method of petroleum hydrocarbon Polluted Soil.
Background technology
Along with industrial expansion, the demand of oil increases considerably, and because of miscarriage or contingency in exploitation, transport, storage, process, can cause environmental pollution, and direct harm humans is produced and life.
The toxicity of the oil arene material becomeing contaminated to soil to people and animal is comparatively large, the materials such as benzene,toluene,xylene wherein, phenols, if through long period larger concentration contact, to cause nausea, headache, the symptom such as dizzy.Multiring aromatic hydrocarbon substance in oil has strong three-induced effect, and by food chain enrichment gradually in animal and plant body, its enrichment in soil has more harmfulness.Therefore, the problem of administering soil petroleum pollution has caused many countries to pay much attention to.But be a difficult problem by the process of petroleum hydrocarbon contaminated soil, the problem of not only just migration transport, also has the problem of economy.
Before the eighties, administer petroleum hydrocarbon contaminated soil and be also only limitted to heat treatment and Chemical Leaching method.Heat treating process is by burning or calcining, namely utilize the incendive feature of petroleum substance, be burn contaminated soil under the condition of 850 ~ 1200 DEG C in temperature, make petroleum substance become gas and depart from soil body, and then removal petroleum hydrocarbons, reach the object of rehabilitating soil.The method needs to carry out mummification to the contaminated soil entering incinerator and shatters process, need to collect to the toxic gas produced in burning process and flying dust, chelation treatment, therefore the method disposal cost is expensive, generally be unwell to the improvement of pollution in wide area soil, be only applicable to the petroleum hydrocarbon contaminated serious soil remediation of small size.Chemical Leaching method and WATER-WASHING METHOD can obtain good deoiling effect, but the problem such as the secondary pollution of chemical reagent used and the emission treatment of water lotion limits its application.
Since the eighties, the bioremediation technology of contaminated soil develops gradually.Biological prosthetic is the concentration utilizing biological vital metabolic activity to reduce venomous injurant in soil environment, makes contaminated soil return to the process of health status.Such as, plant is utilized to the absorption of pollutant and enrichment, root exudates and edaphon to the degraded of pollutant; Utilize the predation of soil animal, decompose organic matter, change the effects such as soil physico-chemical property; Natural existence or the special microorganism cultivated is utilized toxic pollutant to be converted into the treatment technology of nontoxic pollutant under regulatable environmental condition.Microorganism remediation technology be at present research often and relatively ripe a kind of technology, be divided into two large classes, i.e. biology in situ reparation and Ex situ bioremediation according to operation of whether fetching earth.Modal in-situ treatment mode carries out biodegradation in the water saturation district of soil.Except adding nutritive salt, oxygen source (mostly is H
2o
2) outward, also need to introduce microorganism to improve biodegradable ability.Sometimes, dig one group of well in contaminated area, directly inject suitable solution, the microorganism in water is incorporated in soil.Underground water, after some process, can recover and recycle use, before ground water circulation uses, can also add soil conditioner.Ex situ bioremediation mainly comprises in-situ processing method, prefabricated bed process, composting facture, bioreactor and Anaerobic biotreatment method.
The shortcoming of bioremediation technology is that the time is long, take effect slow, effect is large by such environmental effects, need enormous investment, place (transposition) and time, particularly at home urban land fast Development overall background under (in the innoxious fixing process of especially a large amount of building site) be difficult to be used.
The technology of the direct solidification aspect of petroleum hydrocarbon contaminated soil yet there are no too many report.Under normal circumstances, curing/stabilizing technology contaminated soil is tied agent with the chela that can be agglomerated into solid mix, thus by contaminant trap or the technology that is fixed in solid structure, in curing technology, contaminated soil and chela are tied between agent and chemical reaction can not occur, just mechanically by Polluted Soil sealing in the solid product (firming body) of structural integrity, isolation Polluted Soil and the contacting of external environment, thus reach the object of control polluted articles migration, stabilisation refers to contamination transform as not soluble, transfer ability or the less form of toxicity realize that it is innoxious with the risk reduced ecosystem harmfulness.Cured product can transport easily, and without the need to any additional reservoir.The present invention be intended to exploitation one relatively simple and efficiently method process is cured to petroleum hydrocarbon Polluted Soil, to meet the demand of extensive soil remediation, the innoxious solidification being especially applicable to a large amount of building site processes.
Summary of the invention
The object of this invention is to provide a kind of petroleum hydrocarbon Polluted Soil mixed curing agent, and process the method for petroleum hydrocarbon Polluted Soil with this mixed curing agent solidification.
Petroleum hydrocarbon Polluted Soil mixed curing agent of the present invention comprises lime (calcium oxide) 30-50% and the cement quasi-chelate compound 50-70% of independent packaging, and wherein said cement quasi-chelate compound comprises cement 40%, atlapulgite 50% and Na
2s10%.
In mixed curing agent of the present invention, the mixing ratio of lime and cement quasi-chelate compound can change in above-mentioned scope according to situation about using, but preferably mixing ratio is lime: cement quasi-chelate compound=40%:60%.
Following pollutant is mainly comprised: polycyclic aromatic hydrocarbons (PAH) (PAK), phenol and mineral oils petroleum hydrocarbon (MKW) in petroleum hydrocarbon Polluted Soil handled by method of the present invention.According to the mixing ratio of lime and cement quasi-chelate compound in the pollution level (type of pollutant and content mainly affect by PAK and MKW) of soil pollutant and mixed curing agent, the mixing cured dosage added in the contaminated soil of adjustable.
When containing heavy metal in contaminated soil simultaneously, can correspondingly add dithiocarbamate salt in mixed curing agent.
Method of the present invention comprises the steps:
(1) extract pedotheque, measure pollutant type and content;
(2) calculate by pollutant load, add the described mixed curing agent that the contaminated soil body amasss 5-35%;
(3) contaminated soil and mixed curing agent original position be uniformly mixed rear compacting or fill out reposition after being uniformly mixed elsewhere.
In general, the present invention solidify process petroleum hydrocarbon Polluted Soil belong to mild or moderate Polluted Soil, wherein, the type of pollutant and content are PAK<400mg/kg, phenol <5000mg/kg, MKW<25000mg/kg.
The formula calculating the addition of described mixed curing agent according to pollutant load is as follows:
Mixing ratio volume ratio R=(PAK/150+MKW/1000)/5 × 5%.
Such as, when adopting lime: during the mixed curing agent of cement quasi-chelate compound=40%:60%, when the pollutant load in soil is PAK300mg/kg, MKW2000mg/kg, R=4%; When pollutant load is PAK300mg/kg, MKW5000mg/kg, R=7%; When pollutant load is PAK250mg/kg, MKW15000mg/kg, R=16.7%.
Independent packaging is taken apart by mixed curing agent of the present invention before use, lime wherein and cement quasi-chelate compound is mixed, and is then uniformly mixed with contaminated soil.Contaminated soil and mixed curing agent are uniformly mixed rear preferably leaving standstill and fill out reposition again in 30-120 hour.
Contaminated soil and mixed curing agent are uniformly mixed and preferably adopt original position mix and blend, are preferably and use vertical rotary plough to carry out original position mix and blend.The additional advantage of original position mix and blend will be mixed with the contaminated soil extruding of curing agent closely by vertical rotary plough mixing while.As unconditionally, other corresponding mixing machinery also can be used.
If do not have condition to carry out original position mix and blend, also can set up mixing place in side, disposal field, the Polluted Soil excavated backfills original place on the ground with after mixed curing agent Homogeneous phase mixing in mixing field.In order to make whipping process carry out continuously, enough composite pollution soil should be prepared in advance.
In order to check the effect of this method process Polluted Soil, need to leave standstill 30-120 hour after mixed curing agent mixes with Polluted Soil, this can complete side at the scene.
One embodiment of the invention carry out original position mixing to the place of conditions permit to repair, and specifically comprises the following steps:
● sampling detection determines pollutant and concentration in Polluted Soil, original soil intensity;
● determine the Polluted Soil site area and the volume that need reparation;
● calculate the total amount of pollutant in Polluted Soil place;
● calculate the mixed curing agent consumption determining to need;
● factory is transported to scene after preparing mixed curing agent;
● use flip vertical plough mixed curing agent and Polluted Soil to be uniformly mixed;
● direct in-situ is tamped.
In above-mentioned preferred embodiment of the present invention, mixed curing agent at the scene can in situ preparation in situation with good conditionsi.
Another embodiment of the invention is that dystopy mixing reparation is carried out in the place of repairing unconditional original position mixing, specifically comprises the following steps:
● sampling detection determines pollutant levels, original soil intensity;
● determine the Polluted Soil site area and the volume that need reparation;
● calculate the total amount of pollutant in Polluted Soil place;
● calculate the mixed curing agent consumption determining to need;
● factory is transported to scene after preparing mixed curing agent;
● Polluted Soil is excavated to side, place;
● use in this place, side double spiral agitator mixed curing agent and Polluted Soil to be uniformly mixed, then backfill original place, compaction in layers.
In above-mentioned preferred embodiment of the present invention, mixed curing agent at the scene also can in situ preparation in situation with good conditionsi.
Detailed description of the invention
The present invention is further illustrated referring to embodiment.Should be appreciated that the following examples for illustration of content of the present invention non-limiting content of the present invention, any pro forma accommodation and/or change all will fall into protection scope of the present invention.
Embodiment 1
The preparation of mixed curing agent: before use, (comprises cement 40%, atlapulgite 50% and Na by lime and cement quasi-chelate compound
2s10%) mix in the ratio of 30-50%:70-50%.
Embodiment 2
The in-situ solidifying process of petroleum hydrocarbon Polluted Soil:
(1) it is a sample that the 30cm that holes extracts at least 20 grams of soil deeply, at least samples 5 parts, measure pollutant type and content according to Polluted Soil size;
(2) by the mixed volume ratio of pollutant load calculating mixed curing agent with contaminated soil
Mixed volume is than R=(PAK/150+MKW/1000)/5 × 5%;
(3) plough with vertical rotary mixed curing agent embodiment 1 prepared carry out original position mix and blend with contaminated soil by above-mentioned mixed volume ratio and tamp.
Embodiment 3
The dystopy solidification process of petroleum hydrocarbon Polluted Soil:
(1) it is a sample that the 30cm that holes extracts at least 20 grams of soil deeply, at least samples 5 parts, measure pollutant type and content according to Polluted Soil size;
(2) by the mixed volume ratio of pollutant load calculating mixed curing agent with contaminated soil
Mixed volume is than R=(PAK/150+MKW/1000)/5 × 5%;
(3) Polluted Soil is excavated to side, place, add the mixing cured dosage calculated by above-mentioned steps (2) according to its volume;
(4) use in this place, side double spiral agitator mixed curing agent and Polluted Soil to be uniformly mixed, then backfill original place, compaction in layers.
Embodiment 4
Repair soil stabilization and resistance of soil inspection
Test is carried out as follows:
● it is a sample that boring 30cm extracts at least 20 grams of soil deeply, at least samples 5 parts according to Polluted Soil size;
● measure original soil pollutant type and content, calculate the mixed curing agent consumption of needs, mixed curing agent (lime: the cement quasi-chelate compound=40%:60%) consumption used in this experiment is 17% of Polluted Soil volume;
● Polluted Soil and mixed curing agent mix and blend, leave standstill 24 hours;
● the mensuration of compression strength, shear strength and density is carried out to soil after solidification, and adopts Oedometer expansion test Measurement sensibility coefficient;
● assessment solidification effect.
Table 1 is below original soil data, Polluted Soil pollutant load (" PAK " refers to polycyclic aromatic hydrocarbons (PAH), and " MKW " refers to mineral oils petroleum hydrocarbon):
Soil after reparation send its intensity of test in laboratory whether to reach stability criterion, and the soil by machines intensity of detection comprises shear strength and compression strength.
This experiment draws according to a concrete contaminated site reparative experiment, this contaminated site solidification after 24 hours respectively from side slope drill hole sampling pacifically, here be process after soil samples and detecting result (table 2,3):
Table 2 side slope sampling inspection results
| Sample number | P1 | P2 | P3 | P4 |
| Compression strength q(kN/m 2） | 351.85 | 357.76 | 167.6 | 157.15 |
| Shear strength c(kN/m 2） | 175.9 | 178.9 | 83.8 | 78.6 |
| Tolerance (%) | 8.15 | 6,99 | 4,33 | 4,16 |
| Density (g/cm 3） | 1.26 | 1.66 | 1.59 | 1.54 |
Table 3 level land drill hole sampling testing result
| Sample number | P5 | P6 | P7 | P8 |
| Compression strength q(kN/m 2） | 40.84 | 298.24 | 78.47 | 30.72 |
| Shear strength c(kN/m 2） | 20.4 | 149.1 | 39.2 | 15.3 |
| Tolerance (%) | 4.37 | 6.65 | 9.78 | 6.14 |
| Density (g/cm 3） | 1.54 | 1.63 | 1.39 | 1.43 |
Experimental result is evaluated:
After process, the compression strength of soil reflects the effect of solidification, and compression strength is higher, and stability is better, represents that the probability that pollutant is revealed under after this disturbed emotionally condition is lower, thus reaches the object of control polluted articles migration.Solidify this ground after repairing and can be used as building site use, can not be used as to plough, can not excavate and move for other building earthing, but can as the earthing of refuse landfill in situation with good conditionsi.
After process, soil anti-shear strength needs c>=25kN/m
2, it is q=2c that axial compression strength and shear strength are closed, and for meeting this condition, axial compression strength needs q>=50kN/m
2.
Two groups of result of the test displays, only have the compression strength of the Polluted Soil sample after two soil process of holing lower than 50kN/m
2.Because compression strength can improve with the prolongation of time after solidification process, so after leaving standstill 5 days, after process, the compression strength of soil can more than 50kN/m
2.
So, experimental result shows through using mixed curing agent of the present invention and according to the petroleum hydrocarbon contaminated soil of technological process process of the present invention, no matter side slope soil or the native mechanical strength of boring can meet the requirement of original soil, serve good stabilisation and solidification, thus such contaminated soil can be processed effectively, economically.
Claims (9)
1. the mixed curing agent containing the petroleum hydrocarbon Polluted Soil of PAK<400mg/kg, phenol <5000mg/kg, MKW<25000mg/kg, comprise lime 30-50% and the cement quasi-chelate compound 70-50% of independent packaging, wherein said cement quasi-chelate compound comprises cement 40%, atlapulgite 50% and Na
2s10%.
2. mixed curing agent as claimed in claim 1, wherein comprises lime 40%, described cement quasi-chelate compound 60%.
3. mixed curing agent as claimed in claim 1 or 2, wherein also comprises dithiocarbamate salt.
4. with mixed curing agent described in claim 1 or 2 or 3, petroleum hydrocarbon Polluted Soil is cured to the method for process, comprises the following steps:
(1) extract pedotheque, measure pollutant type and content;
(2) calculate by pollutant load, add the described mixed curing agent that the contaminated soil body amasss 5-35%;
(3) contaminated soil and mixed curing agent original position be uniformly mixed rear compacting or fill out reposition after being uniformly mixed elsewhere.
5. solidify the method for process as claimed in claim 4, the wherein said formula calculating the addition of described mixed curing agent by pollutant load is as follows:
Mixed volume is than R=(PAK/150+MKW/1000)/5 × 5%.
6. solidify the method for process as claimed in claim 4, mix with contaminated soil again after the lime in wherein said mixed curing agent and cement quasi-chelate compound first mix.
7. solidify the method for process as claimed in claim 4, wherein said contaminated soil and mixed curing agent are uniformly mixed latter standing 30-120 hour and fill out reposition again.
8. solidify the method for process as claimed in claim 4, wherein the described original position of step (3) stirs and adopts vertical rotary plough to carry out original position mix and blend.
9. solidify the method for process as claimed in claim 4, filling out reposition after being wherein uniformly mixed elsewhere described in step (3) is Polluted Soil is excavated to side, place and mixed curing agent is uniformly mixed rear backfill, compaction in layers.
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