CN105750327B - Method for remediating petroleum hydrocarbon polluted soil ex situ by adopting ozone-biological reactor technology - Google Patents
Method for remediating petroleum hydrocarbon polluted soil ex situ by adopting ozone-biological reactor technology Download PDFInfo
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- CN105750327B CN105750327B CN201610313314.6A CN201610313314A CN105750327B CN 105750327 B CN105750327 B CN 105750327B CN 201610313314 A CN201610313314 A CN 201610313314A CN 105750327 B CN105750327 B CN 105750327B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
- B09C1/105—Reclamation of contaminated soil microbiologically, biologically or by using enzymes using fungi or plants
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Abstract
The invention discloses a method for remediating petroleum hydrocarbon polluted soil ex situ by adopting an ozone-biological reactor technology. The method comprises the following steps: (1) pre-treating petroleum hydrocarbon polluted soil; (2) constructing a biological reactor ex situ by using the pre-treated petroleum hydrocarbon polluted soil; (3) introducing ozone into the biological reactor for performing ozone oxidation treatment; (4) performing remediation treatment by utilizing aerobic microorganisms in the biological reactor. The method has a good effect on remediating the petroleum hydrocarbon polluted soil, and overcomes the disadvantages in the remediation which adopts a single biological technology; the period is short; the cost is lowered; moreover, secondary pollution is avoided; therefore, the method has a good environmental benefit and is suitable for being popularized.
Description
Technical field
The present invention relates to a kind of restorative procedure of petroleum hydrocarbon contaminated soil, and in particular to one kind adopts ozone-biology heap skill
The method of art showering petroleum hydrocarbon contaminated soil, belongs to contaminated soil remediation technical field.
Background technology
As the flourishing and development of Chinese society economy, living standards of the people are improved constantly, vehicles number is sharply increased,
The quantity of corresponding motor vehicles gas station is also growing.And many town and country constructions earlier gas station is made because of factors
Into accidents such as buried tank leakage, pipe leakage, landing oil, oily waste water discharges, enter bulk petroleum hydrocarbons pollutant
Soil layer, causes soil pollution.Petroleum hydrocarbon is entered after soil, can destroy the structure of soil, affects permeability and the plant of soil
Growth.Contaminated soil will cause secondary pollution to surface water and aquifer, and petroleum hydrocarbon contaminant is in grain
Accumulation, gives people class and brings carcinogenic, teratogenesis, mutagenic danger.
At present, have carries out repair process to petroleum hydrocarbon contaminated soil using biological heap recovery technique, and this technology has effect
The really remarkable advantage such as gentle, non-secondary pollution of good, low cost, reaction condition；But the microbial degradation oil under natural surroundingses
Speed is slow, and efficiency is low, it is difficult to meet actual demands of engineering.
The content of the invention
For the defect that the technology of existing biologically rehabilitating soil is present, it is to provide a kind of utilization that the purpose of the present invention is
Ozone combines biological heap technology, the standard compliant reparation petroleum hydrocarbon contaminated soil of efficient, cycle is short, low cost, rehabilitating soil
Method.
In order to realize above-mentioned technical purpose, the invention provides a kind of adopt ozone-biology heap technology showering oil
The method of soil contaminated with hydrocarbons, the method is comprised the following steps：
(1) petroleum hydrocarbon contaminated soil is carried out including the pretreatment adjusted including moisture, pH and nutritional labeling；
(2) biological heap is built with pretreated petroleum hydrocarbon contaminated soil dystopy；
(3) be passed through ozone in the biological heap carries out ozone Oxidation Treatment to petroleum hydrocarbon contaminated soil；
(4) microbial degradation process is carried out to petroleum hydrocarbon contaminated soil using aerobic microbiological in biological heap.
Preferred scheme, the preprocessing process of petroleum hydrocarbon contaminated soil is：Petroleum hydrocarbon contaminated soil is crushed and is sieved
Point, meanwhile, the pH to 6.8～8.0 of the petroleum hydrocarbon contaminated soil is adjusted, moisture content is 50%～55%, in the petroleum hydrocarbon
Appropriate straw, wood flour and addition nitrogenous fertilizer and phosphate fertilizer are blended in contaminated soil, to meet the petroleum hydrocarbon contaminated soil in C:N:P
For (100～130):(10～15):1.
Preferred scheme, tile on the ground one layer of antiseepage film, one layer of coarse sand granulosa is laid in the antiseepage film, in institute
State coarse sand granulosa upper berth and set pretreated petroleum hydrocarbon contaminated soil layer, while arranging inside the petroleum hydrocarbon contaminated soil layer
Ventilation shaft, that is, be built into biological heap.
More preferably scheme, 3～5 meters of biological heap length is wide 1.5～2.5 meters, high 1～2 meter.
More preferably scheme, used as guide layer, its thickness is 5～10cm to coarse sand granulosa.Guide layer is mainly used in biology
The waste liquid that heap is produced is collected and discharges.
More preferably scheme, antiseepage film is high density polyethylene (HDPE) antiseepage film, and its thickness is 2～4mm.
More preferably scheme, ventilation shaft includes a main ventilation pipeline and some ventilation shafts, each ventilation duct
Road with main ventilation pipeline communication, main ventilation pipeline with outside aerating system be connected, described secondary ventilation shaft is distributed in
In the petroleum hydrocarbon contaminated soil layer.
Further preferred scheme, time ventilation shaft is set to 3～4 groups in petroleum hydrocarbon contaminated soil layer, each group time ventilation
It is arranged in parallel up and down by 20～40cm of spacing distance between pipeline, per group time ventilation shaft quantity is 2～3, one group of ventilation duct
It is arranged in parallel by 0.6～1.2m of spacing distance or so between adjacent twice ventilation shafts in road；Described secondary ventilation shaft
On be evenly distributed with micropore.
More preferably scheme, described biological heap is additionally provided with the adding tube and soil gas detection of nutritional labeling and moisture
Equipment.Soil gas testing equipment is mainly used in monitoring the growth of microorganism situation in biological heap；According to environmental monitoring results,
It is properly added nutrient substance and water, it is ensured that growth of microorganism and metabolism environment.
Preferred scheme, takes interruption ventilating mode to be passed through containing ozone gas, to the oil in biological heap in biological heap
Soil contaminated with hydrocarbons carries out oxidation processes, and the time is passed through for continuous 6～8 days containing ozone gas, daily 1～3 time, every time 0.5～
1.5h, the flow that is passed through containing ozone gas is 1～3L/min, and the concentration containing ozone in ozone gas is 10～20mg/L.
Preferred scheme, after the biological heap is by being passed through ozone Oxidation Treatment, further takes interruption ventilating mode to lead to
Enter air, petroleum hydrocarbon contaminated soil is repaired using aerobic microbiological；Air is passed through mode for daily 4～6 times, every time
1.5～3h, while the content of the pH and nutritional labeling and moisture to petroleum hydrocarbon contaminated soil is monitored and adjusts, maintains oil
Soil contaminated with hydrocarbons temperature be 30～35 DEG C, oxygen volume content be 15%～25%, pH be 6.8～8.0, moisture content be 50%～
55%, C:N:P is (100～130):(10～15):1.
More preferably scheme, maintains the aerobic microbiological quantity in biological heap in petroleum hydrocarbon contaminated soil to be 5*108cfu/
Kg～1*109cfu/kg。
Hinge structure, the Advantageous Effects that technical scheme is brought：
Technical scheme first combines ozonation technology and biological heap technology dirty for processing petroleum hydrocarbon
The advantage collaboration of dye soil, ozonation technology and biological heap technology strengthens, and merits and demerits is complementary.Using single ozone oxygen
Although changing, the time is short, efficiency high, corresponding cost is also high, and adopts single microbial degradation, although low cost, without secondary
Pollution, but its degradation efficiency is low, and especially for petroleum hydrocarbon, degraded is very slow, and the cycle is long.Technical scheme is filled
Point using ozone by the petroleum hydrocarbon preliminary oxidation of difficult degradation, preliminary oxidation product can be relatively single to adopt by microorganism fast degradation
With microbial degradation, oxidation efficiency is substantially increased, shorten repairing efficiency；Meanwhile, the micro- life of preliminary oxidation product later use
Thing is degraded, and relatively single ozone oxidation greatlys save cost；The oxygen that particularly ozone decomposed is produced is to add from ozone
Point peripheral region farther out provides oxygen, is conducive to the cultivation of the aerobic oil degradation bacteria in native country so as to become dominant bacteria, favorably
In follow-up microbial degradation.In sum, technical scheme, with efficiency high, cycle is short, low cost, without secondary
The advantage of pollution, can be being applicable.
Specific embodiment
Following examples are intended to further illustrate present invention, rather than limit the protection model of the claims in the present invention
Enclose.
Embodiment 1
The first step, the pretreatment of petroleum hydrocarbon contaminated soil：
Contaminated soil takes from gas station's Polluted area, is coordinated using digging machine and screening crusher, and contaminated soil is broken
Broken and screening process, remove the impurity such as Polluted Soil root system of plant and ratchel, while the bulk soil body is crushed.It is being sieving through
The detection and adjustment of pH are synchronously carried out in journey, soil pH is adjusted to into 6.8～7.5 scope.Straw is blended in contaminated soil
And wood flour, and add appropriate nitrogenous fertilizer and phosphate fertilizer, make C:N:P is about 120:12:1, it is 52% to adjust soil moisture content, and mix is equal
It is even.Wherein, straw is corn straw, and the corn straw of blending and the mass percent of wood flour are respectively 3% and 1%, straw and
Wood flour grinding particle size is 2～4mm；Nitrogenous fertilizer is carbamide or potassium nitrate (KNO3), phosphate fertilizer is potassium dihydrogen phosphate (KH2PO4)。
Second step, the structure of biological heap body：
Biological heap body, long 4 meters, wide 2 meters, high 1.5 meters, biological heap is arranged on smooth clean water mud ground face, and biology is pushed away
Bottom is provided with one layer of antiseepage film (high density polyethylene (HDPE), thickness is 2mm), the uniform laying 5cm thick coarse sand granule in antiseepage film.Will
The petroleum hydrocarbon contaminated soil for taking from gas station contaminated area is uniformly laid to coarse sand granule, in coarse sands layer (guide layer) above 20cm
Place lays the secondary ventilation shaft of the bottom, and per 30cm upwards one layer, totally 3 layers is laid.Per layer is laterally laid 2 ventilation shafts,
Interval 0.8m, is connected to a main ventilation pipeline, and main ventilation pipeline is connected with aerating system (ozonator and aerator).And
Nutrient substance and moisture adding tube and soil gas detection probe are reserved during Da Dui.
3rd step, ozone reparation：
Ozonator is opened, ozone is passed through in biological heap by breather, interruption ventilating mode is taken, using smelly
The oxygen of oxygen solution makes native country highly effective aerobic oil degradation bacteria become dominant bacteria.Be passed through ozone flow be 2L/min, ozone
Concentration is about 15mg/L；Logical ozone 7 days, daily ventilation 2 times, each 1h.
4th step, biological heap reparation：
From the beginning of the 8th day, ozone is changed into air, logical 4 times daily, each duration of ventilation is 2h, is supervised by biotic environment
Control, determines growth of microorganism, metabolism status, and the content of high efficient petroleum degrading bacteria is typically maintained in 5*108Cfu/kg～1*
109cfu/kg.By the monitoring of pH and nutrient and moisture, constantly environmental factorss are adjusted, maintain the life of microorganism
Long and metabolism environment：Soil internal temperature is 32 DEG C；Oxygen content is 20%；PH is 6.8～7.5；Moisture content is 52%, C:N:
P is 120:12:1.
5th step, pollutant analysis：
Biological heap diverse location is sampled, every time same position sample, sample position be 6 (middle 2 points, week
Enclose at 4 points).Main Analysis index is VPH, EPA and TPH.VPH is equivalent to gasoline, predominantly C5～C10Aliphatic hydrocarbon, aromatic hydrocarbons, alkene
Hydrocarbon and cycloalkane, in soil sample VPH analysis methods with reference to EPA method 5035 and EPA method 8015, using stripping trapping-thermal desorption-
Gas chromatography analysis；EPH is equivalent to diesel oil, predominantly C10～C40Between can by dichloromethane extraction and not by adsorption of magnesium silicate
Organic substance summation, in soil sample EPH adopt Accelerate solvent extraction/magnesium silicate purification/gas chromatography analysis, wherein fast solvent
Extraction, magnesium silicate purification and gas chromatographic analysiss refer to respectively EPA method 3545, ISO9377-2:2000 and EPA method 8015；
Total petroleum hydrocarbon (TPH) is VPH and EPH sums in soil.Analysis result is as shown in table 1, as seen from table, by the reparation of 21 days,
All more than 80%, highest clearance reaches more than 87% to the clearance of petroleum hydrocarbon contaminant.
6th step, soil backfill：
After soil disposal terminates, it is qualified after testing after, do place backfill to clearing scene, backfill needs compaction in layers.Place
The principle of reparation is the factor such as the later service condition of present situation and soil for considering soil, by site recovery to former absolute altitude.
The petroleum hydrocarbon analysis result of table 1
Embodiment 2
The present embodiment repairs polycyclic aromatic hydrocarbon pollution.First contaminated soil is built into 3 meters of length, it is wide 1.5 meters, it is high 1.5 meters
Biological heap body.Biological heap is arranged on smooth clean water mud ground face, biology push away bottom be provided with one layer of antiseepage film (high density gather
Ethylene, thickness is 2mm), the uniform laying 5cm thick coarse sand granule in antiseepage film.The petroleum hydrocarbon for taking from gas station contaminated area is dirty
Dye soil is uniformly laid to coarse sand granule, and the secondary ventilation shaft of the bottom is laid at coarse sands layer (guide layer) above 20cm,
One layer, totally 3 layers is laid per 30cm upwards.Per layer is laterally laid 2 ventilation shafts, is spaced 0.6m, is connected to a main ventilation
Pipeline, main ventilation pipeline is connected with aerating system (ozonator and aerator).And during Da Dui reserve nutrient substance
With moisture adding tube and soil gas detection head.Ozone is then passed to, ventilating mode is with embodiment 1.From the beginning of the 8th day, will be smelly
Oxygen changes air into, logical 4 times daily, and each duration of ventilation is 3h, is monitored by biotic environment, determines growth of microorganism, metabolism shape
Condition, the content of high efficient petroleum degrading bacteria is typically maintained in 5*108Cfu/kg～1*109cfu/kg.Contained by pH and nutrient and moisture
Environmental factorss are constantly adjusted by the monitoring of amount, maintain growth and the metabolism environment of microorganism：Soil internal temperature is 35
℃；Oxygen volume content is 25%；PH is 7.0～7.8；Moisture content is 55%, C:N:P is 110:11:1.Weekly to Polluted Soil
Earth takes the 6 point samplings analysis of and 4 points of surrounding at middle 2 points, until the clearance of polycyclic aromatic hydrocarbon reaches stablize, so far, many cyclophanes
The reparation of soil contaminated with hydrocarbons is completed, and analysis method refers to patent of invention CN201410812893.X, and analysis result is as shown in table 2.
As seen from table, the polycyclic aromatic hydrocarbon pollution sample in the present embodiment, clearance 60% or so after the ozone oxidation of a week,
Combined Treatment after one week clearance reach more than 70%, polycyclic aromatic hydrocarbon clearance of the Combined Treatment after the 3rd week is more than 83%,
Clearance to Combined Treatment 4th week polycyclic aromatic hydrocarbon reaches stably, and highest clearance reaches 86.1%.
Table 2PAHs analysis results
Claims (6)
1. the method for a kind of employing ozone-biology heap technology showering petroleum hydrocarbon contaminated soil, it is characterised in that：Including following
Step：
(1) petroleum hydrocarbon contaminated soil is carried out including the pretreatment adjusted including moisture, pH and nutritional labeling；
(2) tile on the ground one layer of antiseepage film, one layer of coarse sand granulosa is laid in the antiseepage film, on the coarse sand granulosa
The pretreated petroleum hydrocarbon contaminated soil layer of laying, while ventilation shaft is set inside the petroleum hydrocarbon contaminated soil layer, i.e.,
It is built into biological heap；Described ventilation shaft includes a main ventilation pipeline and some ventilation shafts, each ventilation shaft
With main ventilation pipeline communication, main ventilation pipeline is connected with the aerating system outside biological heap, and described secondary ventilation shaft is divided equally
Cloth is in the petroleum hydrocarbon contaminated soil layer；Time ventilation shaft is set to 3～4 groups in the petroleum hydrocarbon contaminated soil layer, each group
It is arranged in parallel up and down by 20～40cm of spacing distance between secondary ventilation shaft, per group time ventilation shaft quantity is 2～3, one group
It is arranged in parallel by 0.6～1.2m of spacing distance or so between adjacent twice ventilation shafts in ventilation shaft；Described is secondary logical
Micropore is evenly distributed with wind pipeline；
(3) take interruption ventilating mode to be passed through containing ozone gas in biological heap, the petroleum hydrocarbon contaminated soil in biological heap is entered
Row oxidation processes, are passed through the time for continuous 6～8 days, daily 1～3 time, every time 0.5～1.5h, containing ozone gas containing ozone gas
The flow that is passed through of body is 1～3L/min, and the concentration containing ozone in ozone gas is 10～20mg/L；
(4) microbial degradation process is carried out to petroleum hydrocarbon contaminated soil using aerobic microbiological in biological heap.
2. the method for employing ozone according to claim 1-biology heap technology showering petroleum hydrocarbon contaminated soil, it is special
Levy and be：The preprocessing process of the petroleum hydrocarbon contaminated soil is：Petroleum hydrocarbon contaminated soil is crushed and is sieved, meanwhile,
The pH to 6.8～8.0 of the petroleum hydrocarbon contaminated soil is adjusted, moisture content is 50%～55%, in the petroleum hydrocarbon contaminated soil
The appropriate straw of middle blending, wood flour and addition nitrogenous fertilizer and phosphate fertilizer, to meet the petroleum hydrocarbon contaminated soil in C:N:P for (100～
130):(10～15):1.
3. the method for employing ozone according to claim 1-biology heap technology showering petroleum hydrocarbon contaminated soil, it is special
Levy and be：3～5 meters described of biological heap length, it is wide 1.5～2.5 meters, it is high 1～2 meter；Described coarse sand granulosa as guide layer, its
Thickness is 5～10cm；Described antiseepage film is high density polyethylene (HDPE) antiseepage film, and its thickness is 2～4mm.
4. the method for employing ozone according to claim 1-biology heap technology showering petroleum hydrocarbon contaminated soil, its
It is characterised by：Described biological heap is additionally provided with the adding tube and soil gas testing equipment of nutritional labeling and moisture.
5. the method for employing ozone according to claim 1-biology heap technology showering petroleum hydrocarbon contaminated soil, it is special
Levy and be：After the biological heap is by being passed through ozone Oxidation Treatment, further take interruption ventilating mode to be passed through air, make good use of
Oxygen animalcule is repaired to petroleum hydrocarbon contaminated soil；Air is passed through mode for daily 4～6 times, every time 1.5～3h, while right
The pH and nutritional labeling of petroleum hydrocarbon contaminated soil and the content of moisture are monitored and adjust, and maintain petroleum hydrocarbon contaminated soil temperature
For 30～35 DEG C, it is 6.8～8.0 that oxygen volume content is 15%～25%, pH, and moisture content is 50%～55%, C:N:P is
(100～130):(10～15):1.
6. the method for employing ozone according to claim 5-biology heap technology showering petroleum hydrocarbon contaminated soil, it is special
Levy and be：The aerobic microbiological quantity in biological heap in petroleum hydrocarbon contaminated soil is maintained to be 5*108Cfu/kg～1*109cfu/kg。
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| CN106694534A (en) * | 2017-01-13 | 2017-05-24 | 上格环境科技（上海）有限公司 | Organic bank-soil leaching system for repairing heavy metal and petroleum soil contamination |
| CN108817076B (en) * | 2018-06-08 | 2023-05-05 | 广西博世科环保科技股份有限公司 | Method and system for enhanced restoration of petroleum-contaminated soil by using microbial electrochemical respirator |
| CN108580543A (en) * | 2018-06-28 | 2018-09-28 | 四川省天晟源环保股份有限公司 | A kind of new-type mortar reactor and its operating method for soil remediation |
| CN112317532A (en) * | 2020-11-03 | 2021-02-05 | 北辰(上海)环境科技有限公司 | Biological pile for repairing petroleum hydrocarbon polluted soil |
| CN114850209B (en) * | 2022-04-27 | 2023-04-14 | 中国石油工程建设有限公司华北分公司 | Deep remediation method for high-concentration and high-alkalinity petroleum-polluted soil |
| CN115784546B (en) * | 2023-02-07 | 2023-04-07 | 佛山市铁人环保科技有限公司 | Treatment method of petroleum heavy metal combined pollution slurry |
| CN117084019A (en) * | 2023-08-22 | 2023-11-21 | 中国农业科学院农业环境与可持续发展研究所 | Method for improving utilization efficiency of carbon of soil microorganisms by returning straw to field and applying water and fertilizer |
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| IES86631B2 (en) * | 2014-11-18 | 2016-02-24 | Microgen Biotech Ltd | A process for the remediation of hydrocarbons and/or heavy metal contaminated soil/sludge sediment |
| CN104759459B (en) * | 2015-04-07 | 2017-06-23 | 山东师范大学 | High concentration petroleum pollution soil dystopy in-situ combination biological renovation method |
| CN105234164B (en) * | 2015-11-23 | 2017-12-22 | 中国科学院地理科学与资源研究所 | The heterotopic biological heap gas phase extracting-bio- ventilation prosthetic device and method of a kind of organic polluted soil |
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