CN105772499B - A kind of in-situ combination restorative procedure of Petroleum concentration place soil - Google Patents
A kind of in-situ combination restorative procedure of Petroleum concentration place soil Download PDFInfo
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- CN105772499B CN105772499B CN201610234782.4A CN201610234782A CN105772499B CN 105772499 B CN105772499 B CN 105772499B CN 201610234782 A CN201610234782 A CN 201610234782A CN 105772499 B CN105772499 B CN 105772499B
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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
- B09C1/08—Reclamation of contaminated soil chemically
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
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- Engineering & Computer Science (AREA)
- Soil Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
A kind of in-situ combination restorative procedure of Petroleum concentration place soil, it is related to a kind of soil remediation method, wherein chemical oxidation medicament is made of this method oxidant sodium peroxydisulfate, activator sodium hydroxide or calper calcium peroxide, sustained release agent sodium thiosulfate etc., and microorganism stimulation nutriment is made of sodium phosphate and ammonium sulfate.The molar ratio of sodium peroxydisulfate and activator is 5:1.The amount of sustained release agent is the 1 ~ 5% of oxidant and activation dosage.The molar ratio for promoting the nutriment C:N:P of microorganism growth is 120:10:1, and phosphorus source is sodium phosphate (Na3PO4•12H2O), nitrogen source is ammonium sulfate ((NH4)2SO4).Carbon source is petroleum hydrocarbons, is estimated according to practical pollutant degree.The present invention can achieve the purpose for thoroughly repairing long-term petroleum class contaminated soil, so that the problem of overcoming the reparation of aging contaminated soil microorganism difficulty, chemical oxidation higher cost, having greater environmental impacts, reduces rehabilitation cost.
Description
Technical field
The present invention relates to a kind of soil remediation methods, more particularly to a kind of in-situ combination of Petroleum concentration place soil
Restorative procedure.
Background technique
Petroleum hydrocarbons (TPH, Total petroleum hydrocarbons) refer to can be by CCl4Dissolution, and in wave number
3030 cm-1(≡ CH1 aromatic rings), 2960cm-1(- CH3 methyl) and 2930cm-1(=CH2 methylene) any one has feature suction
The substance of receipts.Mainly hydro carbons (alkane, cycloalkane, aromatic hydrocarbon, alkene can be divided by structure), the followed by few nonhydrocarbon of quantity
Component (contains O, S, N compound, resin and asphalt).Different component pass through in the soil disperse, molecule diffusion, volatilization, absorption,
The effects of chemically reacting and degrading Transport And Transformation is present in underground ring with free state (NAPL), volatilization state, solubilised state and ADSORPTION STATE
In border.Since the toxicity of petroleum hydrocarbons itself and Transport And Transformation in the soil bring very big difficulty to repairing.
In recent years, with the quickening of Urbanization in China and industry transfer paces, occur in city large quantities of by coking
The place of Petroleum concentration caused by the enterprises removes such as factory, steel plant and chemical plant.Such place faces the conversion of land use
And secondary development, such as: commercial land, residential building.Since pollution level is heavier, the time is longer, and place soil pollution is universal
It is relatively deep.Petroleum hydrocarbons in soil are present in inside soil mineral particle and organic matter glassy portion or soil particle
The high-energy adsorption site position on surface has stronger binding force with solid phase of soil or is fettered by its micropore.For such pollution
The method in place, gas phase extracting is difficult to extract out pollutant.And pollutant can only be by slowly spreading or providing higher energy
Amount breaks key and power and micropore constraint gets to solid phase of soil surface, therefore is difficult to biological utilisation.Still further aspect, these
Place is present in down town mostly, and showering may impact ambient enviroment, if pollution level is deeper, excavates
Cost will sharply increase.
The principle of in situ chemical oxidation technology (In-Situ Chemical Oxidation, ISCO) is by oxidant
(Fenton reagent, ozone, sodium peroxydisulfate, potassium permanganate etc.) injection is doped into underground environment, is solved by acid-base reaction, absorption
The effects of suction, dissolution, hydrolysis, ion exchange, redox, precipitating, makes the polluter in underground water or soil be destroyed, drop
Solution is at the nontoxic or smaller substance of harm.Sodium peroxydisulfate is common oxidant in chemical oxidation recovery technique, has preferable water
Dissolubility (20 °C of 550g/L@) and stability.It is decomposable after sodium peroxydisulfate is activated to generate sulfate free radical (SO4),
SO4In have a pair of of lone pair electrons, oxidability (E0=2.60V) it is relatively strong, can be reacted with most of petroleum hydrocarbons with
Achieve the purpose that degradation removal.
Microorganism stimulation (BS), which refers to, converts two for the petroleum hydrocarbons in soil using the metabolic process of microorganism
The repair process of the substances such as carbonoxide, water, fatty acid and organism.Research shows that certain micro-organisms (sulfate reducing bacteria, SRB)
It can use sodium peroxydisulfate reaction product SO4 2-, and the heat that biodegrade generates can also activate sodium peroxydisulfate.For big face
Contamination contaminates the soil of shallower lesser extent, more appropriate using microorganism remediation, in situ chemical oxidation and microbial association reparation
Combination is that cost is relatively low, the technology with feasibility.
For needing the long-term petroleum class contaminated site soil of in-situ immobilization, conventional recovery technique is difficult to remove it, gas
Mutually extracting is only effective to volatile organic matter, introducing inoculating microbe actual effect is poor, the phytoremediation time is longer and can only
Repair that the technical costs such as specific pollutant, thermal desorption are higher, elution technique is more difficult realizes in situ.And sodium peroxydisulfate oxidizing process
Adaptable to pollutant, oxidation effectiveness is good, but there are the secondary pollutions of sulfate to environment.Microbiological anaerobic degraded oil
When pollutant, SO4 2-Required electron acceptor when frequently as microorganism remediation, the SO that activation persulfate generates4 2-It can be by
Sulfate reducing bacteria utilizes.Therefore, sodium peroxydisulfate oxidation technology can combine to preferably send out with microorganism stimulating technology
Respective advantage is waved, to improve the removal efficiency of petroleum hydrocarbons and reduce the secondary pollution of chemical oxidation bring.
Summary of the invention
The purpose of the present invention is to provide a kind of in-situ combination restorative procedure of Petroleum concentration place soil, this method is adopted
The method of the sodium peroxydisulfate alkaline activation taken, which can stimulate to provide for subsequent microorganism, is bordering on neutral pH environment and electron acceptor
Sulfate ion, the surfactant generated after sodium peroxydisulfate petroleum oxidate pollutant can promote pollutant to liquid phase of soil
Conversion, improve the utilization rate of microorganism.The removal efficiency for improving pollutant reduces the sulfate bring that reaction generates
Secondary pollution.
The purpose of the present invention is what is be achieved through the following technical solutions:
The advantages and effects of the present invention are:
1, preparation method provided by the invention has simple process, operational administrative safety, chemical raw material used cheap and easy to get
The advantages that.
2, the present invention stimulates combined remediation method with microorganism using sodium peroxydisulfate oxidation, reduces the dosage of oxidant,
The removal efficiency for improving pollutant reduces the sulfate bring secondary pollution that reaction generates.
3, the method for the sodium peroxydisulfate alkaline activation that the present invention takes can stimulate to provide for subsequent microorganism is bordering on neutrality
PH environment and electron acceptor sulfate ion, the surfactant generated after sodium peroxydisulfate petroleum oxidate pollutant can promote
Into pollutant to the conversion of liquid phase of soil, the utilization rate of microorganism is improved.
4, the present invention is suitable for be had fewer environmental impacts by long-term petroleum class contaminated soil with in-situ immobilization.
Detailed description of the invention
Fig. 1 is the embodiment of the present invention 1 to certain contaminated site Hydrocarbon in Soil concentration comparison chart before and after the processing；
Fig. 2 is that the present invention implements Petroleum concentration place soil in situ chemical oxidation-microorganism stimulation joint Principles
Figure.
Specific embodiment
The following describes the present invention in detail with reference to examples.
The present invention is using sodium peroxydisulfate as oxidant main body, with alkali (sodium hydroxide, calper calcium peroxide etc.) for activation method, with sulphur
Sodium thiosulfate is sustained release agent, nutriment needed for the growth of addition microorganism after the completion of oxidation.
Sodium peroxydisulfate, sodium hydroxide, calper calcium peroxide are white solid powder, technical pure, and when use need to be dissolved in the water: hydrogen
Sodium hydroxide solution concentration is 1mol/L, and sodium peroxydisulfate solution concentration is 1mol/L.Calper calcium peroxide is solid, and dosage (molar ratio) is
The 1/5 of sodium peroxydisulfate.Sustained release agent concentration 1mol/L, dosage are the 1 ~ 5% of oxidant and activation dosage.
The application method of sodium peroxydisulfate oxidating chemicals, this method specifically: activator is uniformly mixed dissolution with sustained release agent
In water, it first injects in sub-surface, then sodium peroxydisulfate is dissolved in water, be subsequently injected into underground.
The application method of microorganism in situ stimulation, this method specifically: after chemical oxidation 7 days (according to the actual situation
Selection), by injecting water or nitrogen to underground to keep reducing environment, being then injected into Institute of Micro-biology needs nitrogen source and phosphorus source to pierce
Swash the growth of microorganism.
The major function of sodium peroxydisulfate is that the sulfate free radical with strong oxidizing property and hydroxyl are generated after overactivation certainly
By base, the pollutant in soil is oxidized to carbon dioxide and water, achievees the purpose that remove pollutant.Calper calcium peroxide it is slow molten
Hydrogen peroxide and hydroxide ion are generated in water, and then activates sodium peroxydisulfate and generates free radicals decontamination.
The molar ratio for promoting the nutriment C:N:P of microorganism growth is 120:10:1, and phosphorus source is sodium phosphate (Na3PO4•
12H2O), nitrogen source is ammonium sulfate ((NH4)2SO4).Carbon source is petroleum hydrocarbons, according to practical groups of contaminants at estimation.
Possibility by nutriment stimulating growth is a kind of sulfate reducing bacteria, it is also possible to including bacterium, fungi or it
Mixed bacterial, specific visual field depending on soil actual conditions.
Oxidant and microbial nutrition substance can be by injection well in-situ injections into underground environment.
Following embodiment is explanation of the invention, and the invention is not limited to following embodiments.
Embodiment 1
It takes the practical Polluted Soil of 10g (petroleum-type concentration 15000mg/kg), addition 5g sodium peroxydisulfate, 0.25 ~ 2g calper calcium peroxide,
0.1g sodium thiosulfate reacts 24 hours.The Polluted Soil of (calper calcium peroxide: sodium peroxydisulfate=1:5), stone after reaction after taking 10g to aoxidize
Oils concentration about 5000mg/kg, pH are 6.67 or so, and 0.018g ammonium sulfate, 0.011g sodium phosphate is added, cultivates 30 days.
Embodiment 2
It takes the practical Polluted Soil of 10g (petroleum-type concentration 15000mg/kg), addition 5g sodium peroxydisulfate, 0.25 ~ 2g calper calcium peroxide,
0.1g sodium thiosulfate reacts 24 hours.The Polluted Soil of (calper calcium peroxide: sodium peroxydisulfate=1:5), stone after reaction after taking 10g to aoxidize
Oils concentration about 5000mg/kg, pH are 6.67 or so, and 0.018g ammonium sulfate, 0.011g sodium phosphate is added, adds external source sulfate
Reducing bacteria is cultivated 30 days.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, without departing from the inventive concept of the premise, can also make several improvements and modifications, these improvements and modifications also should be regarded as
In protection scope of the present invention.
Claims (2)
1. a kind of in-situ combination restorative procedure of Petroleum concentration place soil, which is characterized in that this method is suitable for for one kind
The chemical oxidation of long-term ageing Petroleum concentration soil remediation-microorganism stimulates combined remediation method, and the method includes following
Process: activator being uniformly mixed with sustained release agent and is dissolved in water, and is first injected in sub-surface, then sodium peroxydisulfate is dissolved in water
In, it is subsequently injected into underground；The molar ratio of C:N:P is 120:10:1, and phosphorus source is sodium phosphate, chemical formula Na3PO4·
12H2O, nitrogen source are ammonium sulfate ((NH4)2SO4), carbon source is petroleum hydrocarbons, is estimated according to practical pollutant degree；Oxygen used
Chemical drug agent is made of sodium peroxydisulfate, activator, sustained release agent, and the molar ratio of sodium peroxydisulfate and activator is 5:1, and the amount of sustained release agent is
The 1 ~ 5% of oxidant and activation dosage；Wherein, the sustained release agent is sodium thiosulfate.
2. a kind of in-situ combination restorative procedure of Petroleum concentration place soil according to claim 1, which is characterized in that
The activator is sodium hydroxide, one or more according to the mixture obtained after any proportion mixing in calper calcium peroxide.
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| CN105414166A (en) * | 2015-12-31 | 2016-03-23 | 陕西清扬环境科技有限公司 | Repair method for mercury-polluted soil |
| CN105458000B (en) * | 2016-01-13 | 2018-03-09 | 南京信息工程大学 | The method for repairing mercury contaminated soil using accessory substance ATS (Ammonium thiosulphate) joint pot marigold |
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Effective date of registration: 20201225 Address after: People's Government of Jinshan Town, building 15, Qingshan langu community, Tangquan Road, Jinshan Town, Yuanbao District, Dandong City, Liaoning Province Patentee after: Dandong Jinshan Investment Construction Development Co.,Ltd. Address before: 110044 Liaoning Province, Shenyang City District wanghuanan Street No. 21 Patentee before: SHENYANG University |
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