CN106190131A - A kind of add electrolyte preparations and replenishment method thereof for electronic microorganism remediation - Google Patents

A kind of add electrolyte preparations and replenishment method thereof for electronic microorganism remediation Download PDF

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CN106190131A
CN106190131A CN201610570633.5A CN201610570633A CN106190131A CN 106190131 A CN106190131 A CN 106190131A CN 201610570633 A CN201610570633 A CN 201610570633A CN 106190131 A CN106190131 A CN 106190131A
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soil
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CN106190131B (en
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郭书海
王卅
李凤梅
吴波
张猛
王加宁
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Institute of Applied Ecology of CAS
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00Soil-conditioning materials or soil-stabilising materials
    • C09K17/02Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/08Reclamation of contaminated soil chemically
    • B09C1/085Reclamation of contaminated soil chemically electrochemically, e.g. by electrokinetics
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/10Reclamation of contaminated soil microbiologically, biologically or by using enzymes

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Abstract

The present invention relates to contaminated soil electronic microorganism remediation technical field, be specifically related to a kind of maintain the electronic microbial association of contaminated soil repair in chemical oxidation efficiency and the method for microbial metabolic activity.Electro reclamation process causes water soluble ion salt dosis refracta to reduce, and current intensity weakens, and microorganism may utilize nutrient salts ion and reduces, thus cause electrochemistry directly with indirect oxidation efficiency and the decline of microbial metabolism ability.By measuring current intensity and soil water insoluble ionic concentration change, and add electrolyte medicament, in making soil, inorganic ion concentration meets set kind ion concentration content and total ion concentration content requirement, maintain the efficient repair process of electronic chemical oxidation and microbial metabolism, improve the overall remediation efficiency of contaminated soil.

Description

Electrolyte supplementing preparation for electrokinetic-microbial remediation and supplementing method thereof
Technical Field
The invention relates to the technical field of electrokinetic remediation of polluted soil, in particular to an electrolyte supplementing agent for electrokinetic-microbial remediation and a supplementing method thereof.
Background
The electric remediation technology is a new soil pollution treatment remediation technology, and has been paid more and more attention and researched. By applying an external direct current low-voltage electric field into the polluted soil, the pollutants are oxidized and degraded by utilizing the electrochemical reaction promoted by the surface of the electrode and the current intensity in the electric field. Based on electrokinetic remediation, electrokinetic-microbial remediation technology has been rapidly developed. The stimulation effect of the current intensity on the metabolic activity of the microbial cells improves the capability of the microbes to degrade pollutants in soil to a certain extent, and the cooperative coupling functional mode between the electromotion and the microbes is formed by combining the electromotion effect and the electrochemical oxidation effect, so that the high-efficiency repairing capability is obtained.
Research results show that the content of water-soluble ions capable of moving in soil is closely related to the conductivity of the soil in the process of electric restoration. The current intensity is obviously reduced due to the insufficient ion content, and the direct and indirect oxidation effects of electrochemistry are weakened; the reduction of the content of the major ions associated with the growth and metabolism of the microorganisms also inhibits the degradation of the contaminants by the microorganisms. However, the excessive inorganic ion concentration in the soil promotes the repair system to obtain stronger current intensity and simultaneously generates stronger corrosion action on the electrode material, and accelerates the soil water loss process; meanwhile, the hypertonic nature of high salinity soil environments results in water loss from soil microorganisms, severely compromising the number and metabolic activity of microorganisms.
The method comprises the steps of measuring the content of water-soluble inorganic ions in soil, specially preparing an inorganic ion electrolyte agent, and applying the agent to the polluted soil in the later stage of electrokinetic-microbial remediation according to a set dosage to obtain a proper soil water-soluble ion concentration, so that the high-efficiency degradation capability of electrokinetic chemical oxidation and microbial metabolic activity on soil pollutants is effectively maintained, and a management mode for dynamically regulating and controlling the content of the soil water-soluble ions in the electrokinetic-microbial remediation process is formed.
Disclosure of Invention
The invention aims to provide a supplementary electrolyte preparation for electro-microbial remediation and a supplementary method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a supplemented electrolyte formulation for electro-microbial remediation, comprising: the electrolyte replenishing preparation consists of various inorganic salt ion aqueous solutions; addition of supplementary electrolyte preparation according to QT=(100%~120%)QT-IntCalculate the addition, then press QSup(ion)=W(ion)·QT-QRes(ion)Respectively calculating the concentration of each water-soluble inorganic salt ion in the electrolyte preparation; wherein,
QT=(100%~120%)QT-Int
in the formula, QTThe total ion concentration in the soil after the electrolyte agent is supplemented; qT-IntIs the initial total ion concentration (unit: mu g) of the soil-1Dry soil);
QSup(ion)=W(ion)·QT-QRes(ion)
in the formula, QSup(ion)Is each singleIon replenishment concentration content; qRes(ion)The concentration of single ion residual in the soil after electrokinetic-microbial remediation is shown as follows; w(ion)The proportion (%) of single ions in the total ion content in the soil after the electrolyte is supplemented.
And ensuring that the water content of the soil is maintained at a level of 20-25% under a certain soil water content condition.
The electrolyte replenishing preparation consists of a cation aqueous solution and an anion aqueous solution; wherein the cation is NH4 +、K+、Na+、Ca2+And Mg2+(ii) a The anion being NO3 -、PO4 3-、Cl-And SO4 2-
The electrolyte preparation can be divided into three types of functional ions, and the concentration range of each ion after the electrolyte preparation is applied is quantified according to the endowed function:
after the electrolyte is supplemented, K is in the soil to meet the requirement of the content of nutrient elements+The content accounts for 10 to 15 percent of the total content in the soil; NH (NH)4 +And NO3 -The contents of the components are respectively 3% -6% and 11% -15% of the total content in the soil, and PO4 3-The content accounts for 4-7% of the total content of the soil, and the concentrations of the three are balanced to ensure that the molar ratio of N to P in the soil reaches the level of 8:1-10: 1.
In order to meet the demand of electrochemical indirect oxidation, Cl in soil is filled after electrolyte is supplemented-The content of the soil stabilizer accounts for 26-28% of the total content of the soil.
In order to meet the requirement of the ion conductor in the soil, the content of each ion and the target total ion content (Q) of the soil areT) On the basis of the above calculation, after the electrolyte is supplemented, Na in the soil is added+The content of Ca accounts for 7 to 10 percent of the total content of the soil2+The content of Mg accounts for 9 to 12 percent of the total content of the soil2+The content of SO accounts for 4-7% of the total content of the soil4 2-The content of the active carbon accounts for 16-19% of the total content of the soil so as to maintain the high-level conductivity of the soilAnd the current intensity.
And the concentration range of each ion in the soil after the electrolyte agent is applied is calculated according to a formula III:
QSup(ion)=W(ion)·QT-QRes(ion)(formula three)
Wherein Q isSup(ion)Supplementing the concentration content for each single ion; qRes(ion)The concentration of single ion residual in the soil after electrokinetic-microbial remediation is shown as follows; w(ion)The proportion (%) of single ions in the total ion content in the soil after the electrolyte is supplemented.
The electrolyte agent is prepared according to the supplement amount required by each single ion and the limit of maintaining the water content of the soil to be 20-25%.
And (3) water is supplemented in the electric-microorganism repairing process, and when the total average current intensity in the water supplementing period is less than or equal to 70% of the initial value, the electrolyte supplementing preparation is added, so that the soil conductivity is effectively maintained, and the indirect oxidation and microorganism metabolism capabilities are enhanced.
A method for supplementing electrolyte preparation for electric-microbial remediation is characterized in that water is repeatedly supplemented in the electric-microbial remediation process, when the proportion of the average value of the total current intensity in each water supplementing period to the initial current intensity value of the electric remediation is less than or equal to 70%, the real-time content of each ion in soil is detected by adopting a formula I, and then the total water-soluble ion concentration in the soil after the electrolyte preparation is supplemented is calculated by the real-time content of each ion in the soil through a formula II; then obtaining the total water-soluble ion concentration, and obtaining the concentration of each ion in the electrolyte preparation applied and supplemented by a formula III, thereby effectively maintaining the conductivity of the soil and simultaneously enhancing the indirect oxidation and microbial metabolism capability;
wherein Q isT-Int=∑QInt(ion)
(formula one)
In the formula, QT-IntIs the initial total ion concentration (unit: mu g) of the soil-1Dry soil); qInt(ion)Is the initial concentration of a single ion in the soil;
QT=(100%~120%)QT-Int(formula two)
In the formula, QTThe total ion concentration in the soil after the electrolyte agent is supplemented; qT-IntIs the initial total ion concentration (unit: mu g) of the soil-1Dry soil);
QSup(ion)=W(ion)·QT-QRes(ion)(formula three)
In the formula, QSup(ion)Supplementing the concentration content for each single ion; qRes(ion)The concentration of single ion residual in the soil after electrokinetic-microbial remediation is shown as follows; w(ion)The proportion (%) of single ions in the total ion content in the soil after the electrolyte is supplemented.
The electrolyte replenishing preparation consists of a cation aqueous solution and an anion aqueous solution; wherein the cation is NH4 +、K+、Na+、Ca2+And Mg2+(ii) a The anion being NO3 -、PO4 3-、Cl-And SO4 2-
And (3) performing water supplement in the electric-microorganism repairing process, and determining the proportion of the average value of the total current intensity in the water supplement period to the initial current intensity value of the electric repairing when the water content of the soil is 20-25%.
Electrokinetic-microbial remediation at 1.0-1.5 V.cm-1The voltage gradient DC electric field adopts an electrode switching (electrode reversing) electrifying treatment mode, the switching is carried out once every 2h, the pH of the soil is maintained at 6.5-8.0, and the number of microorganisms in the soil is maintained at 107-108CFU·g-1The level of (c).
The invention has the following advantages and beneficial effects:
1. the electrolyte agent prepared by the invention adjusts the composition and the content of the agent in a targeted manner according to the real-time determination of the species and the quantity of the existing ions in the soil, so as to regulate and control the ion content in the soil to reach a proper level.
2. The electrolyte agent used in the invention not only enhances the conductivity in soil to a better range, but also can provide nutrient elements such as nitrogen, phosphorus, potassium and the like for the growth and metabolism of microorganisms, and is more favorable for promoting the exertion of biostimulation under the condition of creating the condition that the total N/P ratio in soil is 8:1-10: 1; at the same time, the K in the soil is properly increased+The concentration is beneficial to the intracellular osmotic adjustment of the microorganisms so as to maintain the quantity of the abundant microorganisms and the metabolic capability of the high-activity microorganisms.
3. The electrolyte agent used in the invention not only enhances the soil conductivity, maintains the direct oxidation of the electric and electrochemical properties, but also is beneficial to Cl-The resulting indirect oxidation takes place, producing active chlorine (chlorine gas (Cl)2) Chlorine radical (Cl.), hypochlorite (ClO)-) And hypochlorous acid (HClO)) has strong oxidizing power and participates in the process of efficiently oxidizing and degrading pollutants in soil.
4. The electrolyte agent used in the present invention, Cl provided-The near-neutral soil environment (pH 6.5-8.0) created under the mode of electric restoration, which effectively improves the yield and utilization efficiency of active chlorine, and is beneficial to the reaction of indirectly oxidizing pollutants in soil.
Drawings
FIG. 1 is a graph showing the petroleum degradation rate in the example of the present invention, wherein CK is a control, EK-Bio is electro-microbial remediation, and EK-Bio-Elec is electro-microbial remediation with electrolyte chemical regulation.
FIG. 2 is a graph showing the current intensity variation during electrokinetic treatment according to an embodiment of the present invention, wherein EK-Bio is electrokinetic-microbial remediation and EK-Bio-Elec is electrokinetic-microbial remediation with electrolyte chemical regulation.
FIG. 3 is a graph showing the change in microbial population during electro-microbial remediation according to an embodiment of the present invention, wherein EK-Bio is electro-microbial remediation and EK-Bio-Elec is electro-microbial remediation with electrolyte chemical regulation.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
The process of electrolyte agent configuration and application to assist electrokinetic-microbial remediation of contaminated soil is further:
1) adjusting the number of microorganisms in the soil to 10 by adopting an electric-microorganism remediation technology7-108CFU·g-1The water content of the soil is 20-25%, the pH value of the soil is 6.5-8.0, the initial soil environment condition that the soil temperature reaches 20-30 ℃ is repaired, an electrode is inserted, and 1.0-1.5V cm is applied-1The direct current with voltage gradient is used for electric-microbial remediation treatment, and the pole inverting period is 2 hours.
2) Monitoring soil initial respective inorganic ions (NH)4 +、K+、Na+、Ca2+、Mg2+、NO3 -、PO4 3-、Cl-And SO4 2-) And (4) calculating the water-soluble total ion content of the soil.
3) When the proportion of the average value of the total current intensity in the primary water replenishing period to the electric restoration initial current intensity value is less than or equal to 70%, detecting the real-time content of each ion in the soil, comparing and calculating the real-time content with the set standard concentration proportion range of each ion in the soil, determining the configuration component and the concentration of the electrolyte agent, applying the electrolyte agent into the polluted soil according to the set addition amount, and meeting the following standards after replenishing:
a. the total amount of water-soluble inorganic ions in the soil reaches 100 to 120 percent of the total content of the initial soil inorganic ions;
b. the final concentration of each single ion content in the soil meets the requirements of standard concentration range and nutrient element proportion;
c. the water content of the soil reaches 20 to 25 percent, the pH value of the soil reaches 6.5 to 8.0 level, and the number of microorganisms in the soil reaches 107-108CFU·g-1
4) And after the electrolyte agent is supplemented, continuing performing electrokinetic-microbial remediation and monitoring the current intensity and the content of water-soluble inorganic ions in the soil.
EXAMPLE electrokinetic-microbial remediation of Petroleum contaminated soils
The contaminated soil used in the test is petroleum contaminated soil artificially prepared in a laboratory, the petroleum is collected from an oil extraction area of a Liaohe oil field, the soil is sandy loam, grass root impurities visible to the naked eye are removed, the soil is naturally air-dried indoors and is sieved by a 2mm sieve, and the petroleum content is 4% (W/W, g.g.g.g)-1) The contaminated soil of (2). The test was performed after 10 days of configuration and equilibration. Initial test soil conditions were: the pH value of the soil is 6.5, the water content of the soil is 22 percent, and the inorganic ions (content) (mu g) of each component-1Dry soil) were: NH (NH)4 +(45.6±2.3)、K+(85.2±2.7)、Na+(59.7±3.7)、Ca2+(156.9±4.4)、Mg2+(61.3±3.2)、NO3 -(157.2±7.6)、PO4 3-(58.3±4.3)、Cl-(53.9. + -. 3.2) and SO4 2-(228.9±3.9)。
The assay was divided into 3 treatments, Control (CK), electrokinetic-microbial remediation (EK-Bio) and electrokinetic-microbial remediation with electrolyte agent regulation (EK-Bio-Ele). The container box body of the electric contaminated soil treatment device is 22cm in length, 16cm in width and 12cm in height, and 1400g of soil is filled in each test box. The electrode material is graphite electrode, diameter 1cm, height 12cm, applied direct current voltage is 28V, electrode inverting cycle is 2h, and repair cycle is 70 days.
The specific repairing method comprises the following steps:
the culture medium is cultured in inorganic salt medium (0.5 g.L) containing 3% petroleum-1NaCl,0.3g·L-1MgSO4,0.5g·L-1(NH4)2SO4,1.5g·L-1K2HPO4,0.5g·L-1KH2PO4,0.02g·L-1CaCl2,0.02g·L-1FeSO4,0.005g·L-1Yeast powder, pH 7.5) at 28 deg.C and 180rpm min-1Under the condition, the petroleum degradation functional bacteria microorganism (Bacillus cereus) and/or pseudomonas aeruginosa) obtained by shaking enrichment screening culture is mixed into the contaminated soil for the test, so that the content of the soil microorganism reaches 6.7 × 107CFU·g-1And after the components are uniformly mixed, starting the electric repairing process.
And (2) performing water supplement once every 5 days in the repairing process, simultaneously monitoring the change of current intensity in the device in real time, and when the proportion of the average value of the total current intensity in a water supplement period to the initial current intensity value of the electric repairing is less than or equal to 70 percent, determining the concentration of each single ion species in the soil (table 1) and calculating the concentration content of total water-soluble ions. The results of the measurement were as follows:
and calculating the total ion concentration content in the initial soil according to the determined concentrations of the single ion species in the soil and the formula I: 907 μ g-1
And calculating the theoretical value of the concentration of the water-soluble ions in the soil after the electrolyte medicament is supplemented by a formula II: 1088. mu.g.g-1
And determining the theoretical final concentration of each single water-soluble ion according to the theoretical concentration range of each single ion in the soil and the nutrient element requirement required to be met, and calculating the required addition concentration amount of each ion according to a formula III, as shown in Table 1.
The concentration of each ion of the electrolyte agent is determined according to the total mass of the soil and the volume of water supplement required by the water content requirement of the soil, and as shown in table 2, the total volume of the electrolyte agent required to be supplemented is as follows: 16 ml.
And after the electrolyte agent is supplemented, the electrokinetic-microbial remediation treatment is continued.
The current intensity, the petroleum pollutant degradation rate and the microbial count change in the test apparatus are shown in FIGS. 1 to 3.
TABLE 1
TABLE 2
Test results show that the EK-Bio group total petroleum degradation rate reaches 21.1% after 70 days of remediation, when the degradation rate reaches 30.2% after an electrolyte agent is supplemented, the total petroleum degradation rate after 70 days of treatment is improved by 9.1% due to the addition of the electrolyte agent, the current intensity in each water replenishing period is remarkably improved after the electrolyte agent is supplemented during 30 days of treatment, the number of microorganisms is greatly increased, the conductive capability of the soil is remarkably enhanced by the use of the electrolyte agent, the electrochemical oxidation (direct oxidation and indirect oxidation) effect and the metabolic function of petroleum degrading microorganisms are promoted, and the remediation capability of the petroleum polluted soil by the electric-microorganism remediation technology is favorably enhanced.

Claims (6)

1. A supplemented electrolyte formulation for electro-microbial remediation, comprising: the electrolyte replenishing preparation consists of various inorganic salt ion aqueous solutions; addition of supplementary electrolyte preparation according to QT=(100%~120%)QT-IntCalculate the addition, then press QSup(ion)=W(ion)·QT-QRes(ion)Respectively calculating the concentration of each water-soluble inorganic salt ion in the electrolyte preparation;
wherein,
QT=(100%~120%)QT-Int
in the formula, QTThe total ion concentration in the soil after the electrolyte agent is supplemented; qT-IntIs the initial total ion concentration (unit: mu g) of the soil-1Dry soil);
QSup(ion)=W(ion)·QT-QRes(ion)
in the formula, QSup(ion)Supplementing the concentration content for each single ion; qRes(ion)The concentration of single ion residual in the soil after electrokinetic-microbial remediation is shown as follows; w(ion)The proportion (%) of single ions in the total ion content in the soil after the electrolyte is supplemented.
2. A supplemented electrolyte formulation for electro-microbial remediation according to claim 1 wherein: the electrolyte replenishing preparation consists of a cation aqueous solution and an anion aqueous solution; wherein the cation is NH4 +、K+、Na+、Ca2+And Mg2 +(ii) a The anion being NO3 -、PO4 3-、Cl-And SO4 2-
3. A supplemented electrolyte formulation for electro-microbial remediation according to claim 1 wherein: and (3) water is supplemented in the electric-microorganism repairing process, and when the total average current intensity in the water supplementing period is less than or equal to 70% of the initial value, the electrolyte supplementing preparation is added, so that the soil conductivity is effectively maintained, and the indirect oxidation and microorganism metabolism capabilities are enhanced.
4. A method of replenishing a replenishment electrolyte formulation for electrokinetic-microbial remediation, the method comprising: repeatedly supplementing water in the electric-microbial remediation process, when the proportion of the average value of the total current intensity in the period of water supplementation each time to the initial current intensity value of the electric remediation is less than or equal to 70%, detecting the real-time content of each ion in the soil by adopting a first formula, and then calculating the total water-soluble ion concentration in the soil after the electrolyte preparation is supplemented by the real-time content of each ion in the soil through a second formula; then obtaining the total water-soluble ion concentration, and obtaining the concentration of each ion in the electrolyte preparation applied and supplemented by a formula III, thereby effectively maintaining the conductivity of the soil and simultaneously enhancing the indirect oxidation and microbial metabolism capability;
wherein Q isT-Int=∑QInt(ion)
(formula one)
In the formula, QT-IntIs the initial total ion concentration (unit: mu g) of the soil-1Dry soil); qInt(ion)Is the initial concentration of a single ion in the soil;
QT=(100%~120%)QT-Int(formula two)
In the formula, QTThe total ion concentration in the soil after the electrolyte agent is supplemented; qT-IntIs the initial total ion concentration (unit: mu g) of the soil-1Dry soil);
QSup(ion)=W(ion)·QT-QRes(ion)(formula three)
In the formula, QSup(ion)Supplementing the concentration content for each single ion; qRes(ion)The concentration of single ion residual in the soil after electrokinetic-microbial remediation is shown as follows; w(ion)The proportion (%) of single ions in the total ion content in the soil after the electrolyte is supplemented.
5. The method of replenishing a supplemental electrolyte formulation for electro-microbial remediation according to claim 4 wherein: the electrolyte replenishing preparation consists of a cation aqueous solution and an anion aqueous solution; wherein the cation is NH4 +、K+、Na+、Ca2+And Mg2+(ii) a The anion being NO3 -、PO4 3-、Cl-And SO4 2-
6. The method of replenishing a supplemental electrolyte formulation for electro-microbial remediation according to claim 4 wherein: and (3) performing water supplement in the electric-microorganism repairing process, and determining the proportion of the average value of the total current intensity in the water supplement period to the initial current intensity value of the electric repairing when the water content of the soil is 20-25%.
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CN107413837B (en) * 2017-09-04 2023-07-25 西南石油大学 Device for repairing petroleum-heavy metal combined contaminated soil by combining electric and microorganism and application
CN114774129A (en) * 2022-03-29 2022-07-22 中冶南方都市环保工程技术股份有限公司 Electrolyte for electrically repairing hexavalent chromium polluted soil and electric repairing method
CN114774129B (en) * 2022-03-29 2024-01-23 中冶南方都市环保工程技术股份有限公司 Electrolyte for electrically repairing hexavalent chromium polluted soil and electrically repairing method

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