CN107413837B - Device for repairing petroleum-heavy metal combined contaminated soil by combining electric and microorganism and application - Google Patents
Device for repairing petroleum-heavy metal combined contaminated soil by combining electric and microorganism and application Download PDFInfo
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- CN107413837B CN107413837B CN201710786110.9A CN201710786110A CN107413837B CN 107413837 B CN107413837 B CN 107413837B CN 201710786110 A CN201710786110 A CN 201710786110A CN 107413837 B CN107413837 B CN 107413837B
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
- B09C1/085—Reclamation of contaminated soil chemically electrochemically, e.g. by electrokinetics
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- B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
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- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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Abstract
The invention belongs to the field of environmental control and treatment, and relates to a restoration device for petroleum-heavy metal combined polluted soil, which is characterized in that: the device comprises an electric repairing pool structure, a microorganism repairing module and an electrode pH monitoring system structure, wherein the electric repairing pool structure is provided with a soil sample filling pool, a negative electrolytic pool and a positive electrolytic pool which are positioned at two ends of the soil sample filling pool, and a negative electrode and a positive electrode which are connected through a direct current power supply, and the negative electrode and the positive electrode are respectively inserted into the negative electrolytic pool and the positive electrolytic pool; the outer sides of the upper end parts of the negative electrolytic cell and the positive electrolytic cell are provided with electrolyte inlets, and the outer sides of the lower end parts are provided with electrolyte outlets; an interlayer which can separate solid from liquid is adopted between the soil sample filling tank and the electrolytic tank. The outside of the electrolytic cell is provided with an electrolyte inlet and an electrolyte outlet, and the electrolyte is updated and circulated in real time. Ensuring the activity and stable degradation performance of microorganisms; makes up the defects of the simple microorganism repairing technology, and has the advantages of easy operation, low cost, high repairing efficiency and no damage to the original natural environment.
Description
Technical Field
The invention belongs to the field of environmental control and treatment, relates to a device for repairing petroleum-heavy metal combined contaminated soil, and particularly relates to a device for repairing petroleum-heavy metal combined contaminated soil by using an electric-microorganism combination.
Background
Petroleum is the main energy source in the world today, and with the prosperity and development of human socioeconomic, the demand for petroleum in various countries of the world is increasing. However, the technical and management defects are that the leakage or overflow of petroleum and petroleum products during petroleum exploration and exploitation, storage, transportation, refining, processing and use thereof can cause serious environmental pollution, especially the soil with complex pollution caused by petroleum and heavy metals is serious, which endangers the living environment of human beings. Compared with atmospheric pollution and water pollution, the soil heavy metal pollution has the characteristics of long-term property, concealment, irreversibility, incapability of being completely decomposed or consumed and the like, is directly related to agricultural production, and is serious in hazard and difficult to treat. How to effectively prevent and solve the problem of soil petroleum-heavy metal composite pollution is increasingly paid attention to all countries in the world, and how to repair petroleum-heavy metal polluted soil with high efficiency, safety and low cost is one of important subjects in the environmental field.
The microbial remediation technology in the remediation technology has the characteristics of low cost, no damage to the soil environment required by plant growth, safe oxidation of pollutants, no secondary pollution, good treatment effect, simple operation and the like, so that the microbial remediation technology is always the key point of research on the biological petroleum pollution remediation technology in recent years. However, the nutrition in the petroleum-polluted soil is seriously disregulated, and the indigenous microorganisms are insufficient, so that the defects of low pollutant degradation rate, long soil restoration period, difficult degradation of polycyclic aromatic hydrocarbon pollutants and the like exist in the restoration process of the microbial petroleum-polluted soil.
The electric technology is a novel soil remediation technology developed first in the Netherlands and the United states in the 70 th century, and is used for remediation of heavy metal contaminated soil in early stages. Numerous methods and corresponding devices for electrokinetic remediation have also been developed, as have experimental devices for electrokinetic coupled technologies. For example, CN201454977U discloses a device for repairing heavy metal contaminated soil by point dynamic adsorption, the device comprises an electrode made of graphite, the electrode comprises a cathode and an anode, the cathode and the anode are respectively connected with two ends of a direct current power supply, the anode is arranged at the anode, the cathode is arranged at the cathode area, a separator for preventing diffusion of contaminated heavy metal ions, porous material activated carbon for adsorbing heavy metals and heavy metal contaminated soil to be treated are sequentially arranged from the anode area to the cathode area, and the method for switching the electrode is adopted to prevent the increase of the pH of the cathode area and the decrease of the pH of the anode area. CN102896143a discloses an experimental device for repairing contaminated soil by combining electric surfactants, the device comprises a main body and an eluent regulating tank, the upper half part of the main body is filled with uncontaminated soil, the side surface of the main body is provided with an eluent outlet, two electrode chambers are formed between a porous baffle plate of an electrode chamber of the main body and the inner side surface of the main body, and the two electrodes are respectively connected with a direct current power supply. An eluent adjusting tank placed above the main body is injected into the electrode chamber through a valve. The device ensures the adding uniformity of the surfactant and solves the problem of infiltration pollution of the eluent.
Also, for example, CN1899717B discloses a process for repairing heavy metal contaminated soil by combining point power and iron permeable reactive barrier, wherein graphite electrodes are installed on both sides of the soil, an iron wall is installed between the two electrodes and the soil to be treated, a power supply is turned on, metal anions are migrated near an anode under the action of an electric field, and metal cations are migrated near a cathode, and when the heavy metal passes through the iron wall, the heavy metal reacts with the iron wall to be adsorbed, reduced and precipitated. CN102500610a discloses a method for repairing heavy metal contaminated soil by electrodynamic combined drip irrigation, which comprises the steps of installing positive and negative electrodes at two ends of heavy metal contaminated soil, respectively placing adsorbents between the positive and negative electrodes and the contaminated soil, arranging a drip irrigation device above the soil near the adsorbents, slowly dripping electrolyte, buffer solution or complexing agent into the contaminated soil at two sides, periodically switching polarity and yin and yang of the electrodes, and enabling the heavy metal to move by virtue of electrokinetic migration and be adsorbed by the adsorbents so as to reduce the concentration of the heavy metal in the soil. CN204710408047145U discloses an electric combined leaching and repairing device for heavy metal contaminated soil, which comprises a leaching system and an electric repairing system; the leaching system is communicated with the polluted soil tank through a peristaltic pump; a stirrer is arranged in the leaching solution storage tank; the bottom of the polluted soil storage tank in the leaching system is communicated with the electric repairing chamber through a slurry pump. By adopting the device, the heavy metal polluted soil is subjected to chemical leaching, and then the leached soil is subjected to electroremediation.
As described above, although there are many electric combined repairing apparatuses and methods, which have good effects, there are technical problems such as high repairing cost and single repairing.
In recent years, the combined electric-microorganism repairing technology for repairing the petroleum-heavy metal composite polluted soil is started to be adopted, the electric-microorganism combined repairing technology is a new technical research at present, the method is considered to be one of the most promising soil repairing technologies at present, and the method has certain frontier and innovation, but the related research on electric field strengthening microorganism repairing is very few at home and abroad. The experimental device for combining the electric repairing and the microbial repairing agent is rarely involved, and most of electric experimental devices are only provided with an anode tank and a cathode tank without electrolyte, so that the acidic environment generated by the anode of the electrolytic tank is unfavorable for the growth and propagation of microorganisms, the alkaline environment of the cathode causes heavy metal precipitation, the removal rate is reduced, and meanwhile, the growth of microorganisms is unfavorable.
Thus, devices and methods suitable for the combined electro-microbial remediation of petroleum-heavy metal contaminated soil are now desired.
Disclosure of Invention
In order to solve the problems, the invention provides a device for repairing petroleum-heavy metal contaminated soil by using an electric-microorganism combined technology, which can well simulate the condition of repairing the composite contaminated soil by using the electric-microorganism combined technology, and ensure the activity and stable degradation performance of microorganisms; makes up the defects of the simple microorganism repairing technology, and has the advantages of easy operation, low cost, high repairing efficiency and no damage to the original natural environment.
The invention solves the technical problems, and relates to a device for repairing petroleum-heavy metal contaminated soil by using an electric-microorganism combined technology, which is characterized in that: the device comprises an electric repairing pool structure, a microorganism repairing module and an electrode pH monitoring system structure, wherein the electric repairing pool structure is provided with a soil sample filling pool, a negative electrolytic pool and a positive electrolytic pool which are positioned at two ends of the soil sample filling pool, and a negative electrode and a positive electrode which are connected through a direct current power supply, and the negative electrode and the positive electrode are respectively inserted into the negative electrolytic pool and the positive electrolytic pool; the outer sides of the upper end parts of the negative electrolytic cell and the positive electrolytic cell are provided with electrolyte inlets, and the outer sides of the lower end parts are provided with electrolyte outlets; an interlayer which can separate solid from liquid is adopted between the soil sample filling tank and the electrolytic tank. An electrolyte inlet and an electrolyte outlet are arranged on the outer side of the electrolytic cell, and the electrolyte is updated and circulated in real time
The electrode pH monitoring system structure is provided with a pH real-time monitor and an electrolyte replacement tank, one end of the pH real-time monitor is connected with the electrolyte replacement tank, and the electrolyte replacement tank is provided with an anode electrolyte replacement tank and a cathode electrolyte replacement tank; the electrolyte exchange tank is also provided with an inlet peristaltic pump and an outlet peristaltic pump, one end of the peristaltic pump is connected with the electrolyte inlet, the other end of the peristaltic pump extends into the electrolyte exchange tank, one end of the outlet peristaltic pump is connected with the electrolyte outlet, and the other end of the outlet peristaltic pump extends into the electrolyte exchange tank; the change in pH is displayed in real time with a pH real time monitor.
The microbial remediation module comprises N microbial remediation blocks located in an electrokinetic remediation tank.
The electric repairing pool structure is also provided with a top cover, and is positioned at the upper ends of the soil sample filling pool, the negative electrolytic pool and the positive electrolytic pool, and the negative electrode and the positive electrode penetrate through the top cover and are respectively inserted into the negative electrolytic pool and the positive electrolytic pool.
The top cover is provided with air holes, and the number of the air holes is more than or equal to 1.
The top cover is favorable for maintaining temperature, and air holes are formed in the top cover, so that the ventilation and gas exchange of microorganisms are facilitated.
The soil sample filling pool is divided into N small soil chambers, N is more than or equal to 1, and if N is more than or equal to 1, the small soil chambers are separated by a membrane (11).
The N=5, the membrane is an inorganic ceramic membrane, and the cathode electrode and the anode electrode are graphite. An inorganic ceramic membrane is used as a separator for solid-liquid separation.
The specific surface area of the microbial remediation block is 1000m < 2 >/g, and the pore size is 2-50nm. The microbial remediation block is a heavy metal passivating agent for microbial remediation, adopts a novel environment-friendly material to fix microorganisms, has large specific surface area and high porosity, has good adsorption effect on petroleum pollutants, and simultaneously has good adsorption and passivation effects on heavy metals, so that the toxicity of the heavy metals is reduced, and the adsorption and degradation of microorganisms are facilitated. The high porosity can provide a good habitat for microorganisms, accelerate the growth of the microorganisms and improve the degradation rate of the composite pollutants.
The preparation method of the microbial repair block comprises the following steps:
adding porous silicon oxide into a liquid culture medium containing efficient petroleum degrading bacteria, wherein the culture medium is a beef extract culture medium containing inorganic salt, the components of the beef extract are 15-25% of beef extract, 0.5-3% of NaCl, 0.1-5% of NH4SO4, 4 1% of NaH2PO, 0.5% of Na2HPO4, and pH of 7-7.5, and the mass fraction of the porous silicon oxide in the liquid culture medium is 0.1-1%;
step two: culturing at constant temperature for 7 days, centrifuging, and drying to obtain microorganism repairing block loaded with high-efficiency petroleum degrading bacteria.
The preparation method of the porous silicon oxide nano material comprises the following steps:
(1) Tetraethyl orthosilicate (TEOS) is used as a silicon source, and cetyltrimethylammonium bromide (CATB) is used as a template agent; 2.1 ml of 2 mol/L NaoH solution and 0.6 g of CATB were added to 288 ml distilled water, and then heated at 80℃with stirring until the solution became clear;
(2) Then 3 ml TEOS was added dropwise and stirred, and reacted at 80℃for two hours; after the reaction is finished, centrifuging, drying and grinding the obtained solution to obtain white powdery solid;
(3) The template agent is removed by a calcination method, and the specific process is as follows: adding 1.0 g acrylamide, 0.1 mg cross-linking agent N-N methylene bisacrylamide and 25 mg (NH 4) 2S2O8 (ammonium peroxodisulfate) into 10 g suspension containing 5% of nano particles under stirring, and completely dispersing the nano particles in the solution by ultrasonic treatment for 15 min; then heating to 50 ℃ to cause the added organic monomer to carry out polymerization reaction, and drying the obtained solution at 80-100 ℃ overnight; and calcining at 550 ℃ to obtain the porous silica nanomaterial with good dispersion property.
The invention relates to an application of an electric-microorganism combined petroleum-heavy metal polluted soil repairing device, namely an application of microorganism repairing heavy metal passivating agent and electric combined repairing, wherein 5-10% porous silicon oxide loaded with petroleum high-efficiency degrading bacteria is added into petroleum-heavy metal polluted mixed soil after grinding and crushing to obtain heavy metal passivating agent, the heavy metal passivating agent is fully mixed, saturated for 24 hours by inorganic salt and then placed into a soil sample filling pond, compacted, and the repaired mixed polluted soil is obtained after 28 days, and the method specifically comprises the following steps:
(1) And (3) a mounting device: installing an electric repairing pool structure;
(2) Collecting polluted soil samples, airing, crushing, removing tree roots and stones, sieving, mixing with microorganism repairing blocks, saturating with inorganic salt saturated solution for 22-26 hours, and compacting in a soil sample filling pond; wherein the inorganic salt saturated solution comprises the following components in parts by mass: 0.9 part of KH2PO4, 0.1 part of K2HPO4, 0.1 part of NH4NO3, 0.1 part of MgSO4.7H2O, 0.08 part of CaCl2 and 0.01 part of FeCl3.6H2O.
(3) Inserting a cathode electrode and an anode electrode into the cathode electrolytic cell and the anode electrolytic cell respectively, and simultaneously connecting an electrolyte replacement cell, an inlet peristaltic pump, an outlet peristaltic pump and a pH real-time monitor component;
(4) Switching on a power supply, wherein the voltage is 1V/cm;
(5) Starting a pH real-time monitor to prevent the pH from greatly fluctuating;
(6) And (3) measuring and observing: the sample was removed once in 7 days, and then the total petroleum hydrocarbon content and the heavy metal lead (Pb) content were measured.
In the step (5), the pH value in the cathode electrolytic cell is 5.6, and the pH value in the anode electrolytic cell is 8.0.
The invention has the beneficial effects that:
A. by adding electrolyte, circulating in real time and updating periodically, abnormal reduction or increase of pH caused by electrolysis of water can be avoided, and the removal of petroleum and heavy metals is better facilitated.
B. By setting the pH real-time monitoring system, the electrolyte is updated in time, and labor and financial resources are saved.
C. The heavy metal passivating agent for repairing the microorganisms is added, so that the influence of large fluctuation of pH on the activity of the microorganisms can be avoided, the degradation efficiency is influenced, and the continuous performance of electric repair can be ensured. Meanwhile, the metal toxicity can be adsorbed and reduced, and the adsorption and degradation of microorganisms on heavy metals are facilitated.
D. The device can simulate the condition of treating the polluted soil by a microorganism-electric combined technology, greatly improves the previous single effect of electric restoration and microorganism restoration on the polluted soil, and solves the problems that the previous removal rate is low, the microorganism activity is insufficient, and heavy metals are easy to precipitate and difficult to remove due to the increase of pH. And has application prospect and popularization value.
The electric repairing device provided by the invention can well simulate the condition of repairing the composite polluted soil by using an electric-microorganism combined technology, ensures the activity and stable degradation performance of microorganisms, is a device with experimental value and application prospect aiming at the petroleum-heavy metal polluted soil repairing technology in recent years, and has good popularization and application value. Combines with the microorganism technology, establishes the electric-microorganism combined repair technology and starts to repair the organic pollution. The electric field enhanced microorganism repairing technology can make up for the defects of the simple microorganism repairing technology, and has the advantages of easy operation, low cost, high repairing efficiency and no damage to the original natural environment. The novel microorganism repairing heavy metal passivating agent and the electric repairing are combined to treat the composite polluted soil, so that the problem that the composite pollution is unoccupied is solved effectively.
Drawings
FIG. 1 is a schematic view of the structure of the device in the present invention.
Wherein the specific identification is as follows:
1. DC power supply, 2.PH real-time monitor, 3 inlet peristaltic pump, 4 outlet peristaltic pump, 5 electrolyte replacement cell (5-1 anolyte replacement cell, 5-2 catholyte replacement cell), 6 microbial remediation agent, 7 electrolyte inlet, 8 electrolyte outlet, 9 anolyte cell, 10 catholyte cell, 11 inorganic ceramic membrane, 12 top cover, 13 anode electrode, 14 cathode electrode, 15 soil sample filling cell, 16 air holes
Detailed Description
The invention will be described in further detail with reference to the accompanying drawings and detailed description:
example 1
The invention is further described with reference to the drawings and detailed description which follow:
the apparatus of the present invention will be described in further detail below with reference to the drawings and the specific embodiments, but this is merely illustrative of the apparatus and operation of the present invention and is not intended to limit the scope of the invention thereto.
Example 1
The device comprises an electric repairing pool structure, a microorganism repairing module and an electrode pH monitoring system structure, wherein the electric repairing pool structure is provided with a soil sample filling pool, a negative electrolytic pool and a positive electrolytic pool which are positioned at two ends of the soil sample filling pool, and a negative electrode and a positive electrode which are connected through a direct current power supply, and the negative electrode and the positive electrode are respectively inserted into the negative electrolytic pool and the positive electrolytic pool; the outer sides of the upper end parts of the negative electrolytic cell and the positive electrolytic cell are provided with electrolyte inlets, and the outer sides of the lower end parts are provided with electrolyte outlets; an interlayer which can separate solid from liquid is adopted between the soil sample filling tank and the electrolytic tank.
The electrode pH monitoring system structure is provided with a pH real-time monitor and an electrolyte replacement tank, one end of the pH real-time monitor is connected with the electrolyte replacement tank, and the electrolyte replacement tank is provided with an anode electrolyte replacement tank and a cathode electrolyte replacement tank; the electrolyte exchange tank is also provided with an inlet peristaltic pump and an outlet peristaltic pump, one end of the peristaltic pump is connected with the electrolyte inlet, the other end of the peristaltic pump extends into the electrolyte exchange tank, one end of the outlet peristaltic pump is connected with the electrolyte outlet, and the other end of the outlet peristaltic pump extends into the electrolyte exchange tank; the change in pH is displayed in real time with a pH real time monitor. The microbial remediation module comprises N microbial remediation blocks located in an electrokinetic remediation pond.
The number of the pH real-time monitors is 2, and the pH real-time monitors are respectively connected with the anolyte replacement tank and the catholyte replacement tank. The anolyte replacement cell and the anolyte cell are positioned on the same side, and the catholyte replacement cell and the catholyte cell are positioned on the same side.
Example 2
Referring to fig. 1, the device comprises an electric repairing pool structure, a microorganism repairing module and an electrode pH monitoring system structure, wherein the electric repairing pool structure is provided with a soil sample filling pool, a negative electrolytic pool and a positive electrolytic pool which are positioned at two ends of the soil sample filling pool, and a negative electrode and a positive electrode which are connected through a direct current power supply, and the negative electrode and the positive electrode are respectively inserted into the negative electrolytic pool and the positive electrolytic pool; the outer sides of the upper end parts of the negative electrolytic cell and the positive electrolytic cell are provided with electrolyte inlets, and the outer sides of the lower end parts are provided with electrolyte outlets; an interlayer which can separate solid from liquid is adopted between the soil sample filling tank and the electrolytic tank.
The electrode pH monitoring system structure is provided with a pH real-time monitor and an electrolyte replacement tank, one end of the pH real-time monitor is connected with the electrolyte replacement tank, and the electrolyte replacement tank is provided with an anode electrolyte replacement tank and a cathode electrolyte replacement tank; the electrolyte exchange tank is also provided with an inlet peristaltic pump and an outlet peristaltic pump, one end of the peristaltic pump is connected with the electrolyte inlet, the other end of the peristaltic pump extends into the electrolyte exchange tank, one end of the outlet peristaltic pump is connected with the electrolyte outlet, and the other end of the outlet peristaltic pump extends into the electrolyte exchange tank; the change in pH is displayed in real time with a pH real time monitor. The microbial remediation module comprises N microbial remediation blocks located in an electrokinetic remediation pond.
Wherein, still be equipped with electronic restoration pond top cap, be located soil sample filling pond, negative electrolytic cell and positive electrolytic cell upper end, negative electrode and positive electrode pass the top cap and insert respectively in negative electrolytic cell and the positive electrolytic cell. The soil sample filling tank is positioned between the cathode and anode electrolytic tanks and is divided into five small soil chambers, so that sampling analysis is convenient, each soil chamber is separated from the electrolytic tank by a penetrable inorganic ceramic membrane, an electrolyte inlet and an electrolyte outlet are arranged on the outer side of the electrolytic tank, and the electrolyte is updated and circulated in real time; the top cover is favorable for maintaining temperature, and air holes are formed in the top cover, so that the ventilation and gas exchange of microorganisms are facilitated.
The pH real-time monitoring system comprises an electrolyte replacement tank, and the pH real-time monitor is inserted into the electrolyte replacement tank to detect the electrolyte in real time, so that the influence on the activity of petroleum degradation microorganisms and the removal of heavy metals due to the severe fluctuation of pH is prevented. The heavy metal passivating agent nano material for repairing the microorganisms is fully mixed with petroleum-heavy metal composite pollutants and then added into a soil sample filling pool.
Example 3
The preparation method of the microorganism repairing heavy metal passivating agent comprises the following steps: firstly, preparing porous silicon oxide nano material, and then fixing high-efficiency petroleum degrading bacteria as a microorganism repairing heavy metal passivating agent.
The specific surface area of the microbial remediation block is 1000m 2/g, and the pore size is 2-50nm.
The preparation method of the porous silicon oxide nano material comprises the following steps:
(1) Tetraethyl orthosilicate (TEOS) is used as a silicon source, and cetyltrimethylammonium bromide (CATB) is used as a template agent; 2.1 ml of 2 mol/L NaoH solution and 0.6 g of CATB were added to 288 ml distilled water, and then heated at 80℃with stirring until the solution became clear;
(2) Then 3 ml TEOS was added dropwise and stirred, and reacted at 80℃for two hours; after the reaction is finished, centrifuging, drying and grinding the obtained solution to obtain white powdery solid;
(3) The template agent is removed by a calcination method, and the specific process is as follows: adding 1.0 g acrylamide, 0.1 mg cross-linking agent N-N methylene bisacrylamide and 25 mg (NH 4) 2S2O8 (ammonium peroxodisulfate) into 10 g suspension containing 5% of nano particles under stirring, and completely dispersing the nano particles in the solution by ultrasonic treatment for 15 min; then heating to 50 ℃ to cause the added organic monomer to carry out polymerization reaction, and drying the obtained solution at 80-100 ℃ overnight; and calcining at 550 ℃ to obtain the porous silica nanomaterial with good dispersion property.
The preparation method of the microorganism repairing block (microorganism repairing heavy metal passivating agent) comprises the following steps:
adding porous silicon oxide into a liquid culture medium containing efficient petroleum degrading bacteria, wherein the culture medium is a beef extract culture medium containing inorganic salt, the components of the beef extract are 15-25% of beef extract, 0.5-3% of NaCl, 0.1-5% of NH4SO4, 4 1% of NaH2PO, 0.5% of Na2HPO4, and pH of 7-7.5, and the mass fraction of the porous silicon oxide in the liquid culture medium is 0.1-1%;
step two: culturing at constant temperature for 7 days, centrifuging, and drying to obtain microorganism repairing block loaded with high-efficiency petroleum degrading bacteria.
The device is used for treating petroleum-heavy metal polluted soil for example, and electric microorganism combined restoration is carried out.
Example 4
According to the invention, the step of electric-microorganism combined restoration of the petroleum-heavy metal composite pollutant is carried out, namely, the step of microorganism restoration heavy metal passivating agent and electric combined restoration is carried out, 5-10% porous silicon oxide loaded with petroleum high-efficiency degrading bacteria is added into the petroleum-heavy metal polluted mixed soil after grinding and crushing, the heavy metal passivating agent is fully mixed, the mixture is saturated by inorganic salt for 24 hours and then is placed into a soil sample filling pool, and the mixture is compacted, so that the restored mixed polluted soil is obtained after 28 days.
The method comprises the following specific steps:
(1) The device is installed, the size of the device is determined by the amount of the treated soil sample, the connection at the partition plate is ensured to be airtight, and the leakage of particles such as soil is prevented. The structure of the device adopted this time is: the size of the soil sample filling pool is 20 cm multiplied by 4 cm multiplied by 4 cm, and the soil sample filling pool is divided into 5 soil chambers, so that the soil sample filling pool is convenient to sample, the size of the electrolytic pool is 1L, and the size of the electrolytic solution replacing pool is 2L.
(2) The method comprises the steps of airing and crushing a soil sample which is polluted by petroleum and heavy metal lead (Pb) for many years, removing tree roots and stones, sieving with a 2mm sieve, weighing 600g of the polluted soil sample and a microorganism repairing heavy metal passivating agent for full alleviation, and then saturating the soil sample with an inorganic salt saturated solution, wherein the inorganic salt comprises the following components: KH2PO4 0.9, K2HPO4 0.1,NH4NO3 0.1, mgSO4.7H2O 0.1, caCl2 0.08, fecl3.6h2o 0.01, after 24 hours of saturation, the soil samples were divided equally into 5 small soil chambers and compacted.
(3) Inserting an electrode into an electrolytic cell, connecting the electrolytic cell with components such as an electrolyte replacement cell, a peristaltic pump, a pH real-time monitor and the like; the electrode is a graphite electrode, and the specification is 4 cm multiplied by 4 multiplied by cm multiplied by 4 cm.
(4) And (5) switching on a power supply, wherein the voltage is 1V/cm.
(5) And starting the pH real-time monitor to prevent the pH from greatly fluctuating.
(6) The device can directly read the current in the experimental process from a direct current power supply, and the electroosmotic flow can be calculated from the height of electrolyte in the electrolytic cell.
Test one
The soil chamber designed for this test was five small sections, each 7 days was sampled, and then the total petroleum hydrocarbon content and the heavy metal lead (Pb) content were measured. Specific procedures and apparatus using the contents of example 1, the changes in contaminant concentration (mg/kg) over a 28 day period of experimental treatment are shown in the table:
the soil pollutant content after the treatment is less than national regulation after the treatment for 28 days, and a very good effect is obtained.
According to the invention, the electrolytic cell is filled with electrolyte and is replaced periodically; the adsorption material is arranged at the position contacting the anode or the cathode, and the heavy metal passivating agent is repaired by adding microorganisms, so that pollutants can be effectively degraded in a soil chamber, and the pollutants can be migrated; the electrolyte is filled, circulated in real time and updated periodically, and the polarity change of pH can be controlled, so that the removal rate of petroleum and heavy metals is improved.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.
Claims (6)
1. The utility model provides a device with electronic-microorganism combination restoration oil-heavy metal contaminated soil which characterized in that: the device comprises an electric repairing pool structure, a microorganism repairing module and an electrode pH monitoring system structure, wherein the electric repairing pool structure is provided with a soil sample filling pool (15), a cathode electrolytic cell (10) and an anode electrolytic cell (9) which are positioned at two ends of the soil sample filling pool (15), and a cathode electrode (14) and an anode electrode (13) which are connected through a direct current power supply (1), and the cathode electrode (14) and the anode electrode (13) are respectively inserted into the cathode electrolytic cell (10) and the anode electrolytic cell (9); an electrolyte inlet (7) is arranged at the outer side of the upper end parts of the cathode electrolytic cell (10) and the anode electrolytic cell (9), and an electrolyte outlet (8) is arranged at the outer side of the lower end part;
the electrode pH monitoring system is structurally provided with a pH real-time monitor (2) and an electrolyte replacement tank (5), one end of the pH real-time monitor (2) is connected with the electrolyte replacement tank (5), and the electrolyte replacement tank (5) is provided with an anode electrolyte replacement tank (5-1) and a cathode electrolyte replacement tank (5-2); the electrolyte exchange device is also provided with an inlet peristaltic pump (3) and an outlet peristaltic pump (4), wherein one end of the inlet peristaltic pump (3) is connected with an electrolyte inlet (7), the other end of the inlet peristaltic pump extends into the electrolyte exchange tank (5), one end of the outlet peristaltic pump (4) is connected with an electrolyte outlet (8), and the other end of the outlet peristaltic pump extends into the electrolyte exchange tank (5);
the microbial repair module comprises N electric-driven devicesA microbial remediation agent (6) in the remediation pool, wherein the specific surface area of the microbial remediation agent (6) is 1000m 2 And/g, the pore size is 2-50nm, and the microbial restoration agent (6) is prepared by using porous silicon oxide;
the soil sample filling pool (15) is divided into N small soil chambers, and N is more than or equal to 1; if N >1 or more, each small soil chamber is partitioned by a membrane (11);
the preparation method of the microbial restoration agent comprises the following steps:
step one, adding porous silicon oxide into a liquid culture medium containing efficient petroleum degrading bacteria, wherein the culture medium is a beef extract culture medium containing inorganic salt, and the components of the beef extract are 15-25%, 0.5-3% of NaCl and NH 4 SO 4 0.1-5％，NaH 2 PO 4 1％，Na 2 HPO 4 0.5 percent, pH is 7 to 7.5, and the mass fraction of the porous silicon oxide in the liquid culture medium is 0.1 to 1 percent;
step two: culturing at constant temperature for 7 days, centrifuging, and drying to obtain the microorganism repairing agent loaded with high-efficiency petroleum degrading bacteria.
2. The apparatus for the combined remediation of petroleum-heavy metal contaminated soil with electro-microorganisms according to claim 1, wherein: the electric repairing pool structure is also provided with a top cover (12) which is positioned at the upper ends of the soil sample filling pool (15), the cathode electrolytic pool (10) and the anode electrolytic pool (9), and the cathode electrode (14) and the anode electrode (13) penetrate through the top cover (12) and are respectively inserted into the cathode electrolytic pool (10) and the anode electrolytic pool (9).
3. The apparatus for the combined remediation of petroleum-heavy metal contaminated soil with electro-microorganisms according to claim 2, wherein: and air holes (16) are formed in the top cover (12), and the number of the air holes (16) is more than or equal to 1.
4. The apparatus for the combined remediation of petroleum-heavy metal contaminated soil with electro-microorganisms according to claim 1, wherein: the n=5, the membrane (11) is an inorganic ceramic membrane, and the cathode electrode (14) and the anode electrode (13) are graphite.
5. The use of an apparatus for the combined remediation of petroleum-heavy metal contaminated soil with electro-microorganisms according to claim 1, wherein: the method comprises the following steps:
(1) And (3) a mounting device: installing an electric repairing pool structure;
(2) Collecting polluted soil samples, airing, crushing, removing tree roots and stones, sieving, mixing with a microbial repairing agent, saturating with an inorganic salt saturated solution for 22-26 hours, and putting into a soil sample filling pool for compaction; wherein the inorganic salt saturated solution comprises the following components in parts by mass: KH (KH) 2 PO 4 0.9 part, K 2 HPO 4 0.1 part of NH 4 NO 3 0.1 part of MgSO 4 ·7H 2 O0.1 part, caCl 2 0.08 part of FeCl 3 ·6H 2 0.01 part of O;
(3) Respectively inserting a cathode electrode and an anode electrode into the cathode electrolytic cell and the anode electrolytic cell, and simultaneously connecting an electrolyte replacement cell, an inlet peristaltic pump, an outlet peristaltic pump and a pH real-time monitor component;
(4) Switching on a power supply, wherein the power supply voltage is 1V/cm;
(5) Starting a pH real-time monitor to prevent the pH from greatly fluctuating;
(6) And (3) measuring and observing: the sample was removed once in 7 days, and then the total petroleum hydrocarbon content and the heavy metal lead (Pb) content were measured.
6. The use of the device for the combined remediation of petroleum-heavy metal contaminated soil with electro-microorganisms according to claim 5, wherein: in the step (5), the pH value in the cathode electrolytic cell is 5.6, and the pH value in the anode electrolytic cell is 8.0.
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