CN112337559A - Coupling biological strengthening repair device and method for pre-oxidized organic contaminated soil - Google Patents
Coupling biological strengthening repair device and method for pre-oxidized organic contaminated soil Download PDFInfo
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- CN112337559A CN112337559A CN202011249963.7A CN202011249963A CN112337559A CN 112337559 A CN112337559 A CN 112337559A CN 202011249963 A CN202011249963 A CN 202011249963A CN 112337559 A CN112337559 A CN 112337559A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
- B02C23/08—Separating or sorting of material, associated with crushing or disintegrating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C4/00—Crushing or disintegrating by roller mills
- B02C4/02—Crushing or disintegrating by roller mills with two or more rollers
- B02C4/08—Crushing or disintegrating by roller mills with two or more rollers with co-operating corrugated or toothed crushing-rollers
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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
Abstract
The invention relates to a coupling biological strengthening and repairing device for pre-oxidized organic contaminated soil, which comprises a soil screening and crushing device, a medicament mixing device, a spraying device, a bioreactor device, a soil stirring device, an aeration and oxygenation device and a tail gas treatment device (25); soil screening reducing mechanism, medicament mixing arrangement set up in the top of bioreactor device, and spray set and soil agitating unit set up inside the bioreactor device, and aeration oxygenation device sets up in one side of bioreactor device, and the upper wall right side of bioreactor is connected with tail gas processing apparatus (25), and this scheme makes soil and medicament mix the stirring more abundant, has strengthened the repairing effect of organic contaminated soil.
Description
Technical Field
The invention relates to a degradation method, in particular to a device and a method for coupling biological strengthening repair of pre-oxidized organic contaminated soil, and belongs to the technical field of pollution treatment.
Background
At present, a plurality of methods are available for repairing the organic polluted soil, and physical, chemical and biological methods are common technical means. The chemical oxidation method has the advantages of wide application range, high utilization rate, high repairing speed, high efficiency and the like, and can quickly and efficiently remove various organic pollutants in soil, but the problems of easy change of the physicochemical property of the soil, damage to the ecosystem of microorganisms, secondary pollution to the environment and the like caused by excessive addition of chemical oxidants limit the application of the chemical oxidation method.
Compared with other technologies such as chemical oxidation, the microbial remediation technology is more and more concerned by environmental protection and scientific research workers due to the advantages of simple operation, wide application area, low cost, easy maintenance, large degradation potential and the like. But also has the defects of long restoration time, strict requirements on environment and the like, has the phenomenon of poor degradation effect on some high molecular organic matters which are difficult to degrade, and is not suitable for soil poor in nutrition, so that the application in the actual polluted site still has certain limitation.
In order to solve the limitation of a single repair technology and achieve the purpose of efficiently degrading organic pollutants, a plurality of methods can be used for combined repair. Research in recent years shows that chemical oxidation and microorganism combined repair is a feasible repair method and has wide application prospect. In the process of utilizing the microorganisms to repair the organic polluted soil, the single indigenous strain has lower degradation efficiency on the organic pollutants with complex components, and can enrich the diversity of the microorganisms in the polluted soil and promote the propagation and growth of the microorganisms by introducing exogenous degradation bacteria, applying nutrient substances, increasing the concentration of dissolved oxygen and other strengthening technologies, thereby effectively improving the degradation efficiency of the microorganisms on the organic pollutants.
At present, most of treatment devices for repairing organic contaminated soil remove organic matters in soil in a heating mode, so that the characteristics of the soil are changed. The microbial remediation technology has small disturbance on soil characteristics but is harsh on reaction conditions, so that a biological reaction device which is simple in structure, convenient to operate and easy to set the reaction conditions is urgently needed to be developed, the disturbance on the soil characteristics is reduced, and the microbial degradation capacity and efficiency can be improved.
Disclosure of Invention
The invention provides a method for degrading organic matters in a coupling and biological strengthening way after pre-oxidation, aiming at the problems in the prior art. Can reduce or avoid the problems caused by the inadaptability of a single strain to the environment or the selectivity of a carbon source and the like to the maximum extent, and effectively improve the removal rate of organic pollutants.
In order to achieve the purpose, the technical scheme of the invention is that the device for coupling the pre-oxidized organic contaminated soil with the biological enhancement remediation comprises a soil screening and crushing device, a medicament mixing device, a spraying device, a bioreactor device, a soil stirring device, an aeration and oxygenation device and a tail gas treatment device; soil screening reducing mechanism, medicament mixing arrangement set up in the top of bioreactor device, and spray set and soil agitating unit set up inside the bioreactor device, and aeration oxygenation device sets up in one side of bioreactor device, and the upper wall right side of bioreactor is connected with tail gas treatment device.
As an improvement of the invention, the soil screening and crushing device comprises a soil screening and crushing machine, a vibration type sieve plate and a crushing gear, wherein a feeding hole is formed right above the soil screening and crushing machine, the vibration type sieve plate is arranged at the lower end of the feeding hole, a sundry outlet is formed in the left side of the vibration type sieve plate, a sundry collecting bin is arranged below the sundry outlet, the crushing gear is arranged below the vibration type sieve plate, and a discharging pipe below the crushing gear is connected with the feeding hole of the bioreactor device.
As an improvement of the invention, the bioreactor device is set as a bioreactor, the spraying device is set as a nozzle, the inner side of the upper wall of the bioreactor is provided with a medicament storage box and the nozzle, the right side of the upper wall of the bioreactor is connected with a tail gas treatment device, the middle part of the upper wall of the bioreactor is provided with a soil stirring device, the inner side of the lower wall of the bioreactor is provided with an aeration and oxygenation device, and the right side of the lower wall of the bioreactor is provided; soil agitating unit includes (mixing) shaft and spiral blade, goes up (mixing) shaft and lower (mixing) shaft parallel mount, goes up (mixing) shaft and lower (mixing) shaft blade spiral opposite direction, and soil shifts to the right by the stirring shaft propulsion in last stirring district, enters into stirring district down, shifts to the left by stirring shaft propulsion down again, and soil is at the stirring tank inner loop stirring, and the stirring is more abundant.
As an improvement of the invention, the medicament mixing device is arranged as a medicament mixing box, the medicament storage box is connected with the medicament mixing box through a medicament feeding pipe, a medicament stirring paddle is arranged in the medicament mixing box, and a flow regulating valve is arranged between the medicament mixing box and the medicament storage box to control the flow rate of the medicament; the tail gas discharge port is connected to a tail gas treatment device through a pipeline, a pressure gauge and a pressure regulating valve are arranged between the tail gas discharge port and the tail gas treatment device, and activated carbon is arranged in the tail gas treatment device to carry out tail gas adsorption treatment; the aeration oxygenation device comprises an air compressor and an aeration pipe, wherein the aeration pipe is provided with aeration holes, the aeration pipe is embedded in a hard polyvinyl chloride sieve pipe (PVC sieve pipe), and sieve slits are arranged on the PVC sieve pipe.
A restoration method for degrading organic pollutants in soil by means of an oxidation path and a biological enhancement path simultaneously comprises the steps of firstly preferentially adding a strong oxidant into the soil and then carrying out microorganism enhancement. The method comprises the following specific steps: the method comprises the steps of screening and crushing soil, then feeding the soil into a bioreactor, selectively adding a chemical oxidant, efficient degrading bacteria, a biological surfactant, nutrient substances and the like according to the type of the organic polluted soil, uniformly mixing the agents, then spraying the mixed agents onto the soil, adding the agents while stirring, aerating and oxygenating at proper time, and collecting and treating tail gas.
The strong oxidizer is selected from one or more of fenton, ozone, peroxy acid, potassium permanganate, hydrogen peroxide and sodium persulfate, and the usage amount of the strong oxidizer in soil is 1-3%. The oxidation way is carried out by using the oxidation-reduction reaction between a strong oxidant and an organic matter, so that pollutants are converted into stable, low-toxicity or non-toxic substances, the soil pollution concentration is reduced, and the method is favorable for maintaining the living environment required by the degradation of indigenous microorganisms. The microorganism approach is to enhance the degradation of organic matters by enhancing microorganisms, and the enhancing measures can adopt the modes of adding nutrient substances, biosurfactant, high-efficiency degrading bacteria and aeration oxygenation, so that the quantity and activity of various microorganisms in soil can be increased, the degradation speed of the organic matters is increased by fully utilizing the co-metabolism, and organic pollutants are converted into simple inorganic matters.
The high-efficiency degrading bacteria are selected from one or more of trichoderma, aspergillus, bacillus, pseudomonas and acinetobacter, and the microbial inoculum accounts for 0.5-2%.
The nutrient substances comprise an N source and a P source. Wherein, the N source can be one of ammonium sulfate, sodium nitrate and ammonium nitrate; the P source can be one of potassium dihydrogen phosphate, sodium dihydrogen phosphate and sodium dihydrogen phosphate. The content of the nutrient substances is 0.001-1%.
The dissolved oxygen increasing mode can adopt physical aeration or H addition2O2、CaO2And the like. H2O2、CaO2The oxygen release material is 0.05-1%.
The biosurfactant is one of rhamnolipid, fatty peptide, sugar ester, neutral ester and fatty acid. The content of the biosurfactant is 0.01-0.5%.
The organic matters are benzene series, polycyclic aromatic hydrocarbon, chlorobenzene, phenols, chloralkane and petroleum hydrocarbon organic pollution. The concentration of the pollutants is 100-50000 mg/kg.
The use method of the repair material provided by the invention in the process of treating the organic contaminated soil comprises the following steps: and (2) preferentially adding a strong oxidant into the soil, and then adding one or more of nutrient substances, a biosurfactant and efficient degrading bacteria according to the requirements to jointly repair the polluted soil. The method comprises the following specific steps: after the strong oxidant is added into the reagent mixing box, a proper amount of water is added, the strong oxidant is stirred by a stirring paddle to change the reagent from a powder state into a solution state, the solution state is conveyed to the reagent storage box through a reagent feeding pipe, the solution is sprayed onto the soil in the bioreactor by a spray head, the reagent is more easily in full contact reaction with the soil while spraying, and the internal circulation stirring of the container can be realized by an upper stirring device and a lower stirring device; after stirring, maintaining for 3 days; after the maintenance is finished, adding a biological strengthening or biological stimulating material into the soil, opening the aeration device, providing oxygen for aerobic microorganisms, increasing the efficiency and effectiveness of biodegradation, regularly discharging tail gas, stabilizing the pressure in the container, maintaining for 1-3 months, and adding a proper amount of water into the soil during the maintenance period to enable the water content of the soil to be about 30%.
Compared with the prior art, the invention has the following advantages: 1) this equipment makes the stone fall into the debris of lower extreme through vibrations on the sieve of slope and collects the storehouse through setting up vibrations formula sieve, and the soil that falls down from the sieve is smashed through rubbing crusher, has increased the area of contact of soil with the medicament, improves soil improvement effect. Stirring soil through the agitating unit who sets up, the stirring mode of its inner loop has increased mixed effect, and the medicament is followed the shower nozzle blowout of bioreactor upper end simultaneously, forms the process of adding medicine while stirring, can effectively improve the mixing efficiency of soil and medicament, further increases the treatment effect of soil. The aeration device arranged at the lower end can provide oxygen required by the reaction of microorganisms, the activity of the microorganisms and the degradation capability of organic pollutants are improved, and the aeration pipe is sleeved in the PVC sieve pipe, so that the blockage of soil to aeration holes is reduced, and the aeration quantity is increased; 2) the invention combines chemical oxidation and microorganism strengthening technology. The low-concentration oxidant is adopted to pre-oxidize the organic contaminated soil, so that the concentration of the pollutants is reduced, and the toxicity of the soil is reduced; then, two typical microbial remediation technologies of biological enhancement and biological stimulation are used for further degrading organic matters in the soil, so that the capability of degrading the organic matters by microorganisms is improved, and finally, a higher degradation rate is obtained. The method selects a strong oxidant as a pretreatment agent, preferably selects persulfate as a first oxidant, wherein the added catalyst calcium peroxide not only can achieve the purpose of activating persulfate, but also can slowly release oxygen, provide oxygen for the living environment of microorganisms, and enhance the quantity and the degradation rate of the microorganisms. The introduction of calcium peroxide can activate persulfate and simultaneously strengthen microorganisms to degrade organic matters, and hydroxyl and sulfate radicals are generated after the persulfate is activated to accelerate the degradation of the organic matters through an advanced oxidation path; 3) the addition of the exogenous degrading bacteria increases the diversity of microorganisms, can promote the degradation of various pollutants, can effectively reduce or avoid the problem that the pollutants are difficult to degrade due to the single strain, effectively improve the removal rate of organic pollutants, the nitrogen source and the phosphorus source are used as nutrient substances, are favorable for promoting the growth and the reproduction of the microorganisms, can provide a good environment for the microorganisms in the soil, promote the degradation of the microorganisms, and can keep the oxidative repair effect in a system after the repair for a long time, the addition of the nutrient substances and the efficient degrading bacteria after the chemical pre-oxidation can effectively strengthen the microorganisms, improve the environmental adaptability and the competitiveness of the microorganisms, further improve the removal rate of the organic pollutants in the soil, and a new thought is provided for the organic polluted soil repair technology.
Drawings
FIG. 1 is a schematic structural diagram of a coupled biological strengthening repair device after pre-oxidation of organic contaminated soil.
In the figure: 1. soil screening rubbing crusher, 2, the feed inlet, 3, vibrations formula sieve, 4 debris exports, 5 broken gears, 6 debris collection storehouse, 7, the unloading pipe, 8, bioreactor, 9, medicament storage case, 10, the shower nozzle, 11, (mixing) shaft, 12, spiral blade, 13, PVC screen pipe, 14, the screen cut, 15, the aeration pipe, 16, the aeration hole, 17, the discharge gate, 18, air compressor, 19, the medicament mixing box, 20, the medicament stirring rake, 21, flow control valve, 22, the tail gas discharge port, 23, pressure regulating valve, 24, the manometer, 25, the tail gas processing apparatus.
The specific implementation mode is as follows:
for the purpose of enhancing an understanding of the present invention, the following detailed description is given in conjunction with examples.
Example 1: referring to fig. 1, the device for coupling biological strengthening restoration after pre-oxidation of organic contaminated soil comprises a soil screening and crushing device, a medicament mixing device, a spraying device, a bioreactor device, a soil stirring device, an aeration and oxygenation device and a tail gas treatment device 25; the soil screening and crushing device and the medicament mixing device are arranged above the bioreactor device, the spraying device and the soil stirring device are arranged in the bioreactor device, the aeration and oxygenation device is arranged at one side of the bioreactor device, and the right side of the upper wall of the bioreactor is connected with a tail gas treatment device 25; soil screening reducing mechanism includes soil screening rubbing crusher 1, vibrations formula sieve 3 and broken gear 5, wherein is equipped with feed inlet 2 directly over soil screening rubbing crusher 1, and 2 lower extremes of feed inlet have vibrations formula sieve 3, and there is debris export 4 in 3 left sides of vibrations formula sieve, and debris export 4 below is equipped with debris and collects storehouse 6, and 3 below of vibrations formula sieve are equipped with broken gear 5, and unloading pipe 7 of broken gear 5 below is connected with bioreactor device's feed inlet.
The bioreactor device is set as a bioreactor 8, the spraying device is set as a spray head 10,
a medicament storage box 9 and a spray head 10 are arranged on the inner side of the upper wall of the bioreactor 8, a tail gas treatment device 25 is arranged on the right side of the upper wall of the bioreactor 8, a soil stirring device is arranged in the middle of the upper wall, an aeration and oxygenation device is arranged on the inner side of the lower wall, and a discharge hole 17 is arranged on the right side of the lower wall; soil agitating unit includes (mixing) shaft 11 and spiral blade 12, (mixing) shaft and lower (mixing) shaft parallel mount, goes up (mixing) shaft and lower (mixing) shaft blade spiral opposite direction, and soil shifts to the right by the stirring shaft propulsion in last stirring district, enters into stirring district down, shifts to the left by stirring shaft propulsion down again, and soil is at the stirring incasement circulation stirring, and the stirring is more abundant.
The medicament mixing device is arranged as a medicament mixing box 19, the medicament storage box 9 is connected with the medicament mixing box 19 through a medicament feeding pipe, a medicament stirring paddle 20 is arranged in the medicament mixing box 19, and a flow regulating valve 21 is arranged between the medicament mixing box 19 and the medicament storage box 9 for controlling the flow rate of the medicament; the tail gas discharge port 22 is connected to a tail gas treatment device 25 through a pipeline, and a pressure gauge 24 and a pressure regulating valve 23 are arranged between the tail gas discharge port and the tail gas treatment device; the aeration oxygenation device comprises an air compressor 18 and an aeration pipe 15, wherein the aeration pipe 15 is provided with aeration holes 16, the aeration pipe 15 is embedded in a hard polyvinyl chloride screen pipe (PVC screen pipe) 13, and the PVC screen pipe 13 is provided with screen slits 14.
Example 2: referring to fig. 1, a repair method for degrading organic contaminated soil by means of both an oxidation pathway and a biological enhancement pathway, in which a strong oxidant is preferentially added to soil, and then microorganism enhancement is performed, specifically the following steps: the method comprises the steps of screening and crushing soil, then feeding the soil into a bioreactor, selectively adding a chemical oxidant, efficient degrading bacteria, a biological surfactant, nutrient substances and the like according to the type of the organic polluted soil, uniformly mixing the agents, then spraying the mixed agents onto the soil, adding the agents while stirring, aerating and oxygenating at proper time, and collecting and treating tail gas.
The strong oxidizer is selected from one or more of fenton, ozone, peroxy acid, potassium permanganate, hydrogen peroxide and sodium persulfate, and the usage amount of the strong oxidizer in soil is 1-3%. The method is characterized in that a strong oxidant is added into an organic matter polluted site, and the removal of the organic matter is promoted through a physical and chemical action. The oxidation way is carried out by using the oxidation-reduction reaction between a strong oxidant and an organic matter, so that pollutants are converted into stable, low-toxicity or non-toxic substances, the soil pollution concentration is reduced, and the method is favorable for maintaining the living environment required by the degradation of indigenous microorganisms. The microorganism approach is to enhance the decomposition of organic matters by enhancing microorganisms, and the enhancing measures can adopt the modes of adding nutrient substances, biosurfactant, high-efficiency degrading bacteria, aeration, oxygenation and the like, so that the quantity and activity of various microorganisms in soil can be increased, the degradation speed of the organic matters is increased by fully utilizing the co-metabolism, and organic pollutants are converted into simple inorganic matters.
The high-efficiency degrading bacteria are selected from one or more of trichoderma, aspergillus, bacillus, pseudomonas and acinetobacter, and the microbial inoculum accounts for 0.5-2%.
The nutrient substances comprise an N source and a P source, wherein the N source can be one of ammonium sulfate, sodium nitrate and ammonium nitrate; the P source can be one of monopotassium phosphate, sodium monohydrogen phosphate and sodium dihydrogen phosphate, and the content of nutrient substances is 0.001-1%.
The dissolved oxygen can be increased by physical aeration or H addition2O2、CaO2Isooxygen-releasing material, H2O2、CaO2The oxygen release material is 0.05-1%.
The biosurfactant is selected from one of rhamnolipid, fatty peptide, sugar ester, neutral ester and fatty acid, and accounts for 0.01-0.5% of the total weight of the biosurfactant.
The organic matters are benzene series, polycyclic aromatic hydrocarbons, chlorobenzene, phenols, chloralkane and petroleum hydrocarbon organic pollutants, and the concentration of the pollutants is 100-50000 mg/kg.
The application method of the reinforced biological material in repairing the organic polluted soil provided by the invention comprises the following steps: preferentially adding a strong oxidant into the soil, and then adding one or more of nutrient substances, a biosurfactant, degrading bacteria and an oxygen release agent according to the requirements to jointly repair the polluted soil, wherein the specific steps are as follows: after the strong oxidant is added into the agent mixing box 19, a proper amount of water is added, the strong oxidant is stirred by the stirring paddle 20, the agent is changed into a solution state from a powder state, the solution state is conveyed to the agent storage box 9 through the agent adding pipe, the solution is sprayed onto the soil in the bioreactor through the spray head 10, the agent is more easily in full contact reaction with the soil while spraying and stirring, and the internal circulation stirring of the container can be realized by the upper stirring device and the lower stirring device; after stirring, maintaining for 3 days; after the maintenance is finished, adding a biological strengthening or biological stimulating material into the soil, opening the aeration device, providing oxygen for aerobic microorganisms, increasing the efficiency and effectiveness of biodegradation, regularly discharging tail gas, stabilizing the pressure in the container, maintaining for 1-3 months, and adding a proper amount of water into the soil during the maintenance period to enable the water content of the soil to be about 30%.
Example 3:
in the organic contaminated soil of a certain chemical plant of Chongqing, the pollutants are mainly phenanthrene, benzo (alpha) pyrene and nitrobenzene, and the concentrations of the pollutants are respectively 98mg/kg, 76mg/kg and 478 mg/kg. Blank non-additive and strong oxidant addition, biological strengthening-biological stimulation and chemical oxidation-biological stimulation-biological strengthening combined repair experiments are respectively carried out.
Blank no-additive experiment: and adding a proper amount of deionized water into the soil regularly for curing for 3 months.
② experiment by adding strong oxidant: 0.5 percent of hydrogen peroxide and a proper amount of deionized water are added into the soil under the condition of stirring, and the hydrogen peroxide can also slowly release oxygen, thereby providing a good living environment for indigenous aerobic microorganisms and strengthening the capability of the microorganisms for degrading organic matters.
③ Biofortification-biostimulation experiment: adding 0.3% of biosurfactant rhamnolipid into soil, reacting for 1 day, and then adding 2% of high-efficiency degrading bacteria, namely bacillus, 0.08% of sodium nitrate and 0.02% of monopotassium phosphate for carrying out biodegradation experiments.
And fourthly, chemical oxidation-biological stimulation-biological strengthening combined repair experiment: adding 0.3% rhamnolipid into soil, reacting for 1 day, adding 0.5% hydrogen peroxide and a proper amount of deionized water, maintaining for 3 days, and adding 2% phenanthrene high-efficiency degrading bacteria, 0.08% sodium nitrate and 0.02% potassium dihydrogen phosphate.
The 4 experiments were subjected to static culture for 3 months, and the water content of the soil was controlled to about 30% during the culture. After the maintenance is finished, sampling and measuring the concentrations of phenanthrene, benzo (alpha) pyrene and nitrobenzene in the soil. After hydrogen peroxide pre-oxidation, nutrient substances, a surfactant and efficient degrading bacteria are added, the promotion effect on the degradation of phenanthrene, benzo (alpha) pyrene and nitrobenzene in soil is strongest, and the degradation rates are respectively 75%, 78% and 82%. Compared with the oxidation group and the enhanced biological experiment group, the degradation rate is improved by 33 percent to the maximum. After chemical pre-oxidation, nutrients and efficient degrading bacteria are added, so that the degradation of microorganisms on organic matters can be effectively enhanced, and the removal rate of organic pollutants in soil is improved.
Example 4
The experimental soil is taken from soil in a certain petroleum-polluted site, and the oil content reaches 8700 mg/kg. The blank non-additive, chemical oxidation, biological strengthening-biological stimulation and chemical oxidation-biological stimulation-biological strengthening combined system is used for experimental discussion,
blank no-additive experiment: and adding a proper amount of deionized water into the soil regularly for curing for 2 months.
② experiment by adding strong oxidant: 0.5 percent of sodium persulfate and a proper amount of catalyst are added into the soil under the condition of stirring.
③ Biofortification-biostimulation experiment: 1 percent of high-efficiency petroleum hydrocarbon degrading bacteria, 0.05 percent of ammonium nitrate and 0.01 percent of monopotassium phosphate are added into the soil.
And fourthly, chemical oxidation-biological stimulation-biological strengthening combined repair experiment: after 0.5% of sodium persulfate, a proper amount of catalyst and deionized water are added into soil, the mixture is oxidized for 3 days, and then 1% of high-efficiency petroleum hydrocarbon degrading bacteria, 0.05% of ammonium nitrate and 0.01% of monopotassium phosphate are added.
The 4 experiments were subjected to static culture for 2 months, and the water content of the soil was controlled to about 30% during the culture. After the 4 groups of experiments are maintained for a certain time, samples are taken to determine the concentration of petroleum hydrocarbon in the soil. After sodium persulfate is pre-oxidized, nutrients and efficient degrading bacteria are added, so that the effect of degrading petroleum hydrocarbon in soil is strongest and reaches 88%. The concentration of the petroleum pollutants in the soil is reduced from 8700mg/kg to 980mg/kg, and test results show that the removal capacity of the three modes for the oil-containing pollutants in the soil is sequenced as follows: the combined system of chemical oxidation-biostimulation-bioaugmentation > chemical oxidation. Compared with the oxidation group and the enhanced biological experiment group, the degradation rate is respectively improved by 14 percent and 23 percent. After chemical pre-oxidation, nutrient substances and efficient degrading bacteria are added, so that the degradation of the petroleum hydrocarbon by the microorganisms can be effectively enhanced.
The petroleum hydrocarbon pollutants can provide enough carbon sources for the petroleum hydrocarbon degrading bacteria under natural conditions, but cannot provide enough nutrient elements such as nitrogen, phosphorus and the like for the growth of microorganisms. Proper amount of phosphate and nitrate are added in the degradation process of the petroleum hydrocarbon, so that the growth and activity of microorganisms can be effectively promoted, and the microbial degradation speed and the degradation degree of the petroleum hydrocarbon can be effectively improved. Because most of petroleum hydrocarbon is degraded aerobically, the added hydrogen peroxide in the experiment can not only play a role of oxidation, but also can increase the content of dissolved oxygen, and directly enhance the degradation efficiency of microorganisms.
Application example 1:
a device and a method for coupling biological enhanced remediation after pre-oxidation of organic contaminated soil are realized based on a processing device shown in figure 1. The processing device includes: soil screening reducing mechanism, medicament mix with spray set, biological reaction unit, soil agitating unit, aeration oxygenation device and tail gas processing apparatus.
The specific implementation steps are as follows:
in the organic contaminated soil of a certain chemical plant of Chongqing, the pollutants are mainly phenanthrene, benzo (alpha) pyrene and nitrobenzene, and the concentrations of the pollutants are respectively 98mg/kg, 76mg/kg and 478 mg/kg.
Soil enters the screening crusher through the feeding hole, sundries such as large gravels, construction waste and the like in the soil are removed by the vibration type sieve plate, and the soil enters the bioreactor through the discharging pipe after being crushed by the crushing gear. Adding 0.3% of biosurfactant rhamnolipid into a reagent mixing box, reacting for 1 day, adding 0.5% of hydrogen peroxide, adding water, stirring uniformly, spraying into soil, adding medicine while stirring to fully and uniformly mix the soil and the reagent, adding a proper amount of water (the soil moisture content is 30%), and maintaining for 3 days. Adding 2% of efficient degrading bacteria, namely bacillus, 0.08% of sodium nitrate and 0.02% of potassium dihydrogen phosphate, mixing and stirring uniformly, spraying the mixture on soil, adding medicine and stirring, properly increasing the oxygen amount in a bioreactor, improving the environmental adaptability and the degrading capability of microorganisms, further improving the removal rate of organic pollutants in the soil, and enabling tail gas to enter a tail gas treatment device so as to ensure stable air pressure in the bioreactor. The maintenance period is 3 months.
After 3 months of biodegradation, the concentrations of organic pollutants phenanthrene, benzo (alpha) pyrene and nitrobenzene in the soil are reduced to 0.6mg/kg, 0.47mg/kg and 4.5mg/kg, and the degradation rate is over 99 percent. The remediation method can effectively degrade organic matters by means of the device, so as to achieve the purpose of remediation of the polluted soil.
Compared with the embodiment 3, the method for coupling biological enhanced remediation after pre-oxidation of the organic contaminated soil has the advantages that the degradation effect of the organic contaminants is greatly improved by 24% at most by using the device (shown in figure 1). The device can effectively treat the organic contaminated soil by applying the method.
Application example 2:
a device and a method for coupling biological enhanced remediation after pre-oxidation of organic contaminated soil are realized based on a processing device shown in figure 1. The processing device includes: soil screening reducing mechanism, medicament mix with spray set, biological reaction unit, soil agitating unit, aeration oxygenation device and tail gas processing apparatus.
The specific implementation steps are as follows:
the experimental soil is taken from soil in a certain petroleum-polluted site, and the concentration of the petroleum pollutants is 8700 mg/kg.
Soil enters the screening crusher through the feeding hole, sundries such as large gravels, construction waste and the like in the soil are removed by the vibration type sieve plate, and the soil enters the bioreactor through the discharging pipe after being crushed by the crushing gear. Adding 0.5% of sodium persulfate and a proper amount of catalyst into a chemical mixing box, adding water, uniformly stirring, spraying the mixture into soil, adding chemicals while stirring to fully and uniformly mix the soil and the chemical, and adding a proper amount of water (the soil moisture content is 30%) to maintain for 3 days. Then 1% of efficient petroleum hydrocarbon degrading bacteria, 0.05% of ammonium nitrate and 0.01% of potassium dihydrogen phosphate are added into a reagent mixing box, the mixture is uniformly mixed and stirred and then sprayed on soil, the mixture is stirred while adding chemicals, the oxygen amount in a bioreactor is increased in a proper amount, the environmental adaptability and the degradation capability of microorganisms are improved, the removal rate of organic pollutants in the soil is further improved, and tail gas enters a tail gas treatment device to ensure stable air pressure in the bioreactor. The maintenance period is 2 months.
After the maintenance time is over, the concentration of the petroleum pollutants in the soil is reduced from 8700mg/kg to 270mg/kg, and the degradation rate reaches 97%. Test results show that the petroleum hydrocarbon pollutants can be efficiently degraded by adding the surfactant, the nutrient substances and the efficient degrading bacteria after the chemical pre-oxidation. The petroleum hydrocarbon pollutants can provide enough carbon sources for the petroleum hydrocarbon degrading bacteria under natural conditions, but cannot provide enough nutrient elements such as nitrogen, phosphorus and the like for the growth of microorganisms. Proper amount of phosphate and nitrate are added in the degradation process of the petroleum hydrocarbon, so that the growth and activity of microorganisms can be effectively promoted, and the microbial degradation speed and the degradation degree of the petroleum hydrocarbon can be effectively improved. As most of petroleum hydrocarbon is aerobically degraded, the dissolved oxygen content is increased by physical measures, the activity of microorganisms in the environment is effectively improved, and the microbial degradation speed and degree of the petroleum hydrocarbon are improved.
Compared with the embodiment 4, the degradation rate of the petroleum pollutants can be improved by 9% by using the device (figure 1) in the method for coupling biological enhanced remediation after the pre-oxidation of the organic polluted soil. The device can improve the degradation capability of the petroleum hydrocarbon polluted soil by applying the method.
It should be noted that the above-mentioned embodiments are not intended to limit the scope of the present invention, and all equivalent modifications and substitutions based on the above-mentioned technical solutions are within the scope of the present invention as defined in the claims.
Claims (10)
1. The device for coupling and biologically strengthening the restoration of the pre-oxidized organic contaminated soil is characterized by comprising a soil screening and crushing device, a medicament mixing device, a spraying device, a bioreactor device, a soil stirring device, an aeration and oxygenation device and a tail gas treatment device (25); soil screening reducing mechanism, medicament mixing arrangement set up in the top of bioreactor device, and spray set and soil agitating unit set up inside the bioreactor device, and aeration oxygenation device sets up in one side of bioreactor device, and the upper wall right side of bioreactor is connected with tail gas treatment device (25).
2. The device for coupled biological strengthening and repairing after preoxidation of organic contaminated soil according to claim 1, wherein the soil screening and crushing device comprises a soil screening and crushing machine (1), a vibrating sieve plate (3) and a crushing gear (5), wherein a feeding hole (2) is formed right above the soil screening and crushing machine (1), the vibrating sieve plate (3) is arranged at the lower end of the feeding hole (2), a sundry outlet (4) is formed in the left side of the vibrating sieve plate (3), a sundry collecting bin (6) is arranged below the sundry outlet (4), the crushing gear (5) is arranged below the vibrating sieve plate (3), and a discharging pipe (7) below the crushing gear (5) is connected with the feeding hole of the bioreactor device.
3. The coupled biological reinforced restoration device after the pre-oxidation of the organic contaminated soil according to claim 1,
the bioreactor device is set as a bioreactor (8), the spraying device is set as a spray head (10), and the flow is controlled by a regulating valve (21); a medicament storage box (9) and a spray nozzle (10) are arranged on the inner side of the upper wall of the bioreactor (8), a tail gas treatment device (25) is arranged on the right side of the upper wall of the bioreactor (8), a soil stirring device is arranged in the middle of the upper wall, an aeration and oxygenation device is arranged on the inner side of the lower wall, and a discharge hole (17) is arranged on the right side of the lower wall; soil agitating unit includes (mixing) shaft (11) and spiral blade (12), goes up (mixing) shaft and lower (mixing) shaft parallel mount, goes up (mixing) shaft and lower (mixing) shaft blade spiral opposite direction, and soil moves to the right by the stirring shaft propulsion in last stirring district, enters into lower stirring district, moves to the left by stirring shaft propulsion down again, and soil is at the stirring tank inner loop stirring, and the stirring is more abundant.
4. The coupled biological reinforced restoration device after the organic contaminated soil is pre-oxidized according to claim 3,
the drug mixing device is arranged as a drug mixing box (19), the drug storage box (9) is connected with the drug mixing box (19) through a drug adding pipe, a drug stirring paddle (20) is arranged in the drug mixing box (19), and a flow regulating valve (21) is arranged between the drug mixing box (19) and the drug storage box (9) to control the flow rate of drugs; the tail gas discharge port (22) is connected to a tail gas treatment device (25) through a pipeline, and a pressure gauge (24) and a pressure regulating valve (23) are arranged between the tail gas discharge port and the tail gas treatment device; the tail gas device is internally provided with active carbon for tail gas adsorption treatment; the aeration oxygenation device comprises an air compressor (18) and an aeration pipe (15), wherein the aeration pipe (15) is provided with aeration holes (16), the aeration pipe (15) is nested in a hard polyvinyl chloride sieve pipe (PVC sieve pipe) (13), and sieve slits (14) are formed in the PVC sieve pipe (13).
5. The method for repairing organic contaminated soil by coupling after pre-oxidation by adopting the device of any one of claims 1 to 4 is characterized in that the method is a repairing method for degrading organic contamination in soil by means of an oxidation path and a biological strengthening path at the same time, firstly a strong oxidant is preferentially added into the soil, and then microorganism strengthening is carried out, and the method specifically comprises the following steps: the method comprises the steps of screening and crushing soil, then feeding the soil into a bioreactor, selectively adding a chemical oxidant, efficient degrading bacteria, a biological surfactant and nutrient substances according to the type of the organic polluted soil, spraying the mixed agent onto the soil after the mixed agent is uniformly stirred, adding the agent while stirring, aerating and oxygenating at proper time, and collecting and treating tail gas.
6. The method for biologically enhanced restoration according to claim 5, wherein the strong oxidizer is selected from one or more of Fenton, ozone, peroxy acid, potassium permanganate, hydrogen peroxide and sodium persulfate, and the amount of the strong oxidizer used in the soil is 1% to 3%.
7. The method of claim 5, wherein the method of enhancing microorganisms in soil after pre-oxidation comprises both bioaugmentation and biostimulation; wherein the biological strengthening is adding exogenous high-efficiency degrading bacteria or screening and domesticating high-efficiency strains from polluted soil, and the biological stimulation is adding nutrient substances and surfactants and increasing dissolved oxygen.
8. The method for biologically enhanced restoration according to claim 5, wherein the highly effective degrading bacteria is one or more selected from Trichoderma, Aspergillus, Bacillus, Pseudomonas and Acinetobacter, and the microbial inoculum accounts for 0.5-2%; the nutrient substances comprise an N source and a P source, wherein the N source can be one of ammonium sulfate, sodium nitrate and ammonium nitrate; the P source can be one of monopotassium phosphate, sodium monohydrogen phosphate and sodium dihydrogen phosphate, and the content of nutrient substances is 0.001-1%; the increase of dissolved oxygen adopts physical aeration or H addition2O2、CaO2Oxygen-releasing material, H2O2、CaO2The oxygen release material is 0.05-1%.
9. The bioaugmentation restoration method according to claim 7, wherein the surfactant is selected from biosurfactant, one of rhamnolipid, fatty peptide, sugar ester, neutral ester and fatty acid, and the biosurfactant accounts for 0.01-0.5%; the organic matters are benzene series, polycyclic aromatic hydrocarbons, chlorobenzene, phenols, chloralkane and petroleum hydrocarbon organic pollutants, and the concentration of the pollutants is 100-50000 mg/kg.
10. The biological enhanced restoration method according to claim 5, wherein after the strong oxidant is added into the agent mixing box (19), a proper amount of water is added, the agent is stirred by the stirring paddle (20) to be changed from a powder state into a solution state, then the solution is conveyed to the agent storage box (9) through the agent adding pipe, and then the solution is sprayed onto the soil in the bioreactor by the spray head (10), the agent is more easily contacted and reacted with the soil by stirring while spraying, and the internal circulation stirring of the container can be realized by the upper and lower stirring devices; after stirring, maintaining for 3 days; after the maintenance is finished, adding a biological strengthening or biological stimulating material into the soil, opening the aeration device, providing oxygen for aerobic microorganisms, increasing the efficiency and effectiveness of biodegradation, regularly discharging tail gas, stabilizing the pressure in the container, maintaining for 1-3 months, and adding a proper amount of water into the soil during the maintenance period to enable the water content of the soil to be about 30%.
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