CN117225879A - Medicament for rapidly degrading explosive containing in polluted soil and application method thereof - Google Patents

Abstract

The invention belongs to the technical field of soil environmental pollution restoration, and particularly relates to a medicament for biodegrading explosive pollutants in soil and a use method thereof. The medicament comprises a medicament A added before the construction of the biological pile and a medicament B used in the aerobic operation process of the biological pile; the medicament A comprises the following raw materials in parts by mass: 15-25 parts of solid nutrient source, 2-6 parts of pore regulator, 0.10 part of reducing agent, 0.2-1 part of first liquid nutrient source and 0.05 part of first surfactant; the solid nutrient source is any one or a mixture of more than two of domestic sewage pool sludge or pig manure, cow manure, chicken manure, sheep manure and other livestock manure in any proportion; the pore regulator comprises wheat bran and vegetation straw; the first liquid nutrient source comprises a sugar source, fat, a nitrogen source, and an inorganic salt; the first surfactant is an anionic surfactant. The agent provided by the invention can enable the TNT removal rate to be more than 80%, RDX to be more than 60% and HMX to be more than 75%.

Description

An agent for rapidly biodegrading energetic explosives in contaminated soil and its use method

Technical field

The invention belongs to the technical field of soil environmental pollution remediation, and specifically relates to a medicament for rapidly biodegrading energetic explosives in contaminated soil and a method of use.

Background technique

The energetic compound TNT has become a widely used explosive for military and civilian use in various countries due to its high detonation velocity, high heat of explosion and good chemical stability. However, during the production, use and military activities of TNT, a large amount of TNT explosive residues entered water bodies or soil, causing serious environmental pollution. Military agencies in the United States, Canada, and many in Europe and Asia conduct sources of energetic compound contamination, assess the impact of military activities on soil, groundwater, and surface water quality, and develop strategies to remediate and remediate contaminated sites. The state of North Carolina in the United States stipulates that the TNT content in residential soil must not exceed 7.2mg/L. Therefore, the remediation and treatment of soil contaminated by energetic explosives is an urgent problem that needs to be solved in my country.

There are many studies on the remediation of organically contaminated soil by microbial technology, but there are few studies on the biodegradation of soil contaminated by energetic organic compounds. Microbial remediation technology has low application cost, no secondary pollution to the environment, simple operation, and high technical application value. Microorganisms may degrade energetic compounds in two ways: one is to use energetic compounds as the only carbon source and energy to degrade or mineralize them; the other is that certain organic matter cannot be used as the only carbon source and energy source for microorganisms. Energy requires the addition of co-metabolic substrates to degrade energetic compounds in the form of co-metabolism. In addition, exogenous bacteria can be added to degrade energetic compounds under artificially optimized conditions. Microbial remediation technology is economical, environmentally friendly, and has great potential to degrade organic pollutants. It has a unique role and role in the remediation and treatment of soil contaminated by energetic compounds. significance.

Invention patent 202111629257. Compound-enriched degrading plants and TNT energetic compound-enriched degrading plants are planted for symbiotic restoration treatment. After 90 to 120 days of treatment, the TNT purification rate in soil contaminated by energetic compounds is ≥90%.

It is crucial to carry out research on the formulation of co-metabolite substrate materials and their use methods to improve the microbial remediation intensity of soil contaminated by energetic explosives. It can be used for microbial remediation of soil contaminated by energetic compounds that exist in ammunition destruction, military training, and military industrial enterprise factories. Provide a new way.

Contents of the invention

The technical problem to be solved by this invention is: specific microorganisms in traditional bioremediation technology only degrade specific compound types, and site conditions and environmental factors have a greater impact on the efficiency of microbial remediation and the remediation time is long.

In a first aspect, the present invention provides a medicament for biodegrading explosive pollutants in soil. The medicament includes a medicament A added before the construction of the biopile and a medicament B used during the aerobic operation of the biopile; the medicament A It includes the following parts by mass of raw materials: 15 to 25 parts of solid nutrient source, 2 to 6 parts of pore regulator, 0.10 part of reducing agent, 0.2 to 1 part of first liquid nutrient source, 0.05 part of first surfactant; the solid The nutrient source is any one or a mixture of two or more in any proportion of domestic sewage tank sludge or pig manure, cow manure, chicken manure, sheep manure and other livestock and poultry manure; the pore regulator includes wheat bran and vegetation straw; the The first liquid nutrient source includes sugar source, fat, nitrogen source and inorganic salt; the first surfactant is an anionic surfactant.

The medicament B is a solution, and the solute includes a second liquid nutrient source and a second surfactant. The total concentration of the second liquid nutrient source and the second surfactant is 0.1 to 0.2%. The second liquid nutrient source and the second surfactant are The mass ratio of the two surfactants is 7:3 to 5:5; the second liquid nutrient source includes sugar source, nitrogen source and inorganic salt.

Preferably, the first liquid nutrient source includes 5% to 80% molasses, 1% to 2% KH ₂ PO ₄ , 0.1% to 10% urea, 10% to 50% sodium sulfide, and 10% to 15% sulfurous acid. Iron and 10% to 20% soybean oil, the sum of the mass percentages of the above components is 100%.

Preferably, the second liquid nutrient source includes 30% to 40% glucose, 8% to 12% superphosphate, 2% to 4% urea, 2% to 4% potassium chloride, and 30% to 40% liquid organic food. Fertilizer, 16% to 20% sodium thiosulfate and 16% to 20% iron sulfite, the sum of the mass percentages of the above components is 100%.

Preferably, the second surfactant includes 16% to 20% butyl acetate, 2% to 4% lauryl phosphate, 30% to 40% rhamnolipid, and 16% to 20% dodecyl sulfate. Sodium and 6% to 10% anionic surfactant, the sum of the mass percentages of the above components is 100%.

Further, the concentration of the agent B solution is 0.116%, and the solute composition is glucose 17.24%, superphosphate 4.31%, urea 1.72%, potassium chloride 1.72%, supernatant after filtration of crushed microbial organic fertilizer 17.24%, Sodium thiosulfate 8.62%, iron sulfite 8.62%, butyl acetate 8.62%, lauryl phosphate 1.72%, rhamnolipid 17.24%, sodium lauryl sulfate 8.62%, anionic surfactant 4.31%.

Preferably, the reducing agent is iron powder with a diameter of no more than 100 μm.

Preferably, in the pore regulator, wheat bran accounts for 60%-80% of the total mass of the pore regulator; vegetation straw accounts for 20%-40% of the total mass of the pore regulator, and the length is between 2-3cm.

In a second aspect, the present invention provides a method for using the agent described in the first aspect for bioremediation of explosive-contaminated soil: the agent A and the explosive-contaminated soil are mixed and stirred for anaerobic remediation. No more than 20 parts by mass of contaminated soil shall be mixed; after anaerobic remediation is completed, aerobic remediation shall be carried out, and Agent B shall be added during aerobic remediation for remediation.

Preferably, the method also includes pretreatment of contaminated soil and construction of biological piles; pretreatment of contaminated soil includes: using screening equipment to remove non-soil materials such as stones and construction waste, and using crushing equipment to crush large-size soil blocks. , making the soil uniform and free of non-soil materials such as stones and construction waste; using lime to increase soil pH, or using sulfur, ammonium sulfate, aluminum sulfate, and aluminum sulfite to reduce soil pH to a pH between 6 and 9 between;

The construction of bio-pile body includes: after mixing the contaminated soil and chemicals evenly, the construction of bio-pile body is carried out. A drip irrigation pipe network system is installed on the top of the biopile, and the biopile is wrapped and covered to achieve the sealing effect of the biopile; the biopile is equipped with a ventilation pipe network, external air extraction equipment and waste gas treatment devices to ensure the safety of the biopile during aerobic operation. ventilation.

Further, after the construction of the biological pile is completed, the operation mode is anaerobic and aerobic intermittent operation;

According to the pattern of first anaerobic and then aerobic, and the repeated cycle operation is anaerobic:aerobic=10d:5d. During anaerobic operation, keep the pile closed and do not ventilate or add Agent B; during aerobic operation, open the ventilation valve and air extraction equipment to ventilate the pile, increase the oxygen content in the soil, and provide intermittent aeration to microorganisms. environment, and adding agent B during the aerobic stage to ensure water and nutrient sources during operation; through aerobic and anaerobic intermittent operation, microorganisms are strengthened to degrade energetic compound pollutants in the soil.

Beneficial effects achieved by the present invention: The agent and its use method proposed by the present invention can effectively reduce the concentration of pollutants in the contaminated original soil including energetic materials such as TNT, RDX and HMX. After 30 days of biopile operation, the energetic compounds The removal rate of TNT can reach more than 80%, the removal rate of RDX can reach more than 60%, and the removal rate of HMX can reach more than 75%.

Detailed ways

The present invention will be further described below in conjunction with examples.

The experimental methods used in the following examples are conventional methods unless otherwise specified.

Materials, reagents, etc. used in the following examples can all be obtained from commercial sources unless otherwise specified.

The following examples further illustrate the present invention so that those skilled in the art can better understand and implement the present invention, but the examples are not intended to limit the present invention.

Example 1

Select the soil contaminated by energetic compounds from the explosive-contaminated site to implement the chemical formula. The contaminated soil will be pre-treated and mixed evenly with the chemical, and the bio-pile system will be constructed. The biopile agent contains solid nutrient sources: 12 parts of sludge, 5 parts of pig manure, and 1 part of cow manure; pore regulator: 1 part of crushed straw, 2.6 parts of wheat bran; reducing agent: 0.1 part of reduced iron powder; liquid nutrient source a: 0.02 parts of molasses, 0.005 parts of potassium dihydrogen phosphate, 0.02 parts of urea, 0.1 parts of sodium sulfide, 0.1 parts of iron sulfite, 0.005 parts of soybean oil; surfactant a: 0.05 parts of anionic surfactant. In Example 1, a total of three bioreactors were constructed and operated.

After the reactor is built, it is first operated under anoxic conditions for 10 days, and then under aerobic conditions for 5 days. One cycle lasts 15 days. During the anoxic operation, the reactor body needs to remain sealed; during the aerobic operation, the exhaust equipment operates in a cycle of starting for 30 minutes and then shutting down for 30 minutes. The ventilation volume is: 100m 3 /h on days 1-2, and 100m ³ /h on days 3-4. 200m ³ /h, 100m ³ /h on the 5th day. At the same time, agent B needs to be sprayed into the pile through the drip irrigation pipe network to adjust the internal environment of the pile. During the aerobic operation, the daily dosage of Agent B is: 0.2m ³ per day on the 1st to 2nd days, 0.3m ³ per day on the 3rd to 4th days, and 0.5m ³ on the 5th day.

After testing, the TNT concentration in the selected contaminated original soil was approximately 133.02 mg/kg, the RDX concentration was approximately 45.91 mg/kg, and the HMX concentration was approximately 9.18 mg/kg. After 15 days of biopile operation, the removal rate of the energetic compound TNT of concern was approximately 96.56%, the removal rate of RDX was approximately 93.84%, and the removal rate of HMX was approximately 96.80%. After running for 2 cycles for a total of 30 days, the removal rate of the energetic compound TNT is about 97.48%, the removal rate of RDX is about 93.04%, and the removal rate of HMX is about 92.97%.

Example 2

Select the soil contaminated by energetic compounds from the explosive-contaminated site to implement the chemical formula. The contaminated soil will be pre-treated and mixed evenly with the chemical, and the bio-pile system will be constructed. The biopile agent contains solid nutrient sources: 17 parts of pig manure, 0.5 parts of cow manure; pore regulator: 1 part of crushed straw, 2.6 parts of wheat bran; reducing agent: 0.1 parts of reduced iron powder; liquid nutrient source a: 0.6 parts of molasses , 0.005 parts of potassium dihydrogen phosphate, 0.001 parts of urea, 0.1 parts of sodium sulfide, 0.1 parts of iron sulfite, 0.005 parts of soybean oil; surfactant a: 0.05 parts of anionic surfactant. In Example 2, a total of three bioreactors were constructed and operated.

After the reactor is built, it is first operated under anoxic conditions for 10 days, and then under aerobic conditions for 5 days. One cycle lasts 15 days. During the anoxic operation, the reactor body needs to remain sealed; during the aerobic operation, the exhaust equipment operates in a cycle of starting for 30 minutes and then shutting down for 30 minutes. The ventilation volume is: 100m 3 /h on days 1-2, and 100m ³ /h on days 3-4. 200m ³ /h, 100m ³ /h on the 5th day. At the same time, agent B needs to be sprayed into the pile through the drip irrigation pipe network to adjust the internal environment of the pile. During the aerobic operation, the daily dosage of Agent B is: 0.2m ³ per day on the 1st to 2nd days, 0.3m ³ per day on the 3rd to 4th days, and 0.5m ³ on the 5th day.

After testing, the TNT concentration in the selected contaminated original soil was approximately 55.85 mg/kg, the RDX concentration was approximately 49.41 mg/kg, and the HMX concentration was approximately 1.36 mg/kg. After 15 days of biopile operation, the removal rate of the energetic compound TNT of concern was approximately 83.91%, the removal rate of RDX was approximately 64.49%, and the removal rate of HMX was approximately 62.82%. After running for 2 cycles for a total of 30 days, the removal rate of the energetic compound TNT is about 98.72%, the removal rate of RDX is about 88.35%, and the removal rate of HMX is about 77.93%.

Based on the content of energetic pollutants before and after the addition of the biocomposite agent during the operation of the embodiment, as well as the time of the repair operation, it can be seen that the agent and its use method of the present invention have the characteristics of rapid biodegradation of energetic pollutants.

Claims (10)

1. The preparation method is characterized in that the preparation method comprises the steps of adding a preparation A before the construction of a biological pile and a preparation B used in the anaerobic and aerobic intermittent operation process of the biological pile; the medicament A comprises the following raw materials in parts by mass: 15-25 parts of solid nutrient source, 2-6 parts of pore regulator, 0.10 part of reducing agent, 0.2-1 part of first liquid nutrient source and 0.05 part of first surfactant; the solid nutrient source is any one or a mixture of more than two of domestic sewage pool sludge or livestock manure in any proportion; the pore regulator comprises wheat bran and vegetation straw; the first liquid nutrient source comprises a sugar source, fat, a nitrogen source, and an inorganic salt; the first surfactant is an anionic surfactant;

the medicament B is a solution, the solute comprises a second liquid nutrition source and a second surfactant, the total concentration of the second liquid nutrition source and the second surfactant is 0.1-0.2%, and the mass ratio of the second liquid nutrition source to the second surfactant is 7:3-5:5; the second liquid nutrient source includes a sugar source, a nitrogen source, and an inorganic salt.

2. The agent for the rapid biodegradation of an explosive-containing chemical in contaminated soil as claimed in claim 1, wherein said first liquid nutrient source comprises 5% to 80% molasses, 1% to 2% kh ₂ PO ₄ 0.1 to 10 percent of urea, 10 to 50 percent of sodium sulfide, 10 to 15 percent of ferrous sulfite and 10 to 20 percent of soybean oil, wherein the sum of the mass percentages of the components is 100 percent.

3. The agent for the rapid biodegradation of an explosive-containing chemical in contaminated soil according to claim 1, wherein the second liquid nutrient source comprises 30% -40% glucose, 8% -12% superphosphate, 2% -4% urea, 2% -4% potassium chloride, 30% -40% liquid organic fertilizer, 16% -20% sodium thiosulfate and 16% -20% ferric sulfite, and the sum of the above components is 100% by mass.

4. The agent for the rapid biodegradation of an explosive-containing chemical in contaminated soil according to claim 1, wherein the second surfactant comprises 16% to 20% butyl acetate, 2% to 4% lauryl phosphate, 30% to 40% rhamnolipid, 16% to 20% sodium dodecyl sulfate and 6% to 10% anionic surfactant, the sum of the above components being 100% by mass.

5. The agent for the rapid biodegradation of an explosive-containing chemical in contaminated soil according to claim 3 or 4, wherein the concentration of the agent B solution is 0.116%, and the solute components are 17.24% glucose, 4.31% superphosphate, 1.72% urea, 1.72% potassium chloride, 17.24% liquid organic fertilizer, 8.62% sodium thiosulfate, 8.62% ferric sulfite, 8.62% butyl acetate, 1.72% lauryl phosphate, 17.24% rhamnolipid, 8.62% sodium dodecyl sulfate, and 4.31% anionic surfactant.

6. The agent for the rapid degradation of an explosive-containing chemical in contaminated soil according to claim 1, wherein the reducing agent is iron powder, and the diameter is not more than 100 μm.

7. The agent for the rapid biodegradation of explosives in contaminated soil according to claim 1, wherein wheat bran in the pore regulator accounts for 60% -80% of the total mass of the pore regulator; the vegetation straw accounts for 20-40% of the total mass of the pore regulator, and the length is between 2 cm and 3 cm.

8. A method of using the agent of claim 1 for bioremediation of explosive-contaminated soil, comprising the steps of: mixing and stirring the agent A and explosive-polluted soil for anaerobic remediation, wherein each 1 part by mass of the agent A is mixed with not more than 20 parts by mass of the polluted soil; after the anaerobic repair is finished, performing aerobic repair, and adding a reagent B for repair during the aerobic repair.

9. The method of use of claim 8, further comprising contaminated soil pretreatment and bio-stack construction; the pretreatment of the polluted soil comprises the following steps: removing non-soil substances such as stones and construction waste by adopting screening equipment, and crushing large-particle-size soil blocks by adopting crushing equipment so that the soil is uniform and the non-soil substances such as stones and construction waste are not contained; lime is adopted to increase the pH value of the soil, or sulfur, ammonium sulfate, aluminum sulfate and aluminum sulfite are adopted to reduce the pH value of the soil, so that the pH value is between 6 and 9;

the construction of the biological pile body comprises the following steps: after the contaminated soil and the medicament are uniformly mixed, the biological pile body is built; a drip irrigation pipe network system is arranged at the top of the biological pile and wraps and covers the biological pile body so as to realize the sealing effect of the pile body; the pile body is provided with a ventilation pipe network, and is externally connected with an air extraction device and a waste gas treatment device, so that ventilation of the pile body during aerobic operation is ensured.

10. The method of claim 9, wherein the operation mode is an anaerobic-aerobic intermittent operation mode after the completion of the construction of the biological reactor;

according to the mode of anaerobic and then aerobic, and anaerobic: aerobic = 10d:5d, repeatedly and circularly running in a mode; when in anaerobic operation, the pile body is kept airtight, and ventilation or addition of the medicament B is not carried out; when in aerobic operation, the ventilation valve and the air extraction equipment are opened to ventilate the pile body, so that the oxygen content in the soil is improved, an intermittent aerobic environment is provided for microorganisms, and the agent B is added in an aerobic stage, so that the moisture and nutrient sources in the operation period are ensured.