CN110436728B - Method for in-situ stabilization repair of lead-polluted bottom mud by iron-based material and microorganisms - Google Patents
Method for in-situ stabilization repair of lead-polluted bottom mud by iron-based material and microorganisms Download PDFInfo
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- CN110436728B CN110436728B CN201910876916.6A CN201910876916A CN110436728B CN 110436728 B CN110436728 B CN 110436728B CN 201910876916 A CN201910876916 A CN 201910876916A CN 110436728 B CN110436728 B CN 110436728B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/008—Sludge treatment by fixation or solidification
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/02—Biological treatment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
Abstract
The invention discloses a method and a reagent for repairing lead polluted bottom mud by iron-based material and microorganism in-situ stabilization. The reagent comprises an iron-based material and sulfate reducing bacteria liquid, wherein the iron-based material is obtained by reacting iron-containing silicate minerals and oxalic acid in an aqueous medium at the temperature of 55-120 ℃. The reagent is added into the lead-polluted bottom mud, the immobilization efficiency of lead is more than 97%, the in-situ mode is adopted for repair, no additional device is needed, the lead stabilization efficiency is high, the cost is low, and no secondary pollution is caused.
Description
Technical Field
The invention relates to a lead (II) polluted bottom sediment remediation reagent, in particular to a reagent for remedying lead (II) polluted bottom sediment by an iron-based material and microorganisms, a reagent for remedying lead (II) polluted bottom sediment and a method, and belongs to the technical field of ecological remediation of heavy metal polluted soil.
Background
With the rapid development of domestic economy and society, the problem of heavy metal pollution caused by the heavy metal pollution has attracted strong attention of all social circles. Lead is a biotoxic heavy metal with wide distribution and strong accumulation capacity in heavy metal pollution, the lead pollution mainly comes from mining, metal smelting and processing, IT manufacturing, domestic sewage discharge, use and combustion of lead-containing gasoline and the like, the lead discharge amount is about 6 million tons every year in China, and lead deposition in bottom mud is easily caused by discharge of lead-containing wastewater.
Lead in the bottom mud is contacted with water flow for a long time, so that the chemical state of the lead is unstable, and the lead is often used as a main pollution source for rivers and water sources. Lead has strong accumulation, and through the enrichment of food chain, lead in human body can be combined with various enzymes to interfere with various physiological activities of organism, seriously damage nerve, digestion, immunity and reproductive system of human, threaten human health, and low dosage of lead can affect the development of central nerve and skeleton of human. Therefore, the problem of lead contamination in the bottom sludge and its repair have become one of the issues of great concern.
The repairing mode of the lead polluted bottom mud mainly comprises ectopic repairing and in-situ repairing. The ectopic remediation is only suitable for the small-area and sudden heavily polluted soil due to the characteristics of high cost, large engineering quantity and the like, and the in-situ remediation is an economic, efficient, reasonable and sustainable treatment technology. The in-situ repair method mainly comprises physical repair, biological repair, chemical repair and the like.
The chemical remediation method reduces the biological effectiveness of heavy metals by selecting a proper soil conditioner to adsorb, oxidize, reduce and precipitate the heavy metals, and becomes a research hotspot of remediation of the polluted soil in recent years due to the characteristics of convenient operation and rapid treatment, but secondary pollution is easily caused by the addition of chemical reagents. Therefore, the key to the chemical remediation method is to find a chemical agent or material that is low in cost, simple to prepare, and environmentally friendly.
The microbial remediation is one of the main bioremediation methods, and is a method for fixing/stabilizing and remedying lead polluted bottom mud by adding microorganisms into a polluted environment so as to convert heavy metals from a free state to a combined state. The microbial remediation method has the advantages of low treatment cost, small disturbance to the surrounding environment, no secondary pollution, less suitable microbial resources and less obvious remediation effect. The sulfate reducing bacteria is a strict anaerobic microorganism which utilizes sulfate to carry out growth and metabolism, and the generated sulfide can fix various heavy metal cations, so the sulfate reducing bacteria is a good microbial inoculum for in-situ immobilization and restoration of heavy metal polluted bottom mud.
On the other hand, because the environmental conditions of the bottom mud are complex, such as low oxygen content, large mobility, many interference factors and the like, a single repair method cannot achieve a good repair effect, and therefore, two or more methods need to be combined to perform curing/stabilizing repair on the lead-polluted bottom mud, so that good repair indexes can be achieved, and optimal allocation of resources can also be achieved.
Disclosure of Invention
Aiming at the defects of the existing related repair technology of the lead-polluted river sediment, the first purpose of the invention is to provide a reagent for realizing the efficient repair of lead in the lead-polluted river sediment by coupling an iron-based material with microorganisms, the reagent for repairing the bottom sediment is low in raw material cost and easy to obtain, the stability rate of lead in the lead-polluted bottom sediment is more than 97%, and the reagent is particularly suitable for the continuous and stable repair of the lead-polluted river sediment.
The second purpose of the invention is to provide a method for repairing lead-polluted bottom sediment by iron-based material in cooperation with microorganism in-situ stabilization, wherein the stabilizing rate of lead in the lead-polluted bottom sediment is more than 97% by using the iron-based material in cooperation with a microorganism lead-polluted bottom sediment stabilizing agent.
In order to realize the technical purpose, the invention provides a reagent for in-situ stabilization repair of lead polluted bottom mud by an iron-based material in cooperation with microorganisms, which comprises the iron-based material and sulfate reducing bacteria liquid; the iron-based material is obtained by reacting iron-containing silicate minerals and oxalic acid in an aqueous medium at the temperature of 55-120 ℃.
Preferably, the iron-containing silicate mineral comprises at least one of biotite, iron aluminum garnet, crossed stones, fayalite, glauberite, trapezite, neon, calcium iron pyroxene, magnesium iron amphibole and amphibole. After the iron-containing silicate minerals react with oxalic acid, ferrous oxalate complex precipitates are generated and loaded on the silicate minerals in situ, so that stable loading and dispersion of the ferrous oxalate complex are realized.
In a preferable scheme, the particle size of the iron-containing silicate mineral is 45-150 mu m.
In the preferable scheme, the liquid-solid ratio of the iron-containing silicate mineral to the oxalic acid and the water is 2-5 m L: 1g, and the mass ratio of the iron-containing silicate mineral to the oxalic acid is 1: 2-3: 1.
In a preferable scheme, the reaction time is 0.5-48 h.
Preferably, the ratio of the iron-based material to the sulfate reducing bacteria liquid is 20-100 g/10-500 m L, and the density of active bacteria in the sulfate reducing bacteria liquid is 106～1010And each m L.
The invention also provides an iron-based material and microorganism in-situ stabilization method for repairing the lead polluted bottom mud.
The sulfate reducing bacteria liquid is obtained by directly purchasing a strain Desulfosbrio (Desulfovibriosp. ATCC 7757) and simply performing amplification culture. The adopted culture medium formula is KH2PO40.5g/L,NH4Cl 1g/L,CaCl20.1g/L,MgSO4·7H2O2.5 g/L, sodium lactate 3.5 g/L, pH 6.5, culturing to logarithmic phase for use.
In a preferable scheme, the addition amount of the iron-based material in the reagent relative to the lead-polluted bottom sediment is 20-100 g/kg, and the addition amount of the sulfate reducing bacteria liquid relative to the lead-polluted bottom sediment is 10-500 m L/kg.
According to the preferable scheme, the temperature is controlled to be 15-35 ℃ in the repairing process, and the time is 7-60 days.
The lead content in the lead polluted bottom mud is 50-2000 mg/kg.
The principle of repairing the lead polluted bottom sediment by the iron-based material and the microbial lead polluted bottom sediment stabilizing agent is as follows: the invention is based on the interaction between iron-containing silicate minerals and oxalic acid, uses the oxalic acid to activate the iron component in the iron-containing minerals, and simultaneously solidifies the oxalate to generate the iron-based material of the silicate minerals loaded with the active component of ferrous oxalate, because the k of lead oxalatespK greater than ferrous oxalatespSo that lead can be solidified by generating a lead oxalate precipitate based on ion exchange between ferrous and lead ions, and on the other hand, in an iron-based materialThe oxalate anion can be used as an electron donor for growth and utilization of sulfate reducing bacteria, and further drives stabilization and restoration of lead in the lead polluted bottom sediment, meanwhile, hydrogen sulfide generated by metabolism of the sulfate reducing bacteria can simultaneously sulfide iron released from ferrous oxalate, and the formed ferrous sulfide can further react with the lead in the bottom sediment, so that the lead is converted from a free state into a stable residue state. In conclusion, based on a synergistic action system, a chemical-microorganism-chemical continuous coupling combined remediation system can be constructed, and in-situ efficient and sustainable stabilization remediation of the lead-polluted bottom mud can be promoted.
Compared with the prior art, the technical scheme of the invention has the advantages that:
1) the lead-polluted bottom sediment stabilizing reagent is low in cost, an iron-based material can be simply synthesized by natural minerals, and sulfate reducing bacteria are directly purchased commercially.
2) The stabilizing agent for the lead polluted bottom mud can realize continuous and efficient repair of the lead polluted bottom mud through the synergistic coupling between the sulfate reducing bacteria and the iron-based material, the stability rate of lead in the bottom mud is more than 97%, the mobility of the lead is obviously reduced, the bioavailability of the bottom mud is improved, and the stabilizing agent is particularly suitable for the continuous and stable repair of the lead polluted bottom mud.
3) The method for repairing the lead-polluted bottom sediment is simple and easy to operate, low in repairing cost, environment-friendly and pollution-free, can be applied to large-scale lead-polluted bottom sediment, and has a wide application prospect.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
The lead-polluted bottom sludge is taken from the bottom sludge of the clear pond at the Xiangjiang section of the plant continent, a sample is air-dried and sieved (60 meshes), and the basic property analysis is shown in Table 1.
TABLE 1 basic Properties of the sediment
| pH | 7.8 |
| Organic carbon (g/kg) | 7.88 |
| Organic matter (g/kg) | 13.59 |
| Cation exchange CEC (cmol/kg) | 21.6 |
| Total lead (mg/kg) | 733.68 |
Preparing an iron-based material: mixing fayalite and oxalic acid dihydrate according to the ratio of 2: 1, placing the mixture in a reactor, adding deionized water according to the liquid-solid ratio of 4: 1, sealing the reactor, heating the reactor to 90 ℃ for reaction for 36 hours, and after the reaction is finished, washing, filtering and drying the product.
Culturing sulfate reducing bacteria: desulovibrio sp.ATCC 7757 was inoculated into anaerobic medium (KH)2PO40.5g/L,NH4Cl 1g/L,CaCl20.1g/L,MgSO4·7H2O2.5 g/L, sodium lactate 3.5 g/L), pH is adjusted to 6.5, when the growth reaches the logarithmic phase for standby, the cell density of the bacterial liquid is 2 x 108And each m L.
The method is characterized in that the remediation of lead-polluted bottom mud in an anaerobic environment is simulated, a remediation experiment is carried out in a reactor of 5L, 1kg of bottom mud sample and 2L of deionized water are sequentially added into the reactor and divided into four groups of A, B, C and D, 0.5L of deionized water is added into the group A to serve as a blank control, 50g of iron-based material is added into the group B, 0.5L of sulfate reducing bacteria liquid is added into the group C, 50g of iron-based material and 0.5L of bacteria liquid are added into the group D, and after 30D of simulated remediation reaction, the change of the lead form in the sample is measured, and the result is shown in Table 2.
TABLE 2 morphological changes before and after immobilization of lead contaminated bottom sludge
Example 2
The samples were the same as in example 1.
Preparing an iron-based material: mixing biotite and oxalic acid dihydrate according to the ratio of 3: 2, placing the mixture in a reactor, adding deionized water according to the liquid-solid ratio of 5: 1, sealing the reactor, heating the reactor to 80 ℃ for reaction for 12 hours, and after the reaction is finished, washing, filtering and drying the product.
Culturing sulfate reducing bacteria: desulovibrio sp.ATCC 7757 was inoculated into anaerobic medium (KH)2PO40.5g/L,NH4Cl 1g/L,CaCl20.1g/L,MgSO4·7H2O2.5 g/L, sodium lactate 3.5 g/L), pH is adjusted to 6.5, when the growth reaches the logarithmic phase for standby, the cell density of the bacterial liquid is 3.2 x 108And each m L.
2kg of bottom mud sample and 4L deionized water are sequentially added into the reactor, the reactor is divided into four groups of A, B, C and D, 1L deionized water is added into the group A to serve as a blank control, 100g of iron-based material is added into the group B, 1L sulfate reducing bacteria liquid is added into the group C, 100g of iron-based material and 1L bacteria liquid are added into the group D, and after 90D of simulated repair reaction, the lead morphological change in the sample is measured, and the result is shown in Table 3.
Example 3
The samples were the same as in example 1.
Preparing an iron-based material: mixing the cross stone and oxalic acid dihydrate according to the ratio of 1:2, placing the mixture in a reactor, adding deionized water according to the liquid-solid ratio of 4: 1, sealing the reactor, heating the reactor to 90 ℃ for reaction for 24 hours, and after the reaction is finished, washing, filtering and drying the product.
TABLE 3 morphological changes before and after immobilization of lead contaminated bottom sludge
Culturing sulfate reducing bacteria: desulovibrio sp.ATCC 7757 was inoculated into anaerobic medium (KH)2PO40.5g/L,NH4Cl 1g/L,CaCl20.1g/L,MgSO4·7H2O2.5 g/L, sodium lactate 3.5 g/L), pH is adjusted to 6.5, when the growth reaches the logarithmic phase for standby, the cell density of the bacterial liquid is 3 x 108And each m L.
2kg of bottom mud sample and 4L deionized water are added into the reactor in sequence, the reactor is divided into four groups of A, B, C and D, 0.5L deionized water is added into the group A to serve as a blank control, 100g of iron-based material is added into the group B, 0.5L sulfate reducing bacteria liquid is added into the group C, 100g of iron-based material and 0.5L bacteria liquid are added into the group D, and after the simulated repair reaction is carried out for 60D, the lead form change in the sample is measured, and the result is shown in Table 4.
TABLE 4 morphological changes before and after immobilization of lead-contaminated bottom sludge
| Experiment grouping | Acid extraction state (%) | Reducible state (%) | Oxidizable state (%) | State of residue (%) |
| Raw sample | 57.83 | 20.42 | 6.32 | 15.43 |
| A | 55.28 | 24.81 | 5.82 | 14.09 |
| B | 23.02 | 26.93 | 9.17 | 40.88 |
| C | 18.71 | 7.62 | 10.34 | 63.33 |
| D | 2.91 | 1.68 | 9.62 | 85.79 |
Claims (9)
1. A reagent for in-situ stabilization repair of lead polluted bottom mud by iron-based materials in cooperation with microorganisms is characterized in that: comprises an iron-based material and sulfate reducing bacteria liquid;
the iron-based material is obtained by reacting iron-containing silicate minerals and oxalic acid in an aqueous medium at the temperature of 55-120 ℃.
2. The reagent for repairing the lead polluted bottom mud by the iron-based material in cooperation with the microorganism in-situ stabilization, according to claim 1, is characterized in that: the iron-containing silicate mineral comprises at least one of biotite, iron aluminum garnet, crossed stone, fayalite, Phyllanthus, aegonite, neon, Callerotite, magnesian and Naringite.
3. The reagent for repairing the lead polluted bottom mud by the iron-based material in cooperation with the microorganism in-situ stabilization, according to claim 1, is characterized in that: the particle size of the iron-containing silicate mineral is 45-150 mu m.
4. The reagent for in-situ stabilization restoration of lead polluted bottom mud by the cooperation of the iron-based material and the microorganism as claimed in claim 1, is characterized in that the liquid-solid ratio of the iron-containing silicate mineral to the oxalic acid to the water is 2-5 m L: 1g, and the mass ratio of the iron-containing silicate mineral to the oxalic acid is 1: 2-3: 1.
5. The reagent for in-situ stabilization repair of lead polluted bottom mud by the iron-based material in cooperation with microorganisms according to any one of claims 1 to 4, wherein the reagent comprises: the reaction time is 0.5-48 h.
6. The reagent for in-situ stabilization restoration of lead polluted bottom mud by the cooperation of the iron-based material and the microorganism as claimed in any one of claims 1 to 4, wherein the ratio of the iron-based material to the sulfate reducing bacteria liquid is 20-100 g/10-500 m L, and the density of active bacteria in the sulfate reducing bacteria liquid is 106～1010And each m L.
7. A method for in-situ stabilization repair of lead polluted bottom mud by iron-based materials in cooperation with microorganisms is characterized by comprising the following steps: adding the reagent of any one of claims 1 to 6 into lead polluted bottom mud for remediation.
8. The method for in-situ stabilization restoration of lead-polluted bottom sediment by cooperation of the iron-based material and the microorganism as claimed in claim 7, wherein the addition amount of the iron-based material in the reagent relative to the lead-polluted bottom sediment is 20-100 g/kg, and the addition amount of the sulfate reducing bacteria liquid relative to the lead-polluted bottom sediment is 10-500 m L/kg.
9. The method for in-situ stabilization of lead-polluted bottom mud by the cooperation of the iron-based material and the microorganism according to claim 7, wherein the method comprises the following steps: in the repairing process, the temperature is controlled to be 15-35 ℃, and the time is 7-60 days.
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