CN111362396A - Preparation method and application of polyurethane composite carrier self-generating functional material for in-situ enhanced biological dehalogenation of underground water - Google Patents
Preparation method and application of polyurethane composite carrier self-generating functional material for in-situ enhanced biological dehalogenation of underground water Download PDFInfo
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/005—Combined electrochemical biological processes
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/2806—Anaerobic processes using solid supports for microorganisms
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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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
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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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
- C02F2103/06—Contaminated groundwater or leachate
Abstract
The invention discloses a preparation method and application of a polyurethane composite carrier self-generating functional material for in-situ reinforced biological dehalogenation of underground water, and belongs to the field of underground water pollution remediation. The method solves the problems that in the existing groundwater pollution remediation method, the anaerobic reduction dehalogenation reaction rate is slow, substances except hydrogen are difficult to use as electron donors, and secondary pollution and potential safety hazards of groundwater are easily caused by additionally adding complex organic carbon sources. According to the application, a self-generating functional material is loaded on polyurethane, then a polyurethane composite carrier self-generating functional material is loaded with dehalogenation breathing bacteria, and the polyurethane composite carrier self-generating functional material loaded with the dehalogenation breathing bacteria is used as a biological reaction grid filler for in-situ bioremediation of halogenated organic matter polluted groundwater. The polyurethane composite carrier self-generating functional material provided by the invention can provide an electron donor for dehalogenation respiratory bacteria, simultaneously stimulate cell metabolism and improve microbial activity, and the biological carrier has high strength and no secondary pollution.
Description
Technical Field
The invention relates to a preparation method and application of a polyurethane composite carrier self-generating functional material for in-situ reinforced biological dehalogenation of underground water, belonging to the field of pollution remediation of underground water.
Background
The groundwater is an important fresh water resource and plays an indispensable role in the human survival and development process. The halogenated organic matters cause serious pollution to underground water due to wide application and non-standard disposal in life and industrial and agricultural industries, and have non-trivial harm to public health. Groundwater pollution remediation methods are mainly classified into in-situ remediation methods and ex-situ remediation methods. Wherein, the in-situ remediation method has small disturbance to water, is not easy to diffuse pollution and has better durability, thereby having wide application in groundwater remediation engineering. The underground water in-situ biological dehalogenation technology simulates the self-purification process of a water body, and microorganisms generate reduction dehalogenation reaction under the action of respiration in an anoxic environment to realize dehalogenation and detoxification of halogenated organic matters.
However, since the above-mentioned dehalogenating respiring bacteria by anaerobic reduction dehalogenation hardly use substances other than hydrogen as electron donors, in experiments and engineering, organic carbon sources are usually added to the system, and the electron donors required for dehalogenation of microorganisms are provided by producing hydrogen through fermentation. However, in the groundwater in-situ bioremediation process, secondary pollution and potential safety hazard of groundwater are easily caused by adding of the complex organic carbon source, so that the spontaneous electrical generating functional material which can be applied to groundwater in-situ enhanced biological dehalogenation in a large scale is provided, an electron donor is provided for reducing dehalogenation bacteria, and meanwhile, the secondary pollution risk caused by adding of the complex organic carbon source is reduced, so that the groundwater bioremediation process is enhanced.
Disclosure of Invention
The invention provides a preparation method and application of a polyurethane composite carrier self-generating electricity generating functional material for underground water in-situ enhanced biological dehalogenation, which aims to solve the problems that substances except hydrogen are difficult to utilize as electron donors by dehalogenation breathing bacteria of the existing anaerobic reduction dehalogenation reaction, and the added organic carbon source is easy to cause secondary pollution and potential safety hazard to underground water.
The technical scheme of the invention is as follows:
a polyurethane composite carrier self-generating functional material comprises the following raw materials in parts by mass: 5 parts of polyurethane sponge filler, 50 parts of spontaneous generation electric material and 45 parts of waterborne polyurethane.
Further limited, the self-generating electricity material is tourmaline powder or iron-carbon composite material.
Further limited, the iron-carbon composite material comprises the following components in percentage by weight: 77% of 80-100 mesh iron powder, 16% of 100-200 mesh charcoal powder and 7% of 100 mesh nickel powder.
The preparation method of the polyurethane composite carrier self-generating functional material comprises the following specific operation processes:
firstly, adding a cubic polyurethane sponge filler, a spontaneous electricity generation material and waterborne polyurethane into a stirring tank, stirring and mixing uniformly, and removing redundant adhesive in an extrusion mode to obtain a composite material;
and then, drying the obtained composite material at the temperature of 80 ℃ to obtain the self-generating functional material of the polyurethane composite carrier.
Further, without limitation, the side length of the cubic polyurethane sponge filler is 10-20 mm.
The method for loading the dehalogenation breathing bacteria on the polyurethane composite carrier self-generating functional material comprises the following steps:
placing an aseptic initial culture solution into an anaerobic fermentation tank, adding a target halogenated organic matter with the final concentration of 200 mu mol/L, then inoculating dehalogenation breathing bacteria, culturing at the constant temperature of 30 ℃ for 48-72 h, and obtaining a flocculent dehalogenation breathing bacteria suspension; the target halogenated organic matter can be any other halogenated organic matter besides TCP, and a compound flora domesticated for the specific halogenated organic matter as a target pollutant or a separated single strain is correspondingly adopted, for example, the target halogenated organic matter can be tetrabromobisphenol A, and the correspondingly loaded microorganism is a compound functional flora or a single bacterium with the tetrabromobisphenol A reduction dehalogenation function.
And step two, adding the polyurethane composite carrier self-generating functional material into the anaerobic fermentation tank, continuously culturing, periodically replacing the culture solution during the culture period, supplementing the target halogenated organic matters, and culturing for 20 days to obtain the black polyurethane composite carrier self-generating functional material with the white biological membrane attached to the surface.
Further, without limitation, the pH of the sterile initial culture solution is adjusted by a PBS buffer system, and when the spontaneous electricity generation material of the polyurethane composite carrier functional material is tourmaline, the pH of the sterile initial culture solution is 7.2; when the spontaneous electricity generation material of the functional material of the polyurethane composite carrier is an iron-carbon composite material, the pH value of the sterile initial culture solution is 6.
Further limiting, the dehalogenation respiratory bacteria are anaerobic microorganisms taking halogenated organic matters as electron acceptors, and the inoculation mass is 5% of the mass of the sterile initial culture solution.
More specifically, the anaerobic microorganisms having a haloorganic electron acceptor are dehalogenating respiratory bacteria, including but not limited to, Desulfurobacterium spp (Desulbactobacterium spp.), Dehalobacter spp (Dehalobacter spp.), Geobacterium spp (Geobacterium spp.) of Proteobacteria, Desulfurobacterium spp (Desulfuromone spp.), Anhalobacter dehalogena, Desulfuricus (Desulfurobacterium spp), and Desulfuricus spp (sulfosporotrichium spp.), Deshalococcus spp (Chloromyces spp.).
The method for in-situ reinforced biological dehalogenation of underground water by using the polyurethane composite carrier self-generating electricity generating functional material loaded with the dehalogenation breathing bacteria is characterized in that a biological reaction grating system is installed along the underground water flow direction, and the polyurethane composite carrier self-generating electricity generating functional material loaded with the dehalogenation breathing bacteria is filled in a grating.
Further limiting, the polyurethane composite carrier self-generating functional material loaded with the dehalogenation breathing bacteria can also be used for dehalogenation and detoxification of halogenated organic pollutants in surface water and an anaerobic reactor.
The invention has the following beneficial effects: the method for loading the self-generating material on the reticular polyurethane sponge is more suitable for large-scale production, the self-generating material is more uniformly distributed on the polyurethane sponge by mixing the self-generating material with the stirring tank, and the stirring slurry continuously extrudes and releases the polyurethane sponge, so that the loading capacity of the self-generating material in pores inside the sponge is greatly increased. The self-generating functional material of the polyurethane composite carrier integrates the functions of adsorption and bioremediation, provides electrons for microorganisms, stimulates cell metabolism and improves the activity of the microorganisms, plays a role in strengthening the bioremediation process, and provides a carrier for functional microorganisms, so that the microorganisms are immobilized, and functional bacteria and the strengthening material are prevented from washing away from a polluted area. The polyurethane composite carrier prepared by the invention is used as a filler in a biological reaction grid for in-situ remediation of underground water, so that halogenated organic pollutants transversely diffused in an aquifer can pass through the biological reaction grid along with water flow to realize dehalogenation and detoxification. The material has long lasting action time in the groundwater, is beneficial to material recovery and treatment, reduces the influence of an added substance on the groundwater as much as possible, and is an ideal groundwater in-situ bioremediation functional material.
Drawings
FIG. 1 is a diagram of a polyurethane composite carrier self-generating functional material;
fig. 2 is a graph showing the concentration change of pollutants and products for degrading TCP in a 2L anaerobic serum bottle by using the polyurethane composite carrier self-generating functional material loaded with dehalogenating respiratory bacteria prepared in the specific embodiment 1;
fig. 3 is a graph showing the concentration change of pollutants and products for degrading TCP in a 2L anaerobic serum bottle by using the polyurethane composite carrier self-generating functional material loaded with dehalogenating respiratory bacteria prepared in the specific embodiment 2;
FIG. 4 is a schematic view of the installation structure of the biological reaction grid applied to groundwater in-situ remediation.
Detailed Description
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional in the art and are commercially available to those skilled in the art.
Embodiment mode 1:
firstly, 5g of cube mesh polyurethane sponge filler with the size of 1cm × 1cm × 1cm, 50g of 800-mesh ferroelectrician powder and 45g of aqueous polyurethane adhesive are placed in a stirrer to be fully stirred and mixed, the tourmaline powder is uniformly adhered to the surface and the pores of the polyurethane sponge, the excessive adhesive in the polyurethane sponge is discharged by extrusion, the polyurethane sponge is placed in an oven with the temperature of 80 ℃ to be dried for 12 hours, and the black polyurethane composite carrier self-generating functional material is obtained after the mixture is taken out, as shown in figure 1, wherein the mesh polyurethane sponge filler is AQ-30 polyurethane sponge produced by Aishi technology company, the porosity is 95%, the number of pores is 20/25 mm, the pore diameter is 1.5mm, and the specific surface area is 91000m2/m3(ii) a The waterborne polyurethane is F0401 type produced by Shenzhen Jitian chemical industry Limited, has transparent appearance, viscosity of 300mPa.S, pH value of 5-6 and solid content of 32 +/-5 percent.
Then, a liquid medium was prepared with deionized water according to the following formulation: 1g/L NaCl, 0.2g/L MgCl2·6H2O， 2.31g/L Na2HPO4·12H2O，0.554g/L NaH2PO4·2H2O，0.13g/L NH4Cl，0.3g/L KCl，0.012g/L CaCl20.1mL/L mineral element 1 and 0.1mL/L mineral element 2. The mineral element 1 base liquid comprises the following components in percentage by weight: 0.5mg/L MnCl2·4H2O，0.5mg/L ZnCl2，0.5mg/L NiCl2·6H2O，0.5mg/L H3BO3，0.5mg/LNa2MoO4·2 H2O，2.5mg/L CoCl2·6H2O; the mineral element 2 base solution comprises the following components in percentage by weight: 0.5mg/LNH4VO3，2.5mg/LKI， 10mg/L(NaPO3)16(ii) a Pouring 1.2L of prepared anaerobic culture medium into a 2L serum bottle, blowing off with high-purity nitrogen for 20min for deoxygenation, sealing the container, and sterilizing with high-pressure steam at 121 deg.C for 30min to obtain sterile initial culture solution. Sequentially injecting Na with the final concentration of 2mmol/L into the serum bottle2The method comprises the following steps of preparing an S solution, 3ml of a 2mol/L sodium acetate solution, 1.2ml of vitamins and a final concentration of 200 mu mol/L2, 4, 6-Trichlorophenol (TCP) solution, inoculating dehalogenated respiratory bacteria with the volume of 5% of that of an aseptic initial culture solution, and acclimatizing and culturing the dehalogenated respiratory bacteria in the laboratory to obtain an anaerobic mixed flora for dechlorinating TCP. Finally, 200mL of high purity hydrogen was injected.
Then, the serum bottle is put into a constant temperature incubator at 30 ℃ for culture, and samples are periodically taken during the culture to detect the concentration of the 2,4, 6-trichlorophenol and the dechlorinated products of the 2, 4-dichlorophenol and 4-chlorophenol. When white microbial floc appears in the serum bottle and 2,4, 6-trichlorophenol in the solution begins to degrade and dehalogenation products appear, the serum bottle is opened under the protection of nitrogen, the polyurethane composite carrier self-generating functional material is rapidly put in the serum bottle, and the container is sealed. Continuously placing the serum bottle into a constant-temperature incubator at 30 ℃ for continuous culture, periodically sampling and detecting the concentrations of 2,4, 6-trichlorophenol and dechlorinated products thereof, namely 2, 4-dichlorophen and 4-chlorophenol, and periodically supplementing sodium acetate solution and the 2,4, 6-trichlorophenol. After culturing for 20 days, obviously seeing that a white biological film is attached to the surface of the black polyurethane composite carrier functional material in the serum bottle, finishing the loading of the dehalogenation breathing bacteria by the polyurethane composite carrier functional material, and obtaining the black polyurethane composite carrier self-generating functional material with the white biological film attached to the surface.
Preparing the same liquid culture medium according to the components in another 2L serum bottle, pouring 1.2L of the prepared anaerobic culture medium into the 2L serum bottle, adding 200 particles of the obtained polyurethane composite carrier self-generating functional material attached with the biomembrane into the serum bottle, blowing off the polyurethane composite carrier self-generating functional material by pure nitrogen for 20min to perform oxygen removal treatment, and sealing the container. The above liquid medium is prepared with tap water and is not subjected to sterilization treatment in order to keep as much as possible the complicated environment of in-situ water drainage. Sequentially injecting into a serum bottle to a final concentration of2mmol/L Na2S solution, 3ml of 2mol/L sodium acetate solution, 1.2ml of vitamin, and 100 mu mol/L2, 4, 6-Trichlorophenol (TCP) solution without adding hydrogen. The concentration of the target pollutant TCP and dechlorinated product is detected regularly. The obtained periodic detection results of the target pollutants are shown in fig. 2: after TCP is added for the first time, a large amount of functional materials are immediately adsorbed, and the concentration of residual TCP in the solution is detected to be about 20 mu M on days 2-6, which indicates that the material is saturated in adsorbing TCP. The TCP concentration decreased to 0 on day 8 and the dehalogenation products 2, 4-dichlorophenol and 4-chlorophenol increased significantly, with the 4-chlorophenol concentration increasing to around 25 μ M and the 2, 4-dichlorophenol concentration decreasing to 0 on day 10. At this time, the container was replenished with TCP to a concentration of 135. mu.M, and 24 hours later, the concentration of TCP in the solution was detected to decrease to 0, and the concentration of 4-chlorophenol increased to 48. mu.M. The container was then replenished with TCP to a concentration of 140. mu.M, and 24h later the decrease in TCP concentration in the solution was detected as 0, and the increase in 4-chlorophenol concentration was detected as 70. mu.M. The results show that: under the condition of not adding hydrogen, the self-generating functional material of the polyurethane composite carrier provides a required electron donor for the dehalogenation respiratory bacteria, and plays a role in strengthening the biological dehalogenation reaction. And the material has good adsorbability, and the mode of firstly adsorbing and then degrading greatly increases the repair efficiency.
Embodiment mode 2:
firstly, uniformly mixing 50g of 80-mesh reduced iron powder, 10g of 200-mesh charcoal powder and 4.36g of 100-mesh nickel powder to obtain an iron-carbon composite material, putting 5g of cube mesh polyurethane sponge filler with the size of 1cm × 1cm × 1cm, 50g of the iron-carbon composite material and 45g of aqueous polyurethane adhesive into a stirrer for fully stirring and mixing to ensure that tourmaline powder is uniformly adhered to the surface and in pores of polyurethane sponge, discharging the redundant adhesive in the polyurethane sponge by extrusion, putting the polyurethane sponge into an oven at 80 ℃ for drying for 12 hours, and taking out the polyurethane sponge filler to obtain the black polyurethane composite carrier self-generating functional material, wherein the mesh polyurethane sponge filler is AQ-30 polyurethane sponge produced by Aiqin scientific and has the porosity of 95%, the pore number of 20/25 mm, the pore diameter of 1.5mm and the specific surface area of 91000m2/m3(ii) a The waterborne polyurethane is F0401 type produced by Shenzhen Jitian chemical industry Limited, has transparent appearance, viscosity of 300mPa.S, pH value of 5-6 and solid content of 32 +/-5％。
Then, a liquid medium was prepared according to the following formulation: the method for sterilizing comprises the following steps:
(1) the liquid medium was prepared according to the following formulation: 1g/L NaCl, 0.2g/L MgCl2·6H2O，0.704g/LNa2HPO4·12H2O，2.189g/L NaH2PO4·2H2O，0.13g/L NH4Cl，0.3g/L KCl，0.012g/L CaCl20.1mL/L mineral element 1 and 0.1mL/L mineral element 2. The mineral element 1 base liquid comprises the following components in percentage by weight: 0.5mg/L MnCl2·4H2O，0.5mg/L ZnCl2，0.5mg/L NiCl2·6H2O，0.5mg/L H3BO3，0.5mg/L Na2MoO4·2 H2O，2.5mg/LCoCl2·6H2O; the mineral element 2 base solution comprises the following components in percentage by weight: 0.5mg/LNH4VO3，2.5mg/L KI， 10mg/L(NaPO3)16(ii) a Pouring the prepared anaerobic culture medium into a 2L serum bottle, blowing off high-purity nitrogen for 20min for deoxygenation, sealing the container, and sterilizing with high-pressure steam at 121 deg.C for 30min to obtain sterile initial culture solution. Sequentially injecting Na with the final concentration of 2mmol/L into the serum bottle2The method comprises the following steps of preparing an S solution, 3ml of a 2mol/L sodium acetate solution, 1.2ml of vitamins and a final concentration of 100 mu mol/L2, 4, 6-Trichlorophenol (TCP) solution, inoculating dehalogenated respiratory bacteria with the volume of 5% of that of an aseptic initial culture solution, and acclimatizing and culturing the dehalogenated respiratory bacteria in the laboratory to obtain an anaerobic mixed flora for dechlorinating TCP. Finally, 200mL of high purity hydrogen was injected.
Then, the serum bottle is put into a constant temperature incubator at 30 ℃ for culture, and samples are periodically taken during the culture to detect the concentration of the 2,4, 6-trichlorophenol and the dechlorinated products of the 2, 4-dichlorophenol and 4-chlorophenol. When white microbial floc appears in the serum bottle and 2,4, 6-trichlorophenol in the solution begins to degrade and dehalogenation products appear, the serum bottle is opened under the protection of nitrogen, the polyurethane composite carrier self-generating functional material is rapidly put in the serum bottle, and the container is sealed. Continuously placing the serum bottle into a constant-temperature incubator at 30 ℃ for continuous culture, periodically sampling and detecting the concentrations of 2,4, 6-trichlorophenol and dechlorinated products thereof, namely 2, 4-dichlorophen and 4-chlorophenol, and periodically supplementing sodium acetate solution and the 2,4, 6-trichlorophenol. After culturing for 20 days, obviously seeing that a white biological film is attached to the surface of the black polyurethane composite carrier functional material in the serum bottle, finishing the loading of the dehalogenation breathing bacteria by the polyurethane composite carrier functional material, and obtaining the black polyurethane composite carrier self-generating functional material with the white biological film attached to the surface.
Preparing the same liquid culture medium according to the components in another 2L serum bottle, pouring 1.2L of the prepared anaerobic culture medium into the 2L serum bottle, adding 200 particles of the obtained polyurethane composite carrier self-generating functional material attached with the biomembrane into the serum bottle, blowing off the polyurethane composite carrier self-generating functional material by pure nitrogen for 20min to perform oxygen removal treatment, and sealing the container. The above liquid medium is prepared with tap water and is not subjected to sterilization treatment in order to keep as much as possible the complicated environment of in-situ water drainage. Sequentially injecting Na with the final concentration of 2mmol/L into the serum bottle2S solution, 3ml of 2mol/L sodium acetate solution, 1.2ml of vitamin, and 100 mu mol/L2, 4, 6-Trichlorophenol (TCP) solution without adding hydrogen. The concentration of the target pollutant TCP and dechlorinated product is detected regularly. The obtained target pollutant periodic detection result is shown in fig. 3: after TCP is added for the first time, a large amount of functional materials are immediately adsorbed, the concentration of residual TCP in the solution is detected to be about 10 mu M in days 2-4, and the saturation of the material adsorption TCP is shown. The TCP concentration in the solution decreased slightly on day 6 and the dehalogenation product 2, 4-dichlorophenol concentration increased to 1.7. mu.M. The TCP concentration decreased to 0, 4-chlorophenol concentration increased to 17 μ M in the solution on day 8, and the 2, 4-dichlorophenol concentration decreased again to 0. The 4-chlorophenol concentration in the solution increased to around 22 μ M on day 10. At this time, the container was replenished with TCP to a concentration of 115. mu.M, and 24 hours later, the concentration of TCP in the solution was detected to decrease to 0, and the concentration of 4-chlorophenol increased to 37. mu.M. The vessel was then replenished with TCP to a concentration of 130. mu.M, and 24h later the decrease in TCP concentration in the solution was detected as 0, and the 4-chlorophenol concentration increased to 55. mu.M. The results show that: under the condition of not adding hydrogen, the self-generating functional material of the polyurethane composite carrier provides a required electron donor for the dehalogenation respiratory bacteria, and plays a role in strengthening the biological dehalogenation reaction. And the material has good adsorbability, and the mode of firstly adsorbing and then degrading greatly increases the repair efficiency.
In summary, it can be seen from the specific embodiments 1 and 2 that the polyurethane composite carrier spontaneous electrical functional material prepared from two different spontaneous electrical materials, namely the tourmaline and the iron carbon composite material, can enhance the dehalogenation reaction of the dehalogenation respiratory bacteria on the 2,4, 6-trichlorophenol without adding hydrogen. The self-generating functional material of the polyurethane composite carrier prepared by the iron-carbon material has more obvious adsorption effect due to the existence of the biochar. In the specific implementation mode, a 2L system is adopted to simulate the step of loading the dehalogenation respiratory bacteria on the functional material of the polyurethane composite carrier in production, and the result shows that the method is also suitable for large-scale production. The preparation method of the polyurethane composite carrier self-generating functional material, the loading method of the dehalogenation breathing bacteria and the in-situ bioremediation method of halogenated organic pollution in underground water provided by the invention have obvious advantages in large-scale application and are worthy of further popularization.
As shown in FIG. 4, the method for in-situ enhanced biological dehalogenation of underground water by using the self-generating functional material of the polyurethane composite carrier loaded with the dehalogenation breathing bacteria is characterized in that a biological reaction grid system is arranged along the direction of underground water flow, and the self-generating functional material of the polyurethane composite carrier loaded with the dehalogenation breathing bacteria is filled in a grid.
Claims (10)
1. The self-generating functional material of the polyurethane composite carrier is characterized by comprising the following raw materials in parts by mass: 5 parts of polyurethane sponge filler, 50 parts of spontaneous generation electric material and 45 parts of waterborne polyurethane.
2. The polyurethane composite carrier self-generating functional material according to claim 1, wherein the self-generating material is tourmaline powder or iron carbon composite material.
3. The self-generating functional material of the polyurethane composite carrier as claimed in claim 2, wherein the iron-carbon composite material comprises, by weight, 77% of 80-100 mesh iron powder, 16% of 100-200 mesh charcoal powder and 7% of 100 mesh nickel powder.
4. The preparation method of the polyurethane composite carrier self-generating functional material as claimed in claim 1, which is characterized by comprising the following specific operation processes:
firstly, adding a cubic polyurethane sponge filler, a spontaneous electricity generation material and waterborne polyurethane into a stirring tank, stirring and mixing uniformly, and removing redundant adhesive in an extrusion mode to obtain a composite material;
and then, drying the obtained composite material at the temperature of 80 ℃ to obtain the self-generating functional material of the polyurethane composite carrier.
5. The preparation method of the polyurethane composite carrier self-generating functional material as claimed in claim 4, wherein the side length of the cubic polyurethane sponge filler is 10-20 mm.
6. The method for loading the dehalogenation respiratory bacteria on the polyurethane composite carrier self-generating functional material is characterized by comprising the following steps of:
placing an aseptic initial culture solution into an anaerobic fermentation tank, adding a target halogenated organic matter with the final concentration of 200 mu mol/L, then inoculating dehalogenation breathing bacteria, culturing at the constant temperature of 30 ℃ for 48-72 h, and obtaining a flocculent dehalogenation breathing bacteria suspension;
and step two, adding the polyurethane composite carrier self-generating functional material into the anaerobic fermentation tank, continuously culturing, periodically replacing the culture solution during the culture period, supplementing the target halogenated organic matters, and culturing for 20 days to obtain the black polyurethane composite carrier self-generating functional material with the white biological membrane attached to the surface.
7. The method according to claim 6, wherein the pH of the sterile initial culture solution is adjusted by a PBS buffer system, and when the spontaneous electric generation material of the polyurethane composite carrier functional material is tourmaline, the pH of the sterile initial culture solution is 7.2; when the spontaneous electricity generation material of the functional material of the polyurethane composite carrier is an iron-carbon composite material, the pH value of the sterile initial culture solution is 6.
8. The method according to claim 6, wherein the dehalogenated respiratory bacteria are anaerobic microorganisms with halogenated organic substances as electron acceptors, and the inoculation mass is 5% of the mass of the sterile initial culture solution.
9. The method according to claim 7, wherein the anaerobic microorganism using the halogenated organic substance as the electron acceptor is a complex strain acclimatized using the halogenated organic substance as the target pollutant.
10. The method for in-situ enhanced biological dehalogenation of underground water by using the self-generating functional material of the dehalogenation breathing bacteria-loaded polyurethane composite carrier is characterized in that a biological reaction grid system is arranged along the underground water flow direction, and the self-generating functional material of the dehalogenation breathing bacteria-loaded polyurethane composite carrier is filled in a grid.
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| CN115354010A (en) * | 2022-08-23 | 2022-11-18 | 湖南大学 | Method for increasing content of low-toxicity reduction product in microorganism reduction chlorophenol system |
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| CN115354010B (en) * | 2022-08-23 | 2024-02-06 | 湖南大学 | Method for improving content of low-toxicity reduction products in microbial reduction chlorophenol system |
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