CN114395550A - Method for degrading halogenated organic pollutants by coupling immobilized dissimilatory metal reducing bacteria-driven biohydrogen production-nano palladium - Google Patents
Method for degrading halogenated organic pollutants by coupling immobilized dissimilatory metal reducing bacteria-driven biohydrogen production-nano palladium Download PDFInfo
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- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 53
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- 239000002184 metal Substances 0.000 title claims abstract description 29
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- 238000005859 coupling reaction Methods 0.000 title claims abstract description 19
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 14
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/10—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a carbohydrate
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/04—Enzymes or microbial cells immobilised on or in an organic carrier entrapped within the carrier, e.g. gel or hollow fibres
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
-
- 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
Abstract
A method for degrading halogenated organic pollutants by coupling immobilized dissimilatory metal reducing bacteria-driven biohydrogen production and nano palladium relates to the technical field of halogenated organic pollutant degradation. Utilizing the extracellular reduction capability of the dissimilatory metal reducing bacteria to realize the biosynthesis of the nano palladium in the sodium alginate immobilized microcapsule and load the nano palladium in the microcapsule so as to construct a dissimilatory metal reducing bacteria-nano palladium coupling system; the nanometer palladium is used for activating hydrogen generated by anaerobic metabolism of the dissimilatory metal reducing bacteria to generate active hydrogen so as to realize efficient dehalogenation degradation of halogenated organic pollutants. The integrated coupling degradation method solves the continuous flow bioremediation problem of halogenated organic pollutants, solves the operation danger and cost waste caused by introducing indissolvable hydrogen from an external source through microbial metabolism to produce hydrogen, and can realize high-efficiency in-situ dehalogenation. The degradation method has strong practical application value in the fields of environmental remediation of organic halogenated pollutants and environmental application of dissimilatory metal reducing bacteria.
Description
Technical Field
The invention relates to the technical field of halogenated organic pollutant degradation, in particular to a method for degrading halogenated organic pollutants by coupling biological hydrogen production-nano palladium driven by immobilized dissimilatory metal reducing bacteria.
Background
Halogenated organic pollutants generated by industrial wastewater, pesticides, dyes and bactericides are discharged into an ecological system in a large quantity, and cause serious harm to the environment and human health and safety. Due to their carcinogenic, mutagenic, and cytotoxic properties, halogenated organic pollutants have become potential human carcinogens and priority remediation pollutants.
The current treatment methods for the degradation of halogenated organic pollutants are mainly biological methods, chemical methods and physical methods. Compared with the conventional physical and chemical treatment means, the biological method has the advantages of low cost, simple and convenient operation, environmental friendliness and the like, so that the method for repairing the halogenated organic pollutants with the most application potential is formed. However, halogenated organic contaminants are generally xenobiotics due to the presence of halogenated groups and are poorly biodegradable, which results in slow rates of direct biological degradation. Thus, remediation of halogenated organic pollutants typically requires prior dehalogenation to increase their biodegradability.
At present, the catalytic reduction efficiency of a noble metal catalyst is mainly utilized for reduction and dehalogenation. The noble metal catalyst synthesized under the normal temperature condition has high activity in the aspect of catalytic dehalogenation. Of these noble metal catalysts, nano-palladium has excellent H2Adsorption capacity and excellent selectivity and stability. The nano palladium hydrogenation dehalogenation is mainly due to the activation of H by nano palladium2Active hydrogen is generated and adsorbed on the nano palladium to form Pd-H bonds. When the halogenated organic pollutant is adsorbed on the nano-palladium interface, the active hydrogen and the halogenated organic pollutant are contacted with each other, so that the hydrogenation dehalogenation is realized. However, at present, the nano palladium hydrogenation and dehalogenation needs to be externally introduced with hydrogen. But H2Has low water solubility, which makes its use very inefficient. In addition, H2Belongs to flammable and explosive hazardous gas, has harsh operating conditions and limited practical use.
Shewanella is a particular type of dissimilatory metal-reducing bacterium. Due to its unique extracellular reducing capacity, Shewanella has been used for extracellular reducing repair of numerous contaminants. Although Shewanella bacteria can also have dehalogenation capability on certain halogenated organic pollutants, the low dehalogenation efficiency and the small repair range severely limit the environmental repair application of Shewanella bacteria on the halogenated organic pollutants. However, Shewanella bacteria can biosynthesize nano-palladium particles by dissimilating metal reduction capacity and utilizing Pd (II). The biosynthetic nano palladium can utilize H2Realizing high-efficiency dehalogenation of halogenated organic pollutants.
However, there are three limitations to this repair approach: 1. the biosynthesis and dehalogenation repair of nano-palladium are two completely separated processes. Firstly, free synthesis of nano palladium is needed, and then nano palladium is purified for dehalogenation. The operation process is complicated, and the recovery rate of the nano palladium is low; 2. the dehalogenation process of the nano palladium needs to continuously provide H2. Because of H2The water solubility is extremely low, which results in low practical utilization thereof. In addition H2Belongs to flammable and explosive hazardous gases. This limits its practical use scenarios; 3. the free-state nano palladium mediated dehalogenation is a sequencing batch operation condition and is difficult to continuously and stably operate.
Disclosure of Invention
Aiming at the defects, the invention firstly utilizes sodium alginate to prepare the immobilized globule of the Shewanella bacteria, and then utilizes the Shewanella bacteria in the immobilized globule to biologically synthesize the nano palladium to form a nano palladium-Shewanella bacteria coupling system. In the system, nano palladium produces H through anaerobic metabolism of Shewanella bacteria2And (4) activating, namely realizing the efficient hydrogenation and dehalogenation of the halogenated organic pollutants by using active hydrogen. Therefore, the invention develops a method for degrading halogenated organic pollutants by coupling the immobilized dissimilatory metal reducing bacteria-driven biohydrogen production and nano palladium, thereby providing a new thought, a new technology and a new process for biological treatment of the halogenated organic pollutants.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for degrading halogenated organic pollutants by coupling bio-hydrogen production and nano-palladium driven by immobilized dissimilatory metal reducing bacteria utilizes the extracellular reducing capability of dissimilatory metal reducing bacteria to realize the biosynthesis of nano-palladium in sodium alginate immobilized microcapsules and load the nano-palladium in the microcapsules so as to construct a dissimilatory metal reducing bacteria-nano-palladium coupling system; the hydrogen generated by the anaerobic metabolism of the nanometer palladium activated dissimilatory metal reducing bacteria is utilized in the coupling system to generate active hydrogen so as to realize the efficient dehalogenation degradation of the halogenated organic pollutants.
Further, the method for degrading halogenated organic pollutants by coupling biohydrogen production and nano palladium driven by immobilized dissimilatory metal reducing bacteria comprises the following steps:
(1) preparing a required synthetic culture medium and synthetic wastewater containing halogenated organic pollutants, aerating and sterilizing for later use;
(2) selecting activated dissimilatory metal reducing bacteria monoclonal, inoculating into a liquid culture medium, and performing shake culture under aerobic conditions to a late logarithmic phase;
(3) centrifugally collecting thalli, and then resuspending and washing the thalli twice by using normal saline to prepare a bacterial suspension for later use;
(4) adding the bacterial liquid obtained in the step (3) into a sodium alginate solution in a super clean bench, and uniformly stirring;
(5) preparing bacteria-containing calcium alginate pellets by using a Lange peristaltic pump, connecting one end of each bacteria-containing calcium alginate pellet with a uniformly stirred sodium alginate solution, and dripping one end of each bacteria-containing calcium alginate pellet into a sterile calcium chloride solution for fixation;
(6) adding the immobilized beads into a synthesis culture medium, adding a Pd (II) synthesis precursor solution to synthesize nano-palladium, taking out the beads after the synthesis is finished, and adding the beads into the synthesis wastewater containing halogenated organic pollutants; anaerobic metabolism for producing H by using synthesized nano palladium adsorption dissimilatory metal reducing bacteria2And activated to generate active hydrogen, and the high-efficiency dehalogenation degradation repair of halogenated organic pollutants is realized through the hydrogenation dehalogenation.
The method comprises the steps of firstly immobilizing dissimilatory metal reducing bacteria by using sodium alginate, synthesizing nano palladium under an anaerobic condition, loading the nano palladium on a microcapsule, and finally activating the dissimilatory metal reducing bacteria by using the nano palladium to perform anaerobic metabolism to generate hydrogen and generate active hydrogen, so that the high-efficiency reduction dehalogenation of halogenated organic pollutants is realized. Compared with the prior art, the invention has the beneficial effects that:
1. the integrated coupling degradation method solves the continuous flow bioremediation problem of halogenated organic pollutants. Meanwhile, the method solves the operation danger and cost waste caused by introducing the indissolvable hydrogen through microbial metabolism hydrogen production, and can realize high-efficiency in-situ dehalogenation. The method has the advantages of easily controlled operation conditions and low material cost, and has strong practical application value in the fields of environmental remediation of organic halogenated pollutants and environmental application of dissimilatory metal reducing bacteria.
2. The integrated coupling degradation method solves the problem that the degradation of halogenated organic pollutants by microorganisms is slow, and effectively improves the degradation rate. Meanwhile, the method also avoids the condition that the nano-palladium is required to continuously introduce H for degrading halogenated organic pollutants by an external source2Reduces the safety risk and realizes the continuous production of endogenous hydrogen.
Drawings
FIG. 1 is a graph showing the change in the degradation treatment concentration of 2,4, 6-trichlorophenol in example 1.
FIG. 2 is a graph showing the change in the degradation treatment concentration of chlorobenzene in example 2.
Detailed Description
Example 1
This example evaluates the degradation efficiency of wild type dissimilatory metal-reducing bacterium Shewanella oneidensis MR-1 coupled with nano-palladium on 2,4, 6-trichlorophenol under anaerobic conditions. Shewanella oneidensis MR-1 wild strain was deposited at the American type Collection (ATCC) and the strain number was ATCC 700550 TM. This strain can be purchased directly from the center. The method comprises the following specific steps:
(1) preparing a required synthetic culture medium (HEPES1.191 g/L, sodium chloride 8g/L, potassium chloride 0.2g/L, ammonium sulfate 0.225g/L and sodium formate 1.36g/L), subpackaging 50mL serum bottles (totally 30mL system), preparing required synthetic wastewater (HEPES1.191 g/L, sodium chloride 8g/L, potassium chloride 0.2g/L, ammonium sulfate 0.225g/L, sodium formate 1.36g/L and 2,4, 6-trichlorophenol 10mg/L), aerating and sterilizing for later use.
(2) Shewanella oneidensis MR-1 stored in glycerol was streaked on LB plates and incubated overnight at 30 ℃.
(3) The activated single colony was picked with a sterile toothpick, inoculated into 50mL of LB liquid medium (yeast extract 5g/L, peptone 10g/L, NaCl L0 g/L), and cultured at 30 ℃ and 200rpm to late logarithmic phase.
(4) The cells were collected by centrifugation at 5000rpm for 5 minutes at 4 ℃ and then washed twice with physiological saline to prepare a bacterial suspension.
(5) In a super clean bench, the bacterial liquid obtained in the step (4) is used as OD with final concentration6002 to a 2.5% sodium alginate solution and stirred well using a glass rod.
(6) A Lange peristaltic pump is used for preparing the bacteria-containing calcium alginate pellets, one end of each bacterium-containing calcium alginate pellet is connected with a sodium alginate solution which is uniformly stirred, and the other end of each bacterium-containing calcium alginate pellet is dripped into a sterile calcium chloride solution and fixed for 3 hours.
(7) Adding the immobilized beads into a synthetic medium, and adding Na2PdCl4The solution is used for synthesizing nano palladium, the small ball is taken out after the synthesis is finished and is added into a glass chromatographic column, the synthetic wastewater slowly flows in (the flow rate is 20 mu L/min) through a peristaltic pump, and a water sample is taken out at regular time until the organic matter is completely degraded.
The concentration of 2,4, 6-trichlorophenol was determined by high performance liquid chromatography using a chromatorc 18 column, 5 μm, 4.6 × 250mm, 25 ℃ column temperature, mobile phase methanol: water (containing 0.1% formic acid) at a flow rate of 0.8mL/min 80:20, and a detection wavelength of 293nm using an ultraviolet detector.
The detection result is shown in figure 1, and it can be seen from figure 1 that 10mg/L of 2,4, 6-trichlorophenol is reduced to 1mg/L after 34h of treatment, and the degradation effect is obvious.
Example 2
This example evaluates the degradation efficiency of wild type dissimilatory metal-reducing bacterium Shewanella oneidensis MR-1 in anaerobic conditions coupled with nano-palladium on chlorobenzene. The method comprises the following specific steps:
(1) preparing required synthetic culture medium (HEPES1.191 g/L, sodium chloride 8g/L, potassium chloride 0.2g/L, ammonium sulfate 0.225g/L, sodium formate 1.36g/L), subpackaging 50mL serum bottles (30 mL system in total), preparing required synthetic wastewater (HEPES1.191 g/L, sodium chloride 8g/L, potassium chloride 0.2g/L, ammonium sulfate 0.225g/L, sodium formate 1.36g/L, chlorobenzene 5mg/L), aerating, and sterilizing for later use.
(2) Shewanella oneidensis MR-1 (same as example 1) stored in glycerol was streaked on LB plate and cultured overnight at 30 ℃.
(3) The activated single colony was picked with a sterile toothpick, inoculated into 50mL of LB liquid medium (yeast extract 5g/L, peptone 10g/L, NaCl L0 g/L), and cultured at 30 ℃ and 200rpm to late logarithmic phase.
(4) The cells were collected by centrifugation at 5000rpm for 5 minutes at 4 ℃ and then washed twice with physiological saline to prepare a bacterial suspension.
(5) In a super clean bench, the bacterial liquid obtained in the step (4) is used as OD with final concentration6002 to a 2.5% sodium alginate solution and stirred well using a glass rod.
(6) A Lange peristaltic pump is used for preparing the bacteria-containing calcium alginate pellets, one end of each bacterium-containing calcium alginate pellet is connected with a sodium alginate solution which is uniformly stirred, and the other end of each bacterium-containing calcium alginate pellet is dripped into a sterile calcium chloride solution and fixed for 3 hours.
(7) Adding the immobilized beads into the synthetic medium, and addingNa2PdCl4The solution is used for synthesizing nano palladium, the small ball is taken out after the synthesis is finished and is added into a glass chromatographic column, the synthetic wastewater slowly flows in (the flow rate is 20 mu L/min) through a peristaltic pump, and a water sample is taken out at regular time until the organic matter is completely degraded.
The chlorobenzene concentration was determined by high performance liquid chromatography using a chromatcorc 18 column, 5 μm, 4.6 × 250mm, 25 ℃ column temperature, mobile phase acetonitrile: water at a flow rate of 1mL/min 70:30, and a detection wavelength of 218nm using an ultraviolet detector.
The detection result is shown in fig. 2, and it can be seen from fig. 2 that after 24 hours of degradation, 5mg/L chlorobenzene is completely degraded, and the degradation effect is obvious.
It can be seen from examples 1 and 2 that the immobilized coupling system of nano palladium-Shewanella bacteria is constructed by immobilizing the dissimilatory metal reducing bacteria, synthesizing nano palladium and loading the nano palladium on the surface of the microcapsule. Then the mixture is filled in a glass chromatographic column, and wastewater containing halogenated organic pollutants is introduced. In the system, the nano palladium adsorbs dissimilatory metal reducing bacteria to generate H through anaerobic metabolism2And activated to generate active hydrogen, and the high-efficiency dehalogenation repair of halogenated organic pollutants is realized through the hydrogenation dehalogenation. Therefore, the method for degrading the halogenated organic pollutants by coupling the biological hydrogen production and the nano palladium driven by the immobilized dissimilatory metal reducing bacteria can realize the efficient reduction dehalogenation degradation of the halogenated organic pollutants.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (7)
1. A method for degrading halogenated organic pollutants by coupling bio-hydrogen production driven by immobilized dissimilatory metal reducing bacteria and nano-palladium is characterized in that the extracellular reducing capability of dissimilatory metal reducing bacteria is utilized, the biosynthesis of nano-palladium is realized in sodium alginate immobilized microcapsules, and the nano-palladium is loaded in the microcapsules, so that a dissimilatory metal reducing bacteria-nano-palladium coupling system is constructed; the hydrogen generated by the anaerobic metabolism of the nanometer palladium activated dissimilatory metal reducing bacteria is utilized in the coupling system to generate active hydrogen so as to realize the efficient dehalogenation degradation of the halogenated organic pollutants.
2. The method of claim 1, characterized by the steps of:
(1) preparing a required synthetic culture medium and synthetic wastewater containing halogenated organic pollutants, aerating and sterilizing for later use;
(2) selecting activated dissimilatory metal reducing bacteria monoclonal, inoculating into a liquid culture medium, and performing shake culture under aerobic conditions to a late logarithmic phase;
(3) centrifugally collecting thalli, and then resuspending and washing the thalli twice by using normal saline to prepare a bacterial suspension for later use;
(4) adding the bacterial liquid obtained in the step (3) into a sodium alginate solution in a super clean bench, and uniformly stirring;
(5) preparing bacteria-containing calcium alginate pellets by using a Lange peristaltic pump, connecting one end of each bacteria-containing calcium alginate pellet with a uniformly stirred sodium alginate solution, and dripping one end of each bacteria-containing calcium alginate pellet into a sterile calcium chloride solution for fixation;
(6) adding the immobilized beads into a synthesis culture medium, adding a Pd (II) synthesis precursor solution to synthesize nano-palladium, taking out the beads after the synthesis is finished, and adding the beads into the synthesis wastewater containing halogenated organic pollutants; anaerobic metabolism for producing H by using synthesized nano palladium adsorption dissimilatory metal reducing bacteria2And activated to generate active hydrogen, and the high-efficiency dehalogenation degradation repair of halogenated organic pollutants is realized through the hydrogenation dehalogenation.
3. The method of claim 2, wherein the electron donor used in the synthesis of the nano-palladium in step (1), i.e., the carbon source in the synthetic medium for anaerobic metabolism of the dissimilatory metal-reducing bacteria, is formate.
4. The method of claim 2, wherein the dissimilatory metal-reducing bacteria of step (2) is selected from Shewanella oneidensis MR-1 wild type,purchased from American type Collection (ATCC) and assigned strain number ATCC 700550TM。
5. The method of claim 2, wherein in the step (5), the dissimilatory metal-reducing bacteria are immobilized by sodium alginate, and then nano palladium is synthesized by the dissimilatory metal-reducing bacteria and loaded inside and on the surface of the immobilized beads.
6. The method of claim 2, wherein the Pd (II) synthesis precursor of step (6) is selected from Na2PdCl4。
7. The method of claim 2, wherein the halogenated organic contaminants degraded in step (6) are 2,4, 6-trichlorophenol and chlorobenzene.
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