CN115448468A - Klebsiella-nano iron sulfide @ charcoal-based composite material as well as preparation method and application thereof - Google Patents
Klebsiella-nano iron sulfide @ charcoal-based composite material as well as preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- 241000588748 Klebsiella Species 0.000 claims abstract description 48
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003610 charcoal Substances 0.000 claims abstract description 9
- 239000003673 groundwater Substances 0.000 claims abstract description 4
- 239000000725 suspension Substances 0.000 claims description 15
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
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- -1 ferrous compound Chemical class 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 150000003464 sulfur compounds Chemical class 0.000 claims description 4
- 230000001580 bacterial effect Effects 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
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- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
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- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 14
- 238000001179 sorption measurement Methods 0.000 abstract description 13
- 230000009467 reduction Effects 0.000 abstract description 10
- 238000005067 remediation Methods 0.000 abstract description 4
- 238000010405 reoxidation reaction Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000003911 water pollution Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 239000011206 ternary composite Substances 0.000 description 14
- SFAYBQDGCKZKMH-UHFFFAOYSA-N BNCC Chemical compound BNCC SFAYBQDGCKZKMH-UHFFFAOYSA-N 0.000 description 10
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 241000894006 Bacteria Species 0.000 description 9
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- 239000002351 wastewater Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000001768 carboxy methyl cellulose Substances 0.000 description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 6
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 241001014264 Klebsiella variicola Species 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
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- 230000002195 synergetic effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
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- 239000012880 LB liquid culture medium Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 241001052560 Thallis Species 0.000 description 2
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- 239000011521 glass Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 238000005192 partition Methods 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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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
- C02F3/348—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the way or the form in which the microorganisms are added or dosed
-
- 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
- C02F2003/001—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
-
- 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
- C02F2003/001—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
- C02F2003/003—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms using activated carbon or the like
-
- 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
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2203/00—Apparatus and plants for the biological treatment of water, waste water or sewage
- C02F2203/006—Apparatus and plants for the biological treatment of water, waste water or sewage details of construction, e.g. specially adapted seals, modules, connections
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/08—Nanoparticles or nanotubes
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- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a composite material based on Klebsiella-nano iron sulfide @ charcoal and a preparation method and application thereof. Is formed by loading klebsiella and nano iron sulfide on charcoal. The material enhances the adsorption and reduction performance of chromium and improves the remediation effect of the chromium-polluted groundwater. The method has the characteristics of low price, environmental protection, high efficiency, durability, difficult reoxidation of the reduced chromium and the like, the chromium-removed effect of the chromium-polluted underground water treated by the method can reach 98.7 percent, and the national underground water pollution risk management and control standard can be met.
Description
Technical Field
The invention belongs to the technical field of remediation of heavy metal polluted underground water by using an environment composite material, and particularly relates to a composite material based on Klebsiella-nano iron sulfide @ charcoal, and a preparation method and application thereof.
Background
Chromium is considered one of the most common heavy metals in contaminated ground water, surface water and industrial sites, and is also one of the 20 major pollutants in china, which poses a great threat to the ecological environment and human health. The common valence states of the chromium element are Cr (VI) and Cr (III), the Cr (VI) has good solubility in aqueous solution and strong toxicity, and the Cr (III) is easy to form precipitate and has low toxicity. The current common method for treating chromium-polluted underground water is mainly based on single physical adsorption, single chemical adsorption or physical and chemical combination, such as nano iron, certain nano sulfides, biochar or the combination thereof, and the like, to reduce Cr (VI) into Cr (III). The physical and chemical method has poor recycling rate, is easy to achieve adsorption or reaction saturation, and has the risk of reoxidation of reduced chromium Cr (III) along with the increase of treatment time and poor durability of environmental materials, thereby reducing the treatment effect and increasing the treatment cost.
According to research, the Klebsiella (BNCC 337014, north Nabiont) has good chromium reducibility and potential application prospect in the aspect of chromium pollution treatment; the nano CMC-FeS synthetic material is simple, cheap and easily available, and Fe in the nano FeS 2+ And S 2- The ion pair has strong reduction capability to Cr (VI); the biochar is used as an adsorbent carrier, can protect the stability of the nano FeS, and has good biocompatibility on the Klebsiella. The composite material based on the Klebsiella-nano FeS @ charcoal ternary synergistic effect is prepared and used for repairing chromium-polluted underground water, and the Cr (VI) is subjected to physical-chemical-biological ternary synergistic absorption and reduction simultaneously, so that the defect of poor durability of a physical and chemical environment material is overcome, and the treatment efficiency is improved.
Disclosure of Invention
The invention aims to: provides a composite material based on Klebsiella-nano iron sulfide @ charcoal, a preparation method thereof and a method for repairing chromium pollution. The purpose of the invention is realized by the following modes:
a composite material based on Klebsiella-nano iron sulfide @ charcoal is formed by loading Klebsiella and nano iron sulfide on charcoal.
The preparation method of the composite material comprises the step of adding the biochar loaded with the nano iron sulfide into the Klebsiella suspension to prepare the composite material.
Further, the biochar loaded with the nano iron sulfide is prepared by adding the biochar in the preparation process of the nano iron sulfide, and preferably by adopting a CMC (carboxymethyl cellulose) method.
The preparation process of the charcoal loaded with the nano iron sulfide comprises the following steps: in N 2 In the purging solution, the ferrous compound is dissolved in deionized water and used>99％N 2 Deoxidizing; then adding CMC solution; continuously introducing the biochar under strong magnetic stirring, and finally slowly adding the solution of the sulfur-containing compound into the mixed suspension to prepare the biochar; the sulfur-containing compounds include: at least one of sodium sulfide, sodium thiosulfate and sodium sulfite.
Preferably, the solution of at least one of sodium sulfide, sodium thiosulfate and sodium sulfite is slowly added into the mixed suspension at a rate of 0.01-10 mL/min.
The ferrous compound comprises FeSO 4 Dissolving in deionized water to prepare FeSO with the concentration of 1-5g/L 4 And (3) solution.
Furthermore, the adding amount of the biochar is 500-600mg/L, the preparation concentration range of the sulfur compound solution is 30-40g/L, the volume ratio of the sulfur compound solution to the mixed suspension is not more than 0.1, and the FeS: CMC: the mass ratio of the biochar is 0.8-1.2: 0.8 to 1.2;0.8 to 1.2.
Further, the concentration range of the Klebsiella suspension is 10 7 -10 8 CFU/ml, and the particle size range of the biochar is 1-3mm.
Further, adding the biochar loaded with the nano iron sulfide into the bacterial suspension to a final concentration of 0.1-0.5g L -1 。
The invention also provides application of the composite material based on the Klebsiella-nano iron sulfide @ charcoal in chromium removal.
Further, a PBR wall curtain constructed on the basis of the Klebsiella-nano iron sulfide @ charcoal composite material is used for repairing chromium-polluted underground water.
The PRB simulation device built in the invention is a cuboid with the length and width of 30cm and the height of 80cm, is made of organic glass and is divided into an upper part and a lower partThe middle and lower three layers, the upper and middle layers are filled with fine sand (diameter between 0.25-0.35 mm) and coarse sand (diameter greater than 0.5 mm) to 2/3 of the height of each layer, respectively, and the lower layer is used for collecting sample liquid, and the sample liquid is passed around the device through a DIUMP 5550 peristaltic pump (Kamoer) with the speed of 5.8mL min -1 At a constant flow rate to give an initial concentration of 20mg L -1 The Cr (VI) solution is pumped into the apparatus. The Klebsiella-nano iron sulfide @ charcoal composite material is mixed with the fine sand on the upper layer. The baffle between upper strata and middle level to and middle level and lower floor is provided with a plurality of evenly distributed's hole that leaks, and the aperture size can let solution pass through, but the solid can't pass through.
The method is summarized in the research process of treating chromium-polluted underground water by using the bacteria-material composite environmental material, and is a chromium-polluted underground water remediation method which is simple to operate, low in cost, high in treatment efficiency and good in durability.
The invention has the advantages and positive effects that: (1) Compared with the traditional physical-chemical method for repairing chromium-polluted underground water, the Klebsiella has good chromium reducibility, and Fe in the nano FeS 2+ And S 2- The ion pair Cr (VI) has reduction capability, physical-chemical-biological ternary cooperation and high treatment efficiency; (2) The Klebsiella-nano FeS @ charcoal composite material adopts charcoal with good biocompatibility to fix bacteria and the nano material FeS, so that the shearing resistance of thalli is enhanced, the thalli is not easy to inactivate, nano agents are not easy to poison or agglomerate, the durability of environmental materials is enhanced, the treatment capacity of the environmental materials per unit weight to chromium-polluted groundwater is improved, and the cost is reduced; (3) The use of the Klebsiella with good chromium reduction performance can continuously play a role, and the risk of reoxidation of the reduced chromium Cr (III) is greatly reduced.
The nano FeS @ biochar and the Klebsiella are simple in material, cheap and easy to obtain, PBR constructed based on the Klebsiella-nano FeS @ biochar ternary synergistic composite is used for repairing the chromium-polluted underground water, the method is a physical-chemical-biological combined method for treating the chromium-polluted underground water with low cost, high efficiency and strong durability, and the treatment effect of the Klebsiella (BNCC 337014) -nano FeS @ biochar ternary composite for treating chromium-polluted wastewater is improved by 17.5% and 56.3% compared with the treatment effect of the Klebsiella (BNCC 337014) and the nano FeS @ biochar which are binary composites singly used.
The klebsiella (BNCC 337014) used in the present invention is k.
Drawings
FIG. 1: growth curves of Klebsiella.
FIG. 2 is a schematic diagram: SEM images of klebsiella; before Cr (VI) treatment; (c) Cr (VI) treatment; EDS analysis (b) before Cr (VI) treatment; and (d) Cr (VI).
FIG. 3: the Cr (VI) removing capability of the Klebsiella strain;
(a) Centrifuged versus non-centrifuged comparison, (b) Cr (VI) versus total chromium.
FIG. 4 is a schematic view of: SEM image of CMC-FeS @ biochar; before loading biochar; (b) After the biological carbon is loaded, (c) before the biological carbon is loaded by EDS analysis; and (d) after loading.
FIG. 5: ability of CMC-FeS @ biochar to remove Cr (VI).
FIG. 6: klebsiella-CMC-FeS @ charcoal SEM image and EDS analysis (a) Cr (VI) exists; (b) no Cr (VI), (c) Cr (VI) is contained; (d) Cr (VI) is not contained.
FIG. 7 is a schematic view of: the invention relates to the comparison of the effects of ternary composite materials, binary materials, unitary materials and the like on Cr (VI) removal.
FIG. 8: the ternary composite material has the result of treating 20mg/L Cr (VI) wastewater under different pH values.
FIG. 9: the ternary composite material has the result of treating 20mg/L Cr (VI) wastewater under different ionic strengths.
FIG. 10: the invention relates to a PRB simulation device diagram;
wherein: 1-fine sand reaction layer; 2-k. Variicola H12-CMC-fes @ biochar; 3-a first separator; 4-coarse sand reaction layer; 5-a second separator; 6-a sampling chamber; 7-a peristaltic pump; 8-glass bottle; 9-Cr (VI) solution;
note: a plurality of water leakage holes are uniformly distributed on each layer of the partition plate.
Detailed Description
The following examples are intended to further illustrate the invention without limiting it.
The ternary composite material in the embodiment of the invention is prepared as follows:
(1) Preparation of biochar (biochar): pyrolyzing one or more biomass waste materials such as wheat straw and straw in a muffle furnace at 600 ℃ for 2 hours (under oxygen limitation condition) to obtain biochar with the particle size of 1-3mm.
(2) Preparing CMC-FeS @ biochar: and (2) applying the biochar prepared in the step (1) to the production of CMC-FeS @ biochar. In N 2 While purging the solution, 0.870g of FeSO 4 ·7H 2 O dissolved in 500mL deionized water and N 2 (>99%) was deoxygenated for 1 hour. Then, 27.5mL of a 1% CMC solution was added to the above solution. Next, 275mg of biochar was introduced to the mixture for 1 hour with strong magnetic stirring. Finally, 22.5mL of sodium sulfide solution (33.4 g/L) was added to the suspension, prepared to give a CMC-FeS @ charcoal suspension which was sealed and aged for 24h, filtered with suction and treated with N 2 Purified deionized water wash to remove Na 2 SO 4 And finally freeze-drying and storing. (3) culturing Klebsiella: inoculating the Klebsiella into LB liquid culture medium for enrichment culture. The initial pH of the culture is 4-8, the temperature is 30 ℃, and the rotation speed of a shaking table is 150rpm. Culturing to logarithmic phase, centrifuging culture solution at 5000rpm,10min and 20 deg.C to collect strain. Using bicarbonate buffer (2.5 g/LNaHCO) 3 2.5g/L NaCl, pH 4-8), then suspending the thallus in bicarbonate buffer solution to obtain a suspension with the concentration range of 10 7 -10 8 CFU/ml。
(4) Adding CMC-FeS @ biochar to the bacterial suspension obtained in step (3) to a final concentration of 0.25g L -1 (ii) a The load type Klebsiella-nano FeS @ charcoal ternary composite material is prepared.
(5) The Klebsiella pneumoniae-nano FeS @ charcoal ternary composite material is prepared into a PBR wall curtain for remedying the chromium-polluted underground water.
Example 1:
the wastewater containing 20mg/L Cr (VI) is treated, the pH value is controlled to be 6.0, and the ionic strength is controlled to be 100mM (nitrate ions after sodium nitrate is added, and the actual wastewater is simulated). In the experimental process, the strain dosage and the chemical material dosage are kept consistent among all groups. After 10h of treatment, the removal rates of the CMC-FeS @ biochar group (the mass of the nano FeS @ charcoal in the Klebsiella (BNCC 337014) -nano FeS @ charcoal ternary composite material group) and the Klebsiella (BNCC 337014) (single bacterium) group (the bacterium liquid cultured to the logarithmic phase by the LB liquid culture medium is directly added during chromium removal, the number of the bacterium liquid is the same as that in the Klebsiella (BNCC 337014) -nano FeS @ charcoal ternary composite material group) and the Klebsiella (BNCC 337014) -nano FeS @ charcoal ternary composite material group to Cr (VI) are respectively 61.8%,82.2% and 96.6%.
The Klebsiella (BNCC 337014) -nano FeS @ charcoal of the invention is adopted to treat the waste water of 20mg/L Cr (VI) under different pH values, including pH values of 2,4,6,8 and 10;
from FIG. 8, the Cr (VI) removal effect under neutral conditions is superior to that of the other groups; under the conditions of alkalescence and alkalinity, the removal efficiency of K.variicola H12-CMC-FeS @ biochar on Cr (VI) is lower than that under the conditions of neutrality and subacidity, which shows that the environment of K.variicola H12-CMC-FeS @ biochar has better effect under the conditions of neutrality or subacidity in the process of treating Cr (VI). However, when the pH of the underground water containing Cr (VI) is strong, the removal efficiency of K.variicola H12-CMC-FeS @ biochar on Cr (VI) is obviously reduced, and the removal efficiency is not much different from that under alkaline conditions and moderately alkaline conditions. This is probably because the peracid over-alkali environment will hinder the reduction and adsorption of Cr (VI) by K.variicolH12-CMC-FeS @ biochar. The pH is preferably 4 to 6.
The Klebsiella (BNCC 337014) -nano FeS @ charcoal of the invention is adopted to treat 20mg/L Cr (VI) wastewater under the condition of different ionic strengths, which comprises nitrate 0mM,50mM,100mM,200mM, 300mM. From FIG. 9, it can be seen that K.variicola H12-CMC-FeS @ biochar does not show the same tendency for Cr (VI) removal efficiency in the range of ionic strength of 0 to 300mM, but in general, the greater the ionic strength, the lower the Cr (VI) removal efficiency. In the absence of other ion interference, the K.variicola H12-CMC-FeS @ biochar has the highest Cr (VI) removal efficiency, which shows that the change of the ionic strength can influence the Cr (VI) treatment effect, and the conclusion is also provided for practical application.
Example 2:
a certain amount of Klebsiella-CMC-FeS @ charcoal and sand (weight ratio 1: 30) are mixed together and added into the PRB device, pH is controlled to be 6.0, ionic strength is controlled to be 100mM, and waste water containing 25mg/L of Cr (VI) is treated by a peristaltic pump at a constant flow rate of 5.18mL min -1 And pumping into a PRB device, wherein when the solid-liquid ratio is 30:1 (sand: liquid = kg: L), treatment 3.2h, cr (vi) removal efficiency was about 98.7%.
Example 3:
a certain amount of Klebsiella-CMC-FeS @ charcoal and sand (weight ratio 1: 30) are mixed together and added into the PRB device, pH is controlled to be 3.0 and ionic strength is controlled to be 200mM, and waste water containing 25mg/L of Cr (VI) is pumped into the PRB device at a constant flow rate through a peristaltic pump. When the solid-liquid ratio is 20:1 (sand: liquid = Kg: L), and the Cr (vi) removal efficiency was about 94.0% at 4.8h of treatment.
Comparing the Klebsiella, the CMC-FeS @ charcoal binary composite material and the Klebsiella-CMC-FeS @ charcoal ternary composite material (the materials are all from the example 1) and the chromium removal effect:
1. characteristics of Klebsiella
1. Growth curves of Klebsiella
The Klebsiella reaches the logarithmic phase within 2-16h, the bacteria rapidly grow and reproduce, and the plateau phase is reached after 20 h. See fig. 1.
2. SEM-EDS analysis of Klebsiella, see FIG. 2. In the absence of Cr (VI), as shown in FIG. 2 (a), the cells were short rod-shaped with some shrinkage on the surface and had a length of about 0.5 to 1 μm. The main elements are three elements of C, N and O, and are shown in figure 2 (b). In the case of stress with Cr (VI) added, some cells were disrupted and adhered to each other, as shown in FIG. 2 (c). EDS analysis shows that the main elements of the strain have Cr besides C, N and O, and the result is shown in figure 2 (d), which shows that the strain has adsorption effect on chromium in the solution when the chromium exists.
3. The adsorption and reduction of Cr (VI) by Klebsiella species, FIG. 3,
(a) Centrifuge versus non-centrifuge, (b) Cr (VI) versus total chromium;
the solution in FIG. 3 (a) that was not centrifuged was consistently higher in Cr (VI) than the centrifuged group, probably because after centrifugation the seed species in the sample precipitated at the bottom of the EP tube, whereas adsorption of Cr (VI) by the seed species resulted in a fraction of Cr (VI) precipitating with the seed species and not in the supernatant, resulting in a lower Cr (VI) concentration in the final assay sample. And the strains of the group which are not centrifuged do not precipitate, and the Cr (VI) concentration in the sample solution is higher finally.
The concentrations of Cr (VI) and total chromium at various time points are shown in FIG. 3 (b), and the results of the experiment show that the sample solution has a lower Cr (VI) concentration than total chromium at each time point, indicating that a portion of the Cr (VI) is reduced to Cr (III) by Klebsiella. The concentration difference between Cr (VI) and total chromium is the concentration of Cr (III). The above experiments show that in the presence of Cr (VI), klebsiella has an adsorbing and reducing effect on Cr (VI).
2. CMC-FeS @ charcoal binary composite material characteristic
1. SEM-EDS analysis of CMC-FeS @ biochar)
FIG. 4 is an SEM image (a) before biochar loading; (b) After the loading of the biochar, (a) before the loading of the biochar by EDS analysis; and (b) after loading.
Fig. 4 (a) biochar has abundant pores and rough surface, resulting in larger specific surface area and pore volume, thereby creating more adsorption sites, which makes FeS adsorbed on biochar in large quantities and more uniform. In contrast to biochar, very clear particulate matter with aggregate diameter less than 100nm can be observed on the surface of biochar in fig. 4 (b). This indicates that irregular particles (CMC-FeS @ biochar) are attached to the biochar surface. As can be seen from fig. 4 (C), the EDS detects C, O, si, ca, which are main constituent elements of the biochar. In the biochar-loaded samples, the presence of the elements Fe and S was detected on the surface of the material, see fig. 4 (d). This preliminarily demonstrates the successful loading of FeS on the biochar surface.
2. Capability of CMC-FeS @ biochar in removing Cr (VI)
In FIG. 5, the Cr (VI) concentration in the solution rapidly decreases within the first two hours, and it is possible that when the CMC-FeS @ charcoal material exists, the porous structure provides a large number of adsorption sites for Cr (VI), and the Cr (VI) in the solution is rapidly transferred from the solution to the surface of the CMC-FeS @ charcoal. After two hours, the concentration of Cr (VI) in the solution slowly decreases to be close to steady, and the highest removal rate of Cr (VI) reaches 84 percent.
3. Klebsiella-CMC-FeS @ charcoal ternary composite material characteristic
1. FIG. 6 Krebs-CMC-FeS @ charcoal SEM image and EDS analysis (a) no Cr (VI); (b) with Cr (VI), (c) without Cr (VI); and (d) Cr (VI).
As can be seen from FIG. 6 (a), a large amount of Klebsiella is adsorbed on the surface of the CMC-FeS @ charcoal material, EDS analysis and detection are carried out on the surface of the material, and the existence of N element is found as shown in FIG. 6 (c). This indicates that CMC-FeS @ biochar has formed a complex with Klebsiella. When the potassium dichromate solution is added into the solution, the SEM image of the Klebsiella-CMC-FeS @ biochar is shown in figure 6 (b), the Klebsiella is attached to the surface of the CMC-FeS @ biochar and is more uniform compared with the condition that Cr (VI) does not exist, and the EDS analysis finds that chromium elements exist on the surface of the CMC-FeS @ biochar as shown in figure 6 (d). Shows that the adsorption action exists between the Klebsiella-CMC-FeS @ biochar and the chromium.
2. Crabb-CMC-FeS @ biochar ternary composite material has effect of removing Cr (VI)
In general, the removal rate of Cr (VI) is as follows: klebsiella (H12) + chemical substance mixed group (Klebsiella + charcoal, klebsiella + FeS, klebsiella-CMC-FeS @ charcoal) > Single bacterium H12 group > chemical substance group (charcoal, feS, CMC-FeS @ charcoal).
The number of the bacteria in the group containing the Klebsiella is the same;
the same raw materials in each group are used in the same amount.
The CMC-FeS is the nano FeS prepared by the CMC method.
After 10 hours of experiment, the Cr (VI) removal rates of the CMC-FeS @ charcoal group, the single-bacterium H12 group and the bacteria H12+ CMC-FeS @ charcoal mixed group are 61.8 percent, 82.2 percent and 96.6 percent respectively, the Cr (VI) removal rates of the bacteria H12+ CMC-FeS @ charcoal system are improved by 1.6 times and 1.2 times respectively, and the Cr (VI) removal effect is optimal. CMC-FeS @ charcoal surface adsorption and reduction are the main removal mechanisms in the chromium removal process. The mechanism of Cr (VI) removal during reduction depends primarily on Fe 2+ And S 2- Reducing property of (2). In the foregoing, it was confirmed that there was surface adsorption and reduction of the main mechanism of Cr (VI) removal by Klebsiella. Compared with a CMC-FeS @ biochar and single bacteria treatment system, the removal efficiency of Cr (VI) is greatly improved in a Klebsiella-CMC-FeS @ biochar mixed system. This shows that in the mixed system, the Klebsiella and CMC-FeS @ biochar are synergistic in the Cr (VI) treatment process, but the removal efficiency of the Klebsiella and CMC-FeS @ biochar is not the additive effect.
In the 6 th hour, the removal rate of Cr (VI) in the Klebsiella and CMC-FeS @ biochar mixed system reaches the highest value firstly, and when the heavy metal Cr (VI) with the same quantity is treated, other experimental groups have longer treatment time and lower removal rate compared with the Klebsiella and CMC-FeS @ biochar system.
Compared with the study of sulfide/charcoal binary composite environmental materials reported by Liu et al, the treatment time of the Klebsiella and CMC-FeS @ charcoal system is shortened by about 1/6 under the same condition, and the efficiency is improved by 1.05 times. In situ remediation, some researchers have used nZVI and other chemical methods, which can be more than 95% efficient. But the widespread use of these chemicals causes secondary pollution to the surrounding environment. The conclusion proves that the Klebsiella-CMC-FeS @ charcoal system has the advantages of high efficiency, environmental protection and the like in the aspect of treating the underground water polluted by Cr (VI).
FIG. 7 is a comparison of the effects of ternary composites, binary materials, unitary materials, etc. on Cr (VI) removal.
Claims (10)
1. A composite material based on Klebsiella-nano iron sulfide @ charcoal is characterized in that the composite material is formed by loading Klebsiella and nano iron sulfide on charcoal.
2. The method for preparing the composite material according to claim 1, wherein the composite material is prepared by adding the biochar loaded with the nano iron sulfide to the klebsiella suspension.
3. The preparation method according to claim 2, wherein the biochar loaded with the nano iron sulfide is prepared by adding the biochar in the preparation process of the nano iron sulfide, preferably by adopting a CMC (carboxyl methyl cellulose) method.
4. The production method according to claim 3,
the preparation process of the charcoal loaded with the nano iron sulfide comprises the following steps: in N 2 In the purging solution, the ferrous compound is dissolved in deionized water and used>99％N 2 Deoxidizing; then adding CMC solution; continuously introducing the biochar under strong magnetic stirring, and finally slowly adding the solution of the sulfur-containing compound into the mixed suspension to prepare the biochar; the sulfur-containing compounds include: at least one of sodium sulfide, sodium thiosulfate and sodium sulfite.
5. The method of claim 4, wherein the ferrous compound comprises FeSO 4 Dissolving in deionized water to prepare FeSO with the concentration of 1-5g/L 4 And (3) solution.
6. The preparation method according to claim 4, wherein the addition amount of the biochar is 500-600mg/L, the preparation concentration of the sulfur compound solution is 30-40g/L, the volume ratio of the sulfur compound solution to the mixed suspension is not more than 0.1, and the FeS: CMC: the mass ratio of the biochar is 0.8-1.2: 0.8 to 1.2;0.8 to 1.2.
7. The method of claim 2, wherein the concentration of the Klebsiella bacterium suspension is in the range of 10 7 -10 8 CFU/ml, and the particle size range of the biochar is 1-3mm.
8. The method of claim 2, wherein the nano-iron sulfide-loaded biochar is added to the bacterial suspension to a final concentration0.1-0.5g L -1 。
9. The application of the Klebsiella-nano iron sulfide @ charcoal-based composite material in removing chromium in claim 1.
10. The application of claim 9, wherein the chromium-polluted groundwater is repaired by constructing a PBR wall curtain based on the Klebsiella-nano iron sulfide @ biochar composite material.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005014777A2 (en) * | 2002-10-16 | 2005-02-17 | Board Of Regents, The University Of Texas System | Methods and compositions for increasing the efficacy of biologically-active ingredients |
| CN106966456A (en) * | 2016-01-14 | 2017-07-21 | 南开大学 | A kind of preparation method and application of ferrous sulfide/biology carbon composite |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005014777A2 (en) * | 2002-10-16 | 2005-02-17 | Board Of Regents, The University Of Texas System | Methods and compositions for increasing the efficacy of biologically-active ingredients |
| CN106966456A (en) * | 2016-01-14 | 2017-07-21 | 南开大学 | A kind of preparation method and application of ferrous sulfide/biology carbon composite |
Non-Patent Citations (1)
| Title |
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| RUNLAN YU等: "A high-efficiency Klebsiella variicola H12-CMC-FeS@biochar for chromium removal from aqueous solution", 《SCIENTIFIC REPORTS》, vol. 11, no. 1, pages 2 - 3 * |
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