CN114272905A - Chitosan-biological iron-manganese oxide material and preparation method and application thereof - Google Patents
Chitosan-biological iron-manganese oxide material and preparation method and application thereof Download PDFInfo
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- WQHONKDTTOGZPR-UHFFFAOYSA-N [O-2].[O-2].[Mn+2].[Fe+2] Chemical compound [O-2].[O-2].[Mn+2].[Fe+2] WQHONKDTTOGZPR-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000000463 material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002351 wastewater Substances 0.000 claims abstract description 39
- 229920001661 Chitosan Polymers 0.000 claims abstract description 29
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 27
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 25
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- 238000000034 method Methods 0.000 claims description 29
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- 239000001963 growth medium Substances 0.000 claims description 15
- 229910001868 water Inorganic materials 0.000 claims description 15
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- 239000011572 manganese Substances 0.000 claims description 11
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- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 7
- -1 iron ions Chemical class 0.000 claims description 6
- 229910000616 Ferromanganese Inorganic materials 0.000 claims description 5
- 229910001437 manganese ion Inorganic materials 0.000 claims description 5
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- 238000011081 inoculation Methods 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims description 4
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- 238000001179 sorption measurement Methods 0.000 description 13
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 9
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- 238000002474 experimental method Methods 0.000 description 6
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- FRHBOQMZUOWXQL-UHFFFAOYSA-L ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 description 4
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- 239000004313 iron ammonium citrate Substances 0.000 description 4
- 235000000011 iron ammonium citrate Nutrition 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
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- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 3
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- UCXOJWUKTTTYFB-UHFFFAOYSA-N antimony;heptahydrate Chemical compound O.O.O.O.O.O.O.[Sb].[Sb] UCXOJWUKTTTYFB-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a chitosan-biological iron manganese oxide material and a preparation method and application thereof, the material takes chitosan as a carrier, biological iron manganese oxide is polymerized together to form a spherical composite material, and the preparation method comprises the following steps: 1) screening iron-manganese oxidizing bacteria from mine wastewater and domesticating; 2) the biological iron-manganese oxide is prepared by culturing, centrifuging, freeze drying and grinding the flora; 3) mixing chitosan: the biological iron-manganese oxide is 1:4, the material is applied to the treatment of antimony-containing model wastewater, the composite material can not only remove single-valence antimony, but also simultaneously remove mixed-valence antimony, and the preparation method is simple, stable in reaction, strong in operability, environment-friendly and has wide engineering application potential.
Description
Technical Field
The invention relates to the technical field of functional materials for treating antimony-containing wastewater, in particular to a chitosan-biological iron-manganese oxide material and a preparation method and application thereof.
Background
Antimony exists mainly in the form of sulfide and oxide in nature, has wide application, can be used for automobile brake lining materials, semiconductor elements, battery grids, bearings, power transmission equipment, pipelines, paint pigments and the like, and also can be used as an additive to be applied to glassware and ceramics. As toxic metalloid elements, the toxicity of trivalent antimony is ten times higher than that of pentavalent antimony, and the pollution of antimony from nature and human sources seriously threatens the quality of drinking water and the health of human beings at present. In the 'surface water environmental quality standard' and 'sanitary standard for drinking water' of China, the limited concentration of antimony is set to be 5 mu g/L. Antimony is also recognized by the world health organization, the U.S. environmental protection organization, and the european community as a priority contaminant.
The prior method for removing antimony pollutants in water environment mainly comprises the technologies of an adsorption method, a coagulating sedimentation method, a membrane separation method, an electrochemical method, a microbial redox method and the like. The biological adsorption method has the advantages of high efficiency, environmental protection, strong recycling capability, no secondary pollution, simplicity, convenience and low price, and is widely applied. The common antimony-removing adsorption materials comprise biological iron-manganese oxidizing bacteria, biological carbon, seaweed, iron-manganese oxides and the like. The biological iron-manganese oxidizing bacteria gradually become a research hotspot by using multi-valent elements and good surface activity without secondary pollution.
In actual research, the biological iron-manganese oxide has the defects of easy agglomeration and difficult separation from a water body, and the removal efficiency of heavy metals and the recycling capability of materials are greatly influenced.
And bin, Wujizi and the like prepare a ferro-manganese oxide-microorganism loaded biomass charcoal material (FM-DB) to simultaneously remove Cd (II) and As (III) pollution in a water body. The optimal proportion of the iron-manganese oxide (FMBO) and the pecan peel biomass charcoal (CCSB) in the iron-manganese oxide-microorganism load biomass charcoal material is 3% + 3%, and the maximum removal rate of Cd (II) and As (III) in a binary system is up to 77.29% and 99.94%. However, the ferro manganese oxide-microorganism loaded biomass charcoal material prepared by the modified method in the scheme is difficult to recover from the suspension after being treated. Also, for example, Wang Hua Wei and Lu Zi Juan. And (4) removing the high-antimony leachate by loading the biological manganese oxide on the quartz sand. The environmental engineering technology innovation and the application are collected in discourse of (III) Ed. journal of Industrial building Co., Ltd., 2021,44-50. in the process, a quartz sand reactor is constructed, the removal effect of solid-phase layered polymeric biomanganese oxide generated by loading quartz sand on high-antimony leachate is researched, the removal rate of trivalent antimony by loading layered polymeric biomanganese oxide on quartz sand is in a trend of descending and then ascending in the operation process, and the surface microstructure analysis shows that a large amount of antimony is retained on the surface of quartz sand at the end of reaction, the antimony mainly exists in pentavalent manganese antimonate, and layered polymeric biomanganese oxide still exists. But the material is still in solution without removing pentavalent antimony.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a chitosan-biological iron-manganese oxide material and a preparation method and application thereof.
In order to achieve the purpose, the technical scheme provided by the invention is as follows: a chitosan-biological iron-manganese oxide material takes chitosan as a carrier, biological iron-manganese oxides are polymerized together to form a spherical composite material, and the mass ratio of the chitosan to the biological iron-manganese oxides is 1: 4.
The invention also provides a preparation method of the chitosan-biological iron-manganese oxide material, which comprises the following steps:
(1) screening, enriching and domesticating iron and manganese oxidation mixed strains of a water sample collected from mine wastewater to obtain iron and manganese oxidizing bacteria;
(2) continuously culturing the ferrimanganic oxidizing bacteria to obtain a biological ferrimanganic oxide material;
(3) and (3) preparing the biological iron-manganese oxide and chitosan to obtain the chitosan-biological iron-manganese oxide composite material.
Preferably, the screening, enriching and domesticating of the iron-manganese oxidizing mixed flora in the step (1) comprises: firstly, inoculating a wastewater sample to an enrichment culture medium by 10 percent of inoculation amount, carrying out constant-temperature shaking culture to obtain a ferro-manganese oxidation flora enrichment culture solution, and adjusting the pH value of the culture medium to 6.8-7.2; and then, exogenous manganese ions and iron ions are adopted to pass through a 0.22 mu m organic filter membrane after the preparation of the domestication culture medium is finished, and then are independently added, and the gradient domestication culture is carried out on the enriched culture solution of the iron-manganese oxidizing bacteria to obtain the iron-manganese oxidizing bacteria.
Preferably, the biological iron-manganese oxide precipitate is obtained after the culture solution rich in iron-manganese oxidizing bacteria is continuously cultured for 8-12 days, and the biological iron-manganese oxide material in the step (2) is obtained after uniform grinding.
Preferably, the method for preparing the chitosan-biological iron manganese oxide composite material in the step (3) comprises the following steps: weighing chitosan, dissolving the chitosan in HCl solution, adding the biological iron-manganese oxide material subjected to centrifugation and freeze drying into the solution, rinsing the biological iron-manganese oxide material by NaOH solution, and then repeatedly cleaning and drying the biological iron-manganese oxide material to obtain a solid material.
Preferably, the centrifugation condition of the biological iron-manganese oxide material is 8000rpm/min, and the freeze-drying time of the biological iron-manganese oxide material is 48 h; the concentration of the HCl solution is 0.2mol/L, the concentration of the NaOH solution is 0.4mol/L, the drying temperature is 55 ℃, and the drying time is 48 h.
The invention also provides the application of the chitosan-biological iron-manganese oxide material or the chitosan-biological iron-manganese oxide material prepared by the preparation method in the treatment of antimony-containing model wastewater.
The invention discloses a method for forming a porous structure gap by using chitosan as a load carrier and aggregating biological iron and manganese oxides generated by microbial metabolism. The composite material can remove antimony in a single valence state and can also remove antimony in a mixed valence state simultaneously. The preparation method comprises the following steps: 1) screening iron-manganese oxidizing bacteria from mine wastewater and domesticating; 2) the biological iron-manganese oxide is prepared by culturing, centrifuging, freeze drying and grinding the flora; 3) mixing chitosan: the biological iron-manganese oxide is 1:4, washing and drying to obtain the biological iron-manganese oxide-chitosan spherical composite material. The preparation process is simple, the reaction is stable, the operability is strong, the method can be used for removing the mixed valence antimony in the wastewater, the environment is friendly, and the method has wide engineering application potential.
The invention has the beneficial effects that:
1. the chitosan-biological iron-manganese oxide material used by the invention well solves the problem that the prior iron-manganese oxide removes mixed valence antimony pollutants, has larger specific surface area, and has adsorption capacity to the mixed valence antimony which is far larger than that of pure chitosan and chemically synthesized iron-manganese oxide to Sb (III) and Sb (V).
2. After the biological iron-manganese oxide and the chitosan are coated and compounded, a spherical adsorbent with a larger diameter is formed, the recovery capability of the adsorbent from a water body is stronger, and the reutilization property is more excellent. The biological iron-manganese oxide used in research is a precipitate formed after iron-manganese ions in a water body environment are removed by iron-manganese oxidizing bacteria, and antimony in wastewater is removed by using the precipitate, so that waste utilization is achieved, and the problem of secondary pollution is solved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a scanning electron microscope image of a biological Fe-Mn oxide material and a chitosan-biological Fe-Mn oxide material (CH-BFMO) in example 1 of the present invention;
FIG. 2 is XRD patterns of a biological Fe-Mn oxide material and a chitosan-biological Fe-Mn oxide material (CH-BFMO) in example 1 of the present invention;
FIG. 3 is Langmuir and Freundlich adsorption isotherms for CH-BFMO adsorption of Sb (III) and Sb (V) at different temperatures in example 2 of the present invention;
FIG. 4 is a graph showing the removal performance of CH-BFMO from a mixed solution of Sb (III) and Sb (V) in example 4 of the present invention;
FIG. 5 is a graph showing the effect of different pH and ionic strength on the adsorption of Sb (III) and Sb (V) by CH-BFMO in example 3 of the present invention.
Detailed Description
Reference will now be made in detail to the present preferred embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout.
Referring to fig. 1-5, in a preferred embodiment of the present invention, a chitosan-biological iron-manganese oxide material is prepared by polymerizing biological iron-manganese oxides together to form a spherical composite material, wherein the mass ratio of chitosan to biological iron-manganese oxide is 1: 4.
The invention also provides a preparation method of the chitosan-biological iron-manganese oxide material, which comprises the following steps:
(1) screening, enriching and domesticating iron and manganese oxidation mixed strains of a water sample collected from mine wastewater to obtain iron and manganese oxidizing bacteria;
(2) continuously culturing the ferrimanganic oxidizing bacteria to obtain a biological ferrimanganic oxide material;
(3) and (3) preparing the biological iron-manganese oxide and chitosan to obtain the chitosan-biological iron-manganese oxide composite material.
Further, the screening, enriching and domesticating of the iron-manganese oxidation mixed flora in the step (1) comprises the following steps: firstly, inoculating a wastewater sample to an enrichment culture medium by 10 percent of inoculation amount, carrying out constant-temperature shaking culture to obtain a ferro-manganese oxidation flora enrichment culture solution, and adjusting the pH value of the culture medium to 6.8-7.2; the culture temperature is 28-30 ℃; the rotating speed of the culture is 120 r/min; the enrichment medium comprises the following components: peptone 0.5g/L, glucose 0.3g/L, yeast extract powder 0.2g/L, MnSO4·H2O 0.2g/L，K2HPO4 0.1g/L，MgSO4·7H2O 0.2g/L，NaNO3 0.2g/L，CaCl2 0.1g/L，(NH4)2CO30.1g/L, 0.8g/L ferric ammonium citrate, and the domestication culture medium comprises the components of removing MnSO4·H2O and an enrichment medium of ammonium ferric citrate; secondly, exogenous manganese ions and iron ions are adopted to pass through an organic filter membrane of 0.22 mu m after the preparation of a domestication culture medium is finished, and then are independently added, and the gradient domestication culture is carried out on the enriched culture solution of the iron-manganese oxidizing bacteria to obtain the iron-manganese oxidizing bacteria; the concentration gradient of the exogenous manganese ions is 100-600mg/L, and the concentration gradient of the iron ions is 200-1200 mg/L.
Further, continuously culturing the enriched culture solution of the iron-manganese oxidizing bacteria group for 8-12 days to obtain biological iron-manganese oxide precipitate, and uniformly grinding to obtain the biological iron-manganese oxide material in the step (2).
Further, the method for preparing the chitosan-biological iron manganese oxide composite material in the step (3) comprises the following steps: weighing chitosan, dissolving the chitosan in HCl solution, adding the biological iron-manganese oxide material subjected to centrifugation and freeze drying into the solution, rinsing with NaOH solution, and drying after repeated washing to obtain a solid material.
Further, the centrifugation condition of the biological iron-manganese oxide material is 8000rpm/min, and the freeze drying time of the biological iron-manganese oxide material is 48 h; the concentration of the HCl solution is 0.2mol/L, the concentration of the NaOH solution is 0.4mol/L, the drying temperature is 55 ℃, and the drying time is 48 h.
The invention also provides the application of the chitosan-biological iron-manganese oxide material or the chitosan-biological iron-manganese oxide material prepared by the preparation method in the treatment of antimony-containing model wastewater.
The invention discloses a method for forming a porous structure gap by using chitosan as a load carrier and aggregating biological iron and manganese oxides generated by microbial metabolism. The composite material can remove antimony in a single valence state and can also remove antimony in a mixed valence state simultaneously. The composite material prepared by the preparation method disclosed by the invention is washed by water and dried to obtain the biological iron-manganese oxide-chitosan spherical composite material. The preparation process is simple, the reaction is stable, the operability is strong, the method can be used for removing the mixed valence antimony in the wastewater, the environment is friendly, and the method has wide engineering application potential.
As a preferred embodiment of the present invention, it may also have the following additional technical features:
example 1
The chitosan-biological iron-manganese oxide material (hereinafter referred to as CH-BFMO) in this embodiment takes chitosan as a load carrier to polymerize biological iron-manganese oxides together to form a spherical composite material. The chitosan: the mass ratio of the biological iron-manganese oxide is 1: 4.
in this embodiment, the specific preparation method of the chitosan-biological iron manganese oxide material is as follows:
1) inoculating 10% of water sample of acid mine wastewater to the sterilized enrichment medium, placing the enrichment medium in a shaking table at 28-30 ℃, and culturing at 120 r/min.
Further, the enrichment medium components comprise peptone 0.5g/L, glucose 0.3g/L, yeast extract powder 0.2g/L, MnSO4·H2O 0.2g/L，K2HPO4 0.1g/L，MgSO4·7H2O 0.2g/L，NaNO3 0.2g/L，CaCl2 0.1 g/L，(NH4)2CO30.1g/L, 0.8g/L ferric ammonium citrate, and adjusting the pH value of the culture medium to 6.8-7.2;
during the period, samples are taken every day, the bacteria concentration in the flora is measured by using an ultraviolet spectrophotometer under the wavelength of 660nm, and the contents of Mn and Fe in the samples are measured. When the formation of a precipitate was observed in the culture medium in the Erlenmeyer flask, the formation amount of manganese oxide was measured by the LBB method.
Secondly, acclimating the iron-manganese oxidizing bacteria by adopting a concentration gradient method, wherein a culture medium used for removing MnSO is adopted for acclimation4·H2Enriched medium of O and ferric ammonium citrate, exogenous Mn (II) and Fe (II) after the preparation of the culture medium is finishedAfter passing through a 0.22 μm organic filter, the mixture was added separately.
Setting the concentration of Mn (II) as 100mg/L,200mg/L,300mg/L,400mg/L,500mg/L and 600 mg/L; setting the concentration of Fe (II) to 200mg/L,400mg/L,600mg/L,800mg/L,1000mg/L and 1200 mg/L;
then, PYCM modified culture medium with Mn (II) content of 520mg/L and Fe (II) content of 100mg/L is selected for flora culture to obtain activated ferro-manganese oxidizing flora.
2) Inoculating the activated ferrimanganic oxidizing bacteria according to the inoculation amount of 2%, and continuously culturing for 12 days in a constant-temperature gas bath incubator at 30 ℃ and 120rpm to obtain a large amount of biological ferrimanganic oxide precipitates.
And then, precipitating the biological iron-manganese oxide at 8000rpm, centrifuging, filtering to remove supernatant after centrifugation, repeatedly washing the precipitate with deionized water for three times, placing the precipitate in a vacuum freeze dryer for 48 hours, and finally, uniformly grinding the freeze-dried biological iron-manganese oxide, and storing the ground biological iron-manganese oxide in a dry place for later use.
Finally, dissolving chitosan in 0.2mol/L HCl, uniformly mixing the biological iron-manganese oxide and the chitosan according to the mass ratio of 4:1, transferring the mixture into a 20mL syringe with a needle, slowly dripping the mixed liquid into 0.4mol/L NaOH through the needle at the front end of the syringe, repeatedly washing the obtained particles with deionized water to neutrality, and then placing the particles in a 55 ℃ drying oven for 48 hours to obtain the biological iron-manganese oxide-chitosan spherical composite material.
Further, the chitosan is accurately weighed by 2g, and the prepared biological iron-manganese oxide is 8g
Further, 100mL of the 0.2mol/L HCl solution was required.
As shown in fig. 1 and 2, BFMO is a loose porous structure, presenting a honeycomb shape, in contrast to the CH-BFMO structure, which is more compact and more evenly distributed in the product, and both are amorphous structures.
Example 2
Simulated wastewater treatment containing trivalent antimony and pentavalent antimony at different temperatures by respectively using the chitosan-biological iron-manganese oxide material prepared in example 1 as an adsorbent, and the specific steps are as follows:
first, preparation of a standard stock solution of sb (iii): 1.3708g of antimony potassium tartrate hemihydrate were accurately weighed into deionized water using an electronic analytical balance and were brought to volume in a 1000mL volumetric flask at a concentration of 0.5g/L, and the prepared standard stock solution of Sb (III) was placed in a refrigerator for storage. 40mg/L of simulation wastewater containing Sb (III) and mixed simulation wastewater with two valence states required in the subsequent experiment are prepared by taking the 0.5g/L Sb (III) standard stock solution as a mother solution.
Next, preparation of sb (v) standard stock solution: 2.1739g of potassium pyroantimonate is accurately weighed and poured into a 500mL clean beaker, a proper amount of deionized water is added, the beaker is placed into an ultrasonic cleaner to be heated and dissolved, when the solution is transparent, the solution is cooled to room temperature, the volume is determined in a 1000mL volumetric flask, and the volumetric flask is also placed in a refrigerator to be stored. 40mg/L of simulation wastewater containing Sb (V) and mixed simulation wastewater with two valence states, which are required in the subsequent experiment, are prepared by taking the 1g/L of Sb (V) standard stock solution as a mother solution.
0.06g of CH-BFMO was added to a 100mL polyethylene bottle, and 50mL of 40mg/L of the formulated Sb (III) and Sb (IV) simulated wastewater was added, maintaining the pH at 4.0 + -0.2.
Shaking up, placing in a water bath constant temperature oscillation box at 30 ℃, oscillating at 170rpm,
then sampling is carried out for 5 min, 10 min, 15 min, 20 min, 30 min, 40 min, 60 min, 120 min, 180 min, 240 min, 360 min, 480 min and 600min, filtrate is taken after the sample passes through a 0.22 mu m micro-filtration membrane (organic system), and the concentrations of the residual Sb (III) and Sb (IV) in the filtrate are determined.
By setting different reaction temperatures at 20, 30 and 40 ℃,
as shown in the attached FIG. 3, in the Langmuir model, the adsorption capacity of CH-BFMO to Sb (III) and Sb (V) also increases with the temperature rise, and at 40 ℃, the adsorption capacity to Sb (III) and Sb (V) can reach 51.02mg/g and 34.60mg/g at the maximum.
Example 3
The simulated wastewater containing trivalent antimony and pentavalent antimony prepared in example 2 was treated at different pH with the chitosan-biological iron manganese oxide material prepared in example 1 as an adsorbent, and the specific steps were as follows:
the method is carried out in a 100mL plastic bottle, and the initial pH value of the solution is sequentially adjusted by using 0.1mol/L NaOH or HCl;
1) in a simulated wastewater experiment containing the trivalent antimony, the pH value of wastewater is maintained at 4.0 +/-0.2:
a. 50mL of simulated wastewater containing trivalent antimony of 40mg/L is added into a 100mL plastic bottle, 0.06g of CH-BFMO prepared in example 1 is added, the pH is adjusted to 3.0, the solution is cultured for 3 hours under shaking at 170r/min,
b. 50mL of simulated wastewater containing trivalent antimony of 40mg/L is added into a 100mL plastic bottle, 0.06g of CH-BFMO prepared in example 1 is added, the pH is adjusted to 4.0, the solution is cultured for 3 hours under shaking at 170r/min,
c. 50mL of simulated wastewater containing trivalent antimony of 40mg/L is added into a 100mL plastic bottle, 0.06g of CH-BFMO prepared in example 1 is added, the pH is adjusted to 5.0, the solution is cultured for 3 hours under shaking at 170r/min,
d. 50mL of simulated wastewater containing trivalent antimony 40mg/L is added into a 100mL plastic bottle, 0.06g of CH-BFMO prepared in example 1 is added, the pH is adjusted to 6.0, the solution is cultured for 3 hours under shaking at 170r/min,
2) in a simulation wastewater experiment containing pentavalent antimony, the pH value of wastewater is maintained at 6.0 +/-0.2:
a. 50mL of simulated wastewater containing pentavalent antimony is added into a 100mL plastic bottle, 0.06g of CH-BFMO prepared in example 1 is added, the pH is adjusted to 3.0, the solution is cultured for 4 hours under shaking at 170r/min,
b. 50mL of simulated wastewater containing pentavalent antimony is added into a 100mL plastic bottle, 0.06g of CH-BFMO prepared in example 1 is added, the pH is adjusted to 4.0, the solution is cultured for 4 hours under shaking at 170r/min,
c. 50mL of simulated wastewater containing pentavalent antimony is added into a 100mL plastic bottle, 0.06g of CH-BFMO prepared in example 1 is added, the pH is adjusted to 5.0, the solution is cultured for 4 hours under shaking at 170r/min,
d. 50mL of simulated wastewater containing pentavalent antimony is added into a 100mL plastic bottle, 0.06g of CH-BFMO prepared in example 1 is added, the pH is adjusted to 6.0, the solution is cultured for 4 hours under shaking at 170r/min,
e. 50mL of simulated wastewater containing pentavalent antimony is added into a 100mL plastic bottle, 0.06g of CH-BFMO prepared in example 1 is added, the pH is adjusted to 7.0, the solution is cultured for 4 hours under shaking at 170r/min,
f. 50mL of simulated wastewater containing pentavalent antimony is added into a 100mL plastic bottle, 0.06g of CH-BFMO prepared in example 1 is added, the pH is adjusted to 8.0, the solution is cultured for 4 hours under shaking at 170r/min,
g. 50mL of simulated wastewater containing pentavalent antimony is added into a 100mL plastic bottle, 0.06g of CH-BFMO prepared in example 1 is added, the pH is adjusted to 9.0, the solution is cultured for 4 hours under shaking at 170r/min,
h. 50mL of simulated wastewater containing pentavalent antimony is added into a 100mL plastic bottle, 0.06g of CH-BFMO prepared in example 1 is added, the pH is adjusted to 10.0, the solution is cultured for 4 hours under shaking at 170r/min,
three replicates were set up for each pH experiment.
3) And taking out samples after balancing, and respectively measuring the residual Sb concentration of each sample. The adsorption capacity of the adsorbent is shown in figure 4, the initial pH of the solution is increased, the adsorption of Sb (III) by CH-BFMO is gradually reduced, the adsorption amount of Sb (III) is maximum at the pH of 4.0, and the Sb (V) is adsorbed by CH-BFMO under the optimal pH condition at the pH of 6.0.
Example 4
Static adsorption experiments on the mixed solutions of Sb (III) and Sb (V) by respectively using the chitosan-biological iron manganese oxide material prepared in example 1 as an adsorbent comprise the following specific steps:
1) preparing a mixed-state valence antimony solution: sb (III) and Sb (V) with the same concentration are prepared into a mixed solution of 40mg/L of Sb (III) and Sb (V) according to the proportion of 1:1, namely the mixed solution contains 20mg/L of Sb (III) and 20mg/L of Sb (V).
First, 0.06g of CH-BFMO was accurately weighed into a 100mL polyethylene plastic bottle, and then 50mL of a 40mg/L prepared mixed solution of Sb (III) and Sb (V) was added, maintaining the pH at 4.0. + -. 0.2. Shaking, placing in a water bath constant temperature oscillation tank at 30 deg.C, oscillating at 170rpm for reaction, sampling at 5, 10, 15, 20, 30, 40, 60, 120, 180, 240, 360, 480, and 600min, filtering with 0.22 μm microporous membrane (organic system), collecting filtrate, and determining the concentration of residual total antimony in the filtrate.
Each set of samples was set in triplicate.
The above additional technical features can be freely combined and used in superposition by those skilled in the art without conflict.
The above description is only a preferred embodiment of the present invention, and the technical solutions that achieve the objects of the present invention by basically the same means are all within the protection scope of the present invention.
Claims (7)
1. A chitosan-biological iron manganese oxide material is characterized in that: the material takes chitosan as a carrier, biological iron and manganese oxides are polymerized together to form a spherical composite material, and the mass ratio of the chitosan to the biological iron and manganese oxides is 1: 4.
2. A preparation method of chitosan-biological iron manganese oxide material is characterized by comprising the following steps: the method comprises the following steps:
(1) screening, enriching and domesticating iron and manganese oxidation mixed strains of a water sample collected from mine wastewater to obtain iron and manganese oxidizing bacteria;
(2) continuously culturing the ferrimanganic oxidizing bacteria to obtain a biological ferrimanganic oxide material;
(3) and (3) preparing the biological iron-manganese oxide and chitosan to obtain the chitosan-biological iron-manganese oxide composite material.
3. The method for preparing chitosan-biological iron manganese oxide material according to claim 2, wherein the method comprises the following steps: the screening, enrichment and domestication of the iron-manganese oxidation mixed flora in the step (1) comprises the following steps: firstly, inoculating a wastewater sample to an enrichment culture medium by 10 percent of inoculation amount, carrying out constant-temperature shaking culture to obtain a ferro-manganese oxidation flora enrichment culture solution, and adjusting the pH value of the culture medium to 6.8-7.2; and then, exogenous manganese ions and iron ions are adopted to pass through a 0.22 mu m organic filter membrane after the preparation of the domestication culture medium is finished, and then are independently added, and the gradient domestication culture is carried out on the enriched culture solution of the iron-manganese oxidizing bacteria to obtain the iron-manganese oxidizing bacteria.
4. The method for preparing chitosan-biological iron manganese oxide material according to claim 3, wherein the method comprises the following steps: and (3) continuously culturing the enriched culture solution of the iron-manganese oxidizing bacteria group for 8-12 days to obtain biological iron-manganese oxide precipitate, and uniformly grinding to obtain the biological iron-manganese oxide material in the step (2).
5. The method for preparing chitosan-biological iron manganese oxide material according to claim 4, wherein the method comprises the following steps: the method for preparing the chitosan-biological iron manganese oxide composite material in the step (3) comprises the following steps: weighing chitosan, dissolving the chitosan in HCl solution, adding the biological iron-manganese oxide material subjected to centrifugation and freeze drying into the solution, rinsing the biological iron-manganese oxide material by NaOH solution, and then repeatedly cleaning and drying the biological iron-manganese oxide material to obtain a solid material.
6. The method for preparing chitosan-biological iron manganese oxide material according to claim 5, wherein the method comprises the following steps: the centrifugation condition of the biological iron-manganese oxide material is 8000rpm/min, and the freeze drying time of the biological iron-manganese oxide material is 48 h; the concentration of the HCl solution is 0.2mol/L, the concentration of the NaOH solution is 0.4mol/L, the drying temperature is 55 ℃, and the drying time is 48 h.
7. The application of the chitosan-biological iron-manganese oxide material as claimed in claim 1 or the chitosan-biological iron-manganese oxide material obtained by the preparation method as claimed in any one of claims 2 to 6 in the treatment of model wastewater containing antimony.
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