CN109225151A - Microorganism nano complex and the preparation method and application thereof - Google Patents
Microorganism nano complex and the preparation method and application thereof Download PDFInfo
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- CN109225151A CN109225151A CN201811205924.XA CN201811205924A CN109225151A CN 109225151 A CN109225151 A CN 109225151A CN 201811205924 A CN201811205924 A CN 201811205924A CN 109225151 A CN109225151 A CN 109225151A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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Abstract
The invention belongs to technical field of sewage, a kind of microorganism nano complex is disclosed, it includes microbial strains and metal oxide nanoparticles that it, which constructs component, as fixation support, microbial strains are carried on the metal oxide nanoparticles and construct to form the complex metal oxide nanoparticles.The preparation method of this microorganism nano complex includes mixing microbial strains and metal oxide nanoparticles to be scattered in liquid；4h is reacted under the conditions of being placed in 100 DEG C；Magnetic Isolation after reaction to obtain the final product.Microbial strains of the present invention select bacterial strain Fusarium oxysporum FP-JCCW.The invention also discloses the applications of microorganism nano complex thallium in adsorbed water body, have stronger adsorption capacity, can be used for the repairing and treating of water body thallium pollution, can be used as untapped environment functional material.
Description
Technical field
The invention belongs to technical field of sewage, are related to a kind of high performance composite, this high performance composite is at this
It is known as microorganism nano complex in invention, is the function adsorption material being combined by metal nano material and microbial strains
Material.The present invention gives the preparation method of the microorganism nano complex, and its application in thallium pollution recovery project.
Background technique
A kind of metallic element of high degree of dispersion of element thallium (Tl), belong to hypertoxic type, have it is accumulative, be strong Nervous toxicity
Object.It was found that thallium is 50-80mg to the minimum lethal dose of 70kg adult；The adult normal intake of thallium daily is about 0.056mg,
Daily highest thallium allows intake to be 2mg.If the content of thallium in environmental medium is near or above its threshold value, it is possible to human body
Health and environmental danger.
Thallium element has close stone and close sulphur duality, and the high degree of dispersion in the earth's crust, under specific condition, thallium can also be rich
Integrated mine simultaneously forms independent thallium minerals.Thallium high aggregation in Mine water flow and smelting wastewater, leads to the river near Mineralized Area
The content for flowing thallium in lake is usually very high.Meanwhile thallium is also enriched in containing the plant near Tl mining district, and be mainly distributed on root and
Ye Zhong, secondly in stem, fruit and stem tuber.Since the compound majority of thallium has high volatile, therefore can be with gas in smelting process
State form is migrated in an atmosphere.The ecological effect due to caused by environmental degradation and toxicity have apparent hysteresis, and thallium is dived
It is endangering and is threatening in fact seriously much more than its apparent effect.
Currently, the processing technique of waste water containing thallium mainly includes following methods: (1) chemical precipitation method, by alkaline condition
Thallium is removed to lower concentration by the method for lower precipitating from water body, simple process, easy to operate；But generally existing processing depth
Not enough, the defects of being unable to satisfy the emission request and safety standard of waste water containing thallium.(2) thallium can be enriched in one by ion-exchange
To recycle thallium as commercial product in the solution of a higher concentration, removal rate is high；But ion exchange resin is easily contaminated
Or oxidation and fail, frequently, operating cost height is not suitable for that water is very big, by the water source of heavy metal pollution concentration very little for regeneration
Water warfare.(3) physisorphtion can adsorb contents of many kinds of heavy metal ion, and adsorption capacity is big and has to heavy metal cation strong also
Original work are used；But sorbent used price is more expensive, and service life is short, needs to regenerate after reaching adsorption saturation, operating cost is higher.(4)
Biosorption process, can desorption cycle utilize, material price is low to be easy to get.
Wherein, biosorption process because its have the characteristics that except thallium it is high-efficient, by external interference condition it is small become prospect it is most wide
The wealthy method for removing thallium in water removal.Biological adsorption as a new process can be used for the removal of metal and containing the industry of heavy metal
In terms of the removing toxic substances of sewage, on the other hand, be saturated what the desorption of deposited metal in biological adsorption agent was easily accomplished because they
It is easy to release from adsorbent in washing lotion, at the same time, biological adsorption agent is also regenerated, convenient for recycling.
These advantages and low-down biological adsorption agent price make it have very high commercial value, in terms of the environmental applications of sewage removing toxic substances
There is special competitive advantage.
Summary of the invention
Conventional physical absorption method often uses iron and manganese oxides to handle the metal ion in waste water, but Fe-Mn oxidation as adsorbent
Object mechanical strength is bad, pore structure is not flourishing enough, is not fixed easily in use.In order to solve this technical problem, this hair
The advantage of bright combination biosorption process in the treatment of waste water, selecting to the microbial strains that metal ion has suction-operated is to grind
Study carefully object, using the nano-particle material including iron and manganese oxides nano particle as carrier, it is compound to prepare a kind of high-performance
The microorganism nano complex that body, the i.e. present invention declare protection.
The present invention has studied the influence factor of the microorganism nano complex absorption thallium and in laboratory conditions to it
Characterization of adsorption and mechanism have carried out preliminary analysis, and the practical application for the biological prosthetic engineering of thallium pollution provides theoretical foundation, are
Microorganism nano complex is had laid a good foundation as the development and utilization of novel environmental functional material.
Microorganism nano complex of the present invention, building component includes microbial strains and metal oxide nano
Grain, the metal oxide nanoparticles are carried on the metal oxide and receive as fixation support, the microbial strains
Rice grain constructs to form the complex.
Specifically, one of the preferred embodiment as the microorganism nano complex, the metal oxide are received
Rice grain selects manganese oxide nanoparticles, iron oxide nanoparticles, ferro manganese composite oxides nano particle or manganese oxidation
Object nano particle, the mixture of iron oxide nanoparticles.Further, the manganese oxide nanoparticles select manganese dioxide
Nano particle；The iron oxide nanoparticles select ferroferric oxide nano granules；The ferro manganese composite oxides nanometer
Grain is iron and manganese oxides nano particle of the present invention.In addition, the metal oxide nanoparticles can also select it is above-mentioned each
The mixture of kind nano particle, for example, manganese oxide nanoparticles, the mixture of iron oxide nanoparticles.
As one of the preferred embodiment of the microorganism nano complex, the microbial strains select to metal from
Son has the microbial strains Fusarium oxysporum FP-JCCW of suction-operated.
In addition, the present invention gives the preparation method of the microorganism nano complex, general preparation step packet
It includes: microbial strains and metal oxide nanoparticles being mixed and are scattered in liquid；4h is reacted under the conditions of being placed in 100 DEG C；Instead
Magnetic Isolation is after answering to get the microorganism nano complex.
Specifically, the present invention provides a kind of preparation method of microorganism nano complex, the metal oxidation used
Object nano particle is ferroferric oxide nano granules, using the microorganism nanometer of ferroferric oxide nano granules preparation
Complex is labeled as Fe- microorganism nano complex.The preparation method of this Fe- microorganism nano complex, comprising: by institute
It states ferroferric oxide nano granules and the microbial strains is placed in sterile water；4h is reacted under the conditions of being placed in 100 DEG C；Reaction knot
Magnetic Isolation after beam；80 DEG C of vacuum drying 4h are after washing to get the Fe- microorganism nano complex.
Specifically, the present invention provides a kind of preparation method of microorganism nano complex, the metal oxidation used
Object nano particle be ferroferric oxide nano granules and manganese dioxide nano particle, using the ferroferric oxide nano granules,
The microorganism nano complex of manganese dioxide nano particle preparation is labeled as Fe@Mn microorganism nano complex.It is this
The preparation method of Fe@Mn microorganism nano complex, comprising: potassium permanganate is dissolved in sterile water, appropriate dense salt is added dropwise
Acid, stirring；Ferroferric oxide nano granules and the microbial strains, stirring is added；4h is reacted under the conditions of being placed in 100 DEG C；Instead
Magnetic Isolation after answering；80 DEG C of vacuum drying 4h are after washing to get the Fe@Mn microorganism nano complex.
As one of the preferred embodiment of the nano combined preparation of Fe Mn microorganism, four oxidation three
The mass ratio of ferro element in iron nano-particle and the manganese element in manganese dioxide nano particle is 3:1.
Further, the present invention also provides the preparation methods of the ferroferric oxide nano granules, comprising: by four oxidations
Three-iron is scattered in ethylene glycol, and anhydrous sodium acetate is added, and stirs into uniformly sticky mixed solution；100 DEG C of isothermal reaction 4h；Instead
Magnetic Isolation after answering；80 DEG C of vacuum drying 4h are after washing to get the ferroferric oxide nano granules.
As one of the preferred embodiment of the ferroferric oxide nano granules preparation method, the ferroso-ferric oxide is received
The mass ratio of ferro element and anhydrous sodium acetate in rice grain is 1:8.
In addition, the application The present invention gives the microorganism nano complex in waste water containing thallium processing.
Microorganism nano complex of the present invention, at least has the following beneficial effects or advantage:
Microorganism nano complex of the present invention is a kind of novel function adsorbent material, and building component includes micro- life
Object bacterial strain and metal oxide nanoparticles, metal oxide nanoparticles are carried on as fixation support, microbial strains
Metal oxide nanoparticles construct to form the complex.Further, the present invention with it is green, efficient, highly selective, can return
The research of the microorganism nano complex heavy-metal ion removal for the property received is guiding, has probed into this microorganism nano complex
Preparation method and its mechanism for removing thallium ion.Test result according to the present invention can know, selected metal oxide
Nano particle and the compound mechanism of action for showing synergistic sorption thallium of microbial strains Fusarium oxysporum FP-JCCW,
The absorption property for preparing material is enhanced, to improve its adsorption efficiency.
Microorganism nano complex of the present invention can not only efficiently remove the harmful heavy metal ions in water, but also can be with
The product after use is effectively recycled, the secondary pollution of nano-powder can also be avoided (to remove nuclear pollution extremely in water field of big area
Crucial index).Compared with individually being carried out purifying with ferroferric oxide nano granules or microbial cells, the present invention
The microorganism nano complex had both had the advantages that microbial cells removing heavy metals ion (high adsorption saturation amount, fast absorption
Rate), and have many advantages, such as recyclable, low cost, industrialized production can be achieved.
Detailed description of the invention
Fig. 1 is the X-ray of Fe@Mn microorganism nano complex, Fe- microorganism nano complex and Fe-Mn nano particle
Diffraction analysis figure.
Fig. 2 is the FT-IR of Fe@Mn microorganism nano complex, Fe- microorganism nano complex and Fe-Mn nano particle
Figure.
Fig. 3 is the dosage of Fe@Mn microorganism nano complex, Fe- microorganism nano complex and Fe-Mn nano particle
Influence to absorption thallium.
Fig. 4 is initial thallium concentration to Fe@Mn microorganism nano complex, Fe- microorganism nano complex and Fe-Mn nanometers
The influence of granular absorption thallium.
Fig. 5 is initial pH to Fe@Mn microorganism nano complex, Fe- microorganism nano complex and Fe-Mn nano particle
Adsorb the influence of thallium.
Fig. 6 is shaking speed to Fe@Mn microorganism nano complex, Fe- microorganism nano complex and Fe-Mn nanometers
The influence of grain absorption thallium.
Fig. 7 is that temperature inhales Fe@Mn microorganism nano complex, Fe- microorganism nano complex and Fe-Mn nano particle
The influence of plummet.
Fig. 8 is the infrared spectrum analysis before and after Fe@Mn microorganism nano complex absorption thallium.
Fig. 9 is the infrared spectrum analysis before and after Fe- microorganism nano complex absorption thallium.
Figure 10 is the infrared spectrum analysis before and after Fe-Mn nano particle absorption thallium.
Figure 11 is that Fe@Mn microorganism nano complex absorption thallium front and back XPS full scan spectrum is contrasted.
Figure 12 is that Fe- microorganism nano complex absorption thallium front and back XPS full scan spectrum is contrasted.
Figure 13 is that Fe-Mn nano particle absorption thallium front and back XPS full scan spectrum is contrasted.
Figure 14 is Fe@Mn microorganism nano complex, Fe- microorganism nano complex and Fe-Mn nano particle absorption thallium
Front and back XPS full scan spectrum is contrasted.
Specific embodiment
The present invention is elaborated further below with reference to embodiment.
Embodiment 1
(1) preparation of Fe@Mn microorganism nano complex
Accurately weigh 1g KMnO4Powder is dissolved in 150mL sterile water, and appropriate concentrated hydrochloric acid (dense, 12mol/ is added dropwise
L), then Fe is added in magnetic agitation 15min3O4Nano particle (Fe3O4Ferro element and MnO in nano particle2In nano particle
The mass ratio of manganese element be 3:1) and 1g microbial strains Fusarium oxysporum FP-JCCW bacterium powder, stirring 30min,
In the reaction kettle for the inner liner polytetrafluoroethylene that mixing dispersion solution is transferred to 200mL, it is placed in electric heating constant-temperature blowing drying box 100
DEG C reaction 4h is cooled to room temperature after completion of the reaction, Magnetic Isolation, after being washed several times with distilled water, dehydrated alcohol respectively, 80 DEG C
Vacuum drying 4h, which is placed in desiccator, to be saved, which is Fe@Mn microorganism nano complex.
(2) preparation of Fe- microorganism nano complex
In 150mL sterile water, Fe is added3O4Nano particle and 1g microbial strains Fusarium oxysporum FP-
JCCW bacterium powder stirs 30min, in the reaction kettle for the inner liner polytetrafluoroethylene that mixing dispersion solution is transferred to 200mL, is placed in electricity
100 DEG C of reaction 4h of hot constant temperature blast drying oven are cooled to room temperature after completion of the reaction, and Magnetic Isolation uses distilled water, anhydrous second respectively
After alcohol washing several times, 80 DEG C of vacuum drying 4h are placed in desiccator and save, which is that Fe- microorganism is nano combined
Body.
(3) preparation of Fe-Mn nano particle
Accurately weigh 1g KMnO4Powder is dissolved in 150mL sterile water, and appropriate concentrated hydrochloric acid (dense, 12mol/ is added dropwise
L), then Fe is added in magnetic agitation 15min3O4Nano particle (Fe3O4Ferro element and MnO in nano particle2In nano particle
The mass ratio of manganese element be 3:1), stir 30min, mixing dispersion solution be transferred to the inner liner polytetrafluoroethylene of 200mL
In reaction kettle, 100 DEG C of reaction 4h of electric heating constant-temperature blowing drying box are placed in, after completion of the reaction, are cooled to room temperature, Magnetic Isolation, difference
After being washed several times with distilled water, dehydrated alcohol, 80 DEG C of vacuum drying 4h are placed in desiccator and save, which is to be
Fe-Mn nano particle.
Fe described in the present embodiment3O4Nano particle (hollow structure Fe3O4Magnetic grain) preparation method, comprising: take appropriate Fe3O4
It is dispersed in ethylene glycol, anhydrous Na Ac (Fe is added under ultrasonication3O4The matter of ferro element and anhydrous Na Ac in nano particle
Amount is than being 1:8), uniformly sticky mixed liquor is formed, mixed liquor is transferred in 200ml autoclave, is then kept at 100 DEG C
4h.After reaction, product is taken out when reaction kettle is cooled to room temperature, product is analysed by magnetic, washed, ethyl alcohol is washed several times, finally
It is dried in vacuo 4h at 80 DEG C, which is Fe3O4Nano particle.
Embodiment 2
The present embodiment provides adsorption test and the characterizing method of microorganism nano complex.
(1) test method
With thallous nitrate (TlNO3) it is configured to the stock solution of 1000ppm, then required solution concentration is diluted to ultrapure water
(unless otherwise instructed, the present embodiment 200ppm).During test, appropriate thallium is taken to move into 200mL beaker using liquid, Yu Heng
After warm magnetic stirrer stirring 5min, adjusting pH while stirring, (unless otherwise instructed, the present embodiment pH is 9), with liquid-transfering gun point
Three sample (Fe@Mn microorganism nanometers made from appropriate embodiment 1 are added after not taking 25ml thallium solution to be put into three centrifuge tubes
Complex, Fe- microorganism nano complex and Fe-Mn nano particle), it is put into centrifuge, is centrifuged in 200r/min
4h.After centrifugation, with syringe filter (0.45 μm) extraction 10mL filtrate extraction, then plus 0.2mL nitric acid solution (50%,
V/v) acidification saves, then by sample after distilled water, ethyl alcohol wash three times, is placed in dry tube sealing again and saves, waits to be characterized.
(2) characterizing method
FT-IR analysis, is used in conjunction system using the infrared spectrometer and infrared microscope of German Bruker company, wherein
Infrared spectrometer wave-length coverage is 8000-340cm-1, spectral resolution is better than 0.4cm-1.And the microspectrum of infrared microscope
Range is 8000-650cm-1, there are transmission, reflection and tri- kinds of test patterns of ATR.
X-ray diffraction analysis (X.ray diffraction, XRD) is Bruker company of Germany using instrument
D8Advance type X-ray diffractometer, Cu, K target, wavelength 0.15406nm, voltage 40kV, electric current 30mA, in a manner of continuous scanning
Spectrum, scanning speed 4 are taken the photograph to powdered samples non-directional.(20)/min.
BET analysis, using the full-automatic specific surface area of the multistation of Micromeritics Instrument Corp. U.S.A and opening size test system
(ASAP2460), specific surface area analysis range 0.01m2/ g or more；Pore-size distribution analyst coverage 0.4nm-200nm.
This experiment, can be with microorganisms bacterial strain Fusarium oxysporum FP-JCCW by FT-IR, XRD analysis
The variation of surface potential and functional group characterizes the space structure of various complex crystals, specifies the phase of microbial strains absorption thallium
Interaction process and action site.Sample BET analysis is measured, it is known that the specific surface area after Material cladding, Kong Rong, aperture etc.
The defect of particle effective dispersing method and feasible particle agglomeration is groped in the variation of project.
The present embodiment also carries out Fourier transform infrared spectroscopy FT-IR and X-ray photoelectricity to microorganism nano complex
The characterization such as sub- power spectrum XPS (Kratos Axis Ultra, Japan), to probe into microbial strains Fusarium oxysporum
The variation of FP-JCCW microscopic appearance and functional group in the thallium solution of high concentration, to go deep into the cutting mechanisms of clear thallium.
Embodiment 3
Using 2 the method for embodiment, the present embodiment provides the adsorption test result and characterization of microorganism nano complex
As a result, and carrying out phenetic analysis to Fe@Mn microorganism nano complex.
(1) mode of appearance is analyzed
The Fe@Mn microorganism nano complex of preparation is added in 100mL deionized water, 2min is then sufficiently mixed,
It can be seen that the Fe@Mn microorganism nano complex in deionized water is largely in suspended state, distribution uniform.It will be above-mentioned
After the dry bottling of Fe@Mn microorganism nano complex, stood on the outside of bottle wall by one piece of magnet side, immediately Fe@Mn microorganism nanometer
Composite particle precursor is close to magnet rapidly, it may be said that bright Fe@Mn microorganism nano complex has stronger magnetism.
(2) crystalline structure analysis (XRD)
In order to study the crystalline structure of Fe@Mn microorganism nano complex, respectively to Fe@Mn microorganism nano complex,
Fe- microorganism nano complex and Fe-Mn nano particle have carried out XRD characterization, and characterization result is shown in Fig. 1.As shown in Figure 1, Fe@Mn
The diffraction maximum of microorganism nano complex, Fe- microorganism nano complex and Fe-Mn nano particle equally 2 θ=30.241 °,
35.630 °, 43.284 °, 53.733 °, 57.271 °, 62.925 °, respectively with pdf standard card JCPDS in XRD standard database
Various ferrimanganic crystalline structure diffraction patterns comparisons inside 79-0417 it can be concluded that, the peak shape of three kinds of adsorbents all relatively Fe3O4
The plane (220), (331), (400), (422), (440) and (511) of crystal, may thereby determine that the Fe in adsorbent3O4For face
Heart cubic crystal structure.It can't see MnO in Fe- microorganism nano complex diffraction maximum2Crystal form peak, for the micro- life of Fe@Mn
The diffraction maximum of object nano complex, Fe-Mn nano particle, at twice at 71.5 ° of sweep angle it can be seen that manganese dioxide it is amorphous
Peak, this illustrate the manganese dioxide in nanocomposite be in the form of unbodied existing for.
(3) specific surface area analysis (BET)
For information such as the specific surface area, the apertures that obtain Fe@Mn microorganism nano complex, respectively to Fe@Mn microorganism
Nano complex, Fe- microorganism nano complex and Fe-Mn nano particle have carried out BET characterization, and characterization result is shown in Table 1.
The BET of table 1Fe@Mn microorganism nano complex, Fe- microorganism nano complex and Fe-Mn nano particle is measured
As a result
As it can be seen from table 1 the increase of thallus and the content of manganese will affect the specific surface area of adsorbent material, make Fe@Mn
The specific surface area of microorganism nano complex increases, and as the material in water process, absorption property application prospect is more preferable.Generally
In the case of, aperture existsIt is macropore when above, aperture existsIt is micropore when following, and aperture existsWithRange
Interior is mesoporous, and the average pore size of Fe@Mn microorganism nano complex, Fe- microorganism nano complex and Fe-Mn nano particle existsLeft and right,Hereinafter, belonging to poromerics.This poromerics has high specific surface area, regular
The features such as cellular structure, narrow pore-size distribution, pore size are continuously adjustable, so that it is difficult in many micro-pore zeolite molecular sieves
It plays a role in absorption, the separation of the macromolecular of completion, especially catalysis reaction.It can be seen that Fe@Mn prepared by the present invention is micro-
Biological nano complex, Fe- microorganism nano complex better performances.
(4) infrared spectrum analysis (FT-IR)
Fe@Mn microorganism nano complex, Fe- microorganism nano complex and Fe-Mn nano particle are carried out respectively
FT-IR characterization, characterization result are shown in Fig. 2.
Figure it is seen that 580cm-1Corresponding to Fe-O stretching vibration, and Mn-O stretching vibration characteristic peak appears in 400-
750cm-1Place.And the infrared light spectral peak of Fe Mn microorganism nano complex, Fe-Mn nano particle is then compound because of the two,
400-750cm-1There is overlapping at place, and there are a little offsets, pass through the 400-750cm of a and b-1Neighbouring spectrum compares it is found that Fe@Mn
The iron and manganese oxides Compound Degree of microorganism nano complex is higher.3400cm-1Place's absorption peak belongs to the flexible of surface hydroxyl
Vibration, and sample F e@Mn microorganism nano complex 3400cm-1Neighbouring absorption peak is high compared with remaining two groups of sample, this is because
Hydroxyl (- OH) and imino group (- NH) effect gained on cell wall, so above-mentioned ir data preferably illustrates ferrimanganic oxygen
Compound nano material and microbial strains Fusarium oxysporum FP-JCCW bacterium powder constitute the Fe@Mn microorganism nanometer
Complex.
Embodiment 4
The present embodiment probes into influence of the factors such as sample dosage, initial thallium concentration, initial pH to absorption thallium.
(1) influence of the sample dosage to absorption thallium
Using Fe@Mn microorganism nano complex, Fe- microorganism nano complex and Fe-Mn nano particle as adsorbent,
The sample dosage (biomass) of 5 groups of 0.01mg-0.05mg is respectively set, sets 9 for initial pH, shaking speed is adjusted to
120r/min, the residence time in setting mixing and absorption pond are 50min.
The dosage of Fe@Mn microorganism nano complex, Fe- microorganism nano complex and Fe-Mn nano particle is to suction
The influence of plummet, is shown in Fig. 3.From figure 3, it can be seen that for Fe@Mn microorganism nano complex, with the increasing of biological dosage
Add, the adsorption capacity to thallium is in apparent increasing trend, and highest adsorption capacity has reached 42.5985mg/g, this illustrates Fe@
The sorption potential of Mn microorganism nano complex is pretty good, this is also corresponding with specific surface area analysis conclusion of the front to it.Fe- is micro-
The adsorption capacity variation tendency that biological nano complex is presented is consistent with Fe@Mn microorganism nano complex, and highest absorption is held
Amount reaches 34.07mg/g.And there is no show with the increase of biological dosage for adsorption capacity of the Fe-Mn nano particle to thallium
Apparent trend.
(2) influence of the initial thallium concentration to absorption thallium
Using Fe@Mn microorganism nano complex, Fe- microorganism nano complex and Fe-Mn nano particle as adsorbent,
5 groups of initial thallium concentration, respectively 20mg/L, 50mg/L, 100mg/L, 150mg/L, 200mg/L are respectively set, initial pH is set
9 are set to, temperature is 60 DEG C, adds the adsorbent of 0.02g, shaking speed is adjusted to 120r/min, setting mixing and absorption pond
Residence time is 50min.
Initial thallium concentration is to Fe@Mn microorganism nano complex, Fe- microorganism nano complex and Fe-Mn nano particle
The influence for adsorbing thallium, is shown in Fig. 4.From fig. 4, it can be seen that when thallium initial concentration is increased to 150mg/L from 20mg/L, the micro- life of Fe@Mn
Object nano complex continues to increase the adsorption capacity of thallium, rises to 25mg/g or so from 5mg/g or so, but growth rate is with dense
Degree increases and slows down, and has downward trend when concentration reaches 200mg/L or so.Fe@Mn microorganism nano complex is wider
Concentration range in it is in rising trend, on the one hand, be because in the case where oxidation system reagent dosage is constant, as thallium is dense
The raising of degree, oxidation substrates increasing concentrations, so probability of the adsorbent in conjunction with thallium is bigger, the thallium of absorption is more.On the other hand,
Be bacterial strain surface active site when thallium solution concentration is low sufficiently being occupied by metal ion, when ion concentration increases
When, adsorption capacity increases therewith.But when mass concentration is greater than 150mg/L, adsorption capacity decline, the reason is that higher thallium is first
Beginning concentration will affect the adsorption activity of bacterial strain, to reduce the adsorption capacity of the system.
Fe- microorganism nano complex is under the concentration gradient to the variation tendency of the adsorption capacity of thallium and the micro- life of Fe@Mn
Object nano complex is almost the same, but its adsorption capacity is low compared with Fe@Mn microorganism nano complex, the main reason is that lacking
Manganese element participates in reaction.
Fe-Mn nano particle adsorption capacity increases with the increase of thallium solution concentration, in the dense of 20mg/L to 200mg/L
Downward trend is not occurred in degree range, but is gradually flattened out, and conjecture is that receipts thallium is dense because microbial activity is not present in the system
The problem of degree influences, so finally tend to be saturated to the adsorption capacity of thallium, this with " initial concentration of higher thallium will affect bacterial strain
Adsorption activity, to reduce the adsorption capacity of the system " conclusion it is consistent.
(3) influence of the initial pH to absorption thallium
Using Fe@Mn microorganism nano complex, Fe- microorganism nano complex and Fe-Mn nano particle as adsorbent,
4 to 96 groups of pH variables are respectively set, add the adsorbent of 0.02g, setting temperature is 60 DEG C, and shaking speed is adjusted to
120r/min, the residence time in setting mixing and absorption pond are 50min.
Initial pH adsorbs Fe@Mn microorganism nano complex, Fe- microorganism nano complex and Fe-Mn nano particle
The influence of thallium, is shown in Fig. 5.From fig. 5, it can be seen that Fe@Mn microorganism nano complex adsorbs the optimal pH of thallium 7 or so, at this time
Reaching maximum adsorption capacity is 24.10343mg/g, as pH < 7 or > 7, is reduced to the adsorption capacity of thallium, this is because by force
Acid obtains the three-dimensional structure of bacterium surface ionic species or enzyme active sites under highly basic state and can change, and then influences bacterium
Activity.But when in the case where stronger acids or alkali, it is micro- that the adsorption capacity of Fe@Mn microorganism nano complex is still higher than Fe-
Biological nano complex and Fe-Mn nano particle both compound systems still have compared with high-adsorption-capacity, this illustrates Fe@
Mn microorganism nano complex has stronger tolerance under different pH environment.
(4) influence of the shaking speed to absorption thallium
Using Fe@Mn microorganism nano complex, Fe- microorganism nano complex and Fe-Mn nano particle as adsorbent,
6 groups of speed variables are respectively set, 30r/min, 60r/min, 90r/min, 120r/min, 180r/min, 210r/min are added
The adsorbent of 0.02g, setting temperature are 60 DEG C, and the residence time in setting mixing and absorption pond is 50min.
Shaking speed inhales Fe@Mn microorganism nano complex, Fe- microorganism nano complex and Fe-Mn nano particle
The influence of plummet, is shown in Fig. 6.From fig. 6, it can be seen that different shaking speeds, adsorption capacity is also different, but shaking speed and absorption
Agent is not simple linear relationship to the adsorption capacity of thallium.30 between 180r/min, Fe@Mn microorganism nano complex
The adsorption rate of thallium is constantly increased, up to 33.84567mg/g, optimum speed 180r/min, when revolving speed continues to accelerate
When, adsorption effect is substantially reduced.
(5) influence of the temperature to absorption thallium
Using Fe@Mn microorganism nano complex, Fe- microorganism nano complex and Fe-Mn nano particle as adsorbent,
6 groups of temperature variables are respectively set, 10,20,30,40,50,60 DEG C, adds the adsorbent of 0.02g, shaking speed is adjusted to
120r/min, the residence time in setting mixing and absorption pond are 50min.
Temperature adsorbs thallium to Fe@Mn microorganism nano complex, Fe- microorganism nano complex and Fe-Mn nano particle
Influence, see Fig. 7.From figure 7 it can be seen that Fe@Mn microorganism nano complex, Fe- microorganism nano complex and Fe-Mn receive
There is no what rule, Fe@Mn microorganism nano complex, two kinds of Fe- microorganism nano complex in rice grain and temperature
The adsorption capacity of adsorbent reaches maximum value at 30 DEG C.
Embodiment 5
The present embodiment probes into Fe@Mn microorganism nano complex, Fe- microorganism nano complex and Fe-Mn nano particle
Adsorption mechanism.
(1) infrared spectrum analysis
Fig. 8 is shown in infrared spectrum analysis before and after Fe@Mn microorganism nano complex absorption thallium.Fe- microorganism is nano combined
Fig. 9 is shown in infrared spectrum analysis before and after body absorption thallium.Figure 10 is shown in infrared spectrum analysis before and after Fe-Mn nano particle absorption thallium.
The infrared spectroscopy of these three adsorbent materials is in 300-4000cm-1In the range of.3400cm-1Place's absorption peak belongs to surface hydroxyl
The stretching vibration of base, 1500cm-1The absorption peak at place belongs to the bending vibration of H-O-H, 1111cm-1Neighbouring absorption peak is iron oxygen
The bending vibration of compound surface hydroxylation group is located at 600cm-1To 400cm-1Peak in range belongs to the curved of Fe-O or Mn-O
Bent shock absorption peak.
From figure 8, it is seen that in 3400cm before and after Fe@Mn microorganism nano complex absorption thallium-1Neighbouring absorption peak by
3377cm-13412cm is moved to-1(it is shifted 5cm-1), this is because hydroxyl (- OH) and imino group on somatic cells wall (-
NH caused by) acting on.And in 1542cm-1Absorption peak after nearly absorption thallium significantly increases, this may be because Tl (I) during the reaction
It is converted to Tl (III) and subsequently forms precipitating and be adsorbed to sample surfaces, form more absorption water, after adsorbing thallium, the micro- life of Fe@Mn
The 1061cm of object nano complex infrared spectroscopy-1Absorption peak number near position is reduced but intensity increases, and conjecture causes this kind
The reason of image is that with thallium ion surface complexing may occur for iron carbonyl colloid, so Fe@Mn microorganism nano complex
Thallium adsorbance is increased to keep this peak intensity larger.
(2) surface-element analysis (XPS)
XPS full scan spectrum is contrasted before and after Fe@Mn microorganism nano complex absorption thallium, sees Figure 11.Fe- microorganism nanometer
XPS full scan spectrum is contrasted before and after complex absorption thallium, sees Figure 12.Fe-Mn nano particle adsorbs XPS full scan spectrum before and after thallium
It contrasts, sees Figure 13.Before Fe@Mn microorganism nano complex, Fe- microorganism nano complex and Fe-Mn nano particle absorption thallium
XPS full scan spectrum is contrasted afterwards, sees Figure 14.
Occurs Tl in Figure 11-134fPeak shows that thallium has been adsorbed on above material.It is multiple for sample F e- microorganism nanometer
Zoarium, main peaks are O1s spectrum, this may be to be covered because of its surface by great amount of hydroxy group-OH, and the substance adsorbed is less,
Therefore the O of high content is detected.For sample F e-Mn nano particle, the peak O is removed, secondly peak is Mn2pSpectrum and Fe2p
Spectrum illustrates that ferrimanganic is preferably compound, but the thallium or fewer adsorbed.The absorption of sample F e@Mn microorganism nano complex
There is the presence of the elements such as Tl, Fe, Mn and O in the sediment of thallium, this suggests the formation of Tl-Fe-Mn mixture.It can be with according to Figure 14
Know, the peak intensity of three kinds of sample Tl gradually increases, and shows that Tl content is more and more in solid phase surface component.Due to Tl initial concentration
Identical, this has indicated that more Tl have been adsorbed in sample F e@Mn microorganism nano complex, and the S2p of three kinds of samples
Spectrum is very weak, nearly imperceptible on full scan spectrogram.
Further narration is done to the present invention above in conjunction with embodiment, but present invention is not limited to the embodiments described above,
Within the knowledge of one of ordinary skill in the art, it can also make without departing from the purpose of the present invention
Various change.
Claims (10)
1. microorganism nano complex, building component includes microbial strains and metal oxide nanoparticles, the metal
For oxide nano particles as fixation support, the microbial strains are carried on the metal oxide nanoparticles building shape
At the complex.
2. microorganism nano complex according to claim 1, which is characterized in that the metal oxide nanoparticles choosing
With manganese oxide nanoparticles, iron oxide nanoparticles, ferro manganese composite oxides nano particle or Mn oxide nanometer
Grain, the mixture of iron oxide nanoparticles.
3. microorganism nano complex according to claim 1, which is characterized in that the microbial strains are selected to metal
Ion has the microbial strains Fusarium oxysporum FP-JCCW of suction-operated.
4. the preparation method of microorganism nano complex described in any one of claim 1-3 comprising: by microbial strains and
Metal oxide nanoparticles mixing is scattered in liquid；4h is reacted under the conditions of being placed in 100 DEG C；Magnetic Isolation after reaction,
Up to the microorganism nano complex.
5. the preparation method of microorganism nano complex according to claim 4, which is characterized in that the metal oxide
Nano particle selects ferroferric oxide nano granules, and it is multiple to prepare the microorganism nanometer using the ferroferric oxide nano granules
Fit method includes: that the ferroferric oxide nano granules and the microbial strains are placed in sterile water；It is placed in 100 DEG C
Under the conditions of react 4h；Magnetic Isolation after reaction；80 DEG C of vacuum drying 4h are nano combined to get the microorganism after washing
Body.
6. the preparation method of microorganism nano complex according to claim 4, which is characterized in that the metal oxide
Nano particle selects ferroferric oxide nano granules and manganese dioxide nano particle, using the ferroferric oxide nano granules,
The method of microorganism nano complex described in manganese dioxide nano particle preparation includes: that potassium permanganate is dissolved in sterile water, by
It is added dropwise to appropriate concentrated hydrochloric acid, is stirred；Ferroferric oxide nano granules and the microbial strains, stirring is added；It is placed in 100 DEG C of items
4h is reacted under part；Magnetic Isolation after reaction；80 DEG C of vacuum drying 4h are after washing to get the microorganism nano complex.
7. the preparation method of microorganism nano complex according to claim 6, which is characterized in that the ferroso-ferric oxide
The mass ratio of ferro element in nano particle and the manganese element in manganese dioxide nano particle is 3:1.
8. the preparation method of the microorganism nano complex according to any one of claim 5-7, which is characterized in that described
The preparation method of ferroferric oxide nano granules includes: to disperse ferroso-ferric oxide in ethylene glycol, and anhydrous sodium acetate is added, stirs
Mix uniformly sticky mixed solution；100 DEG C of isothermal reaction 4h；Magnetic Isolation after reaction；80 DEG C of vacuum drying after washing
4h is to get the ferroferric oxide nano granules.
9. the preparation method of microorganism nano complex according to claim 8, which is characterized in that the ferroso-ferric oxide
The mass ratio of ferro element and anhydrous sodium acetate in nano particle is 1:8.
10. application of the microorganism nano complex described in any one of claim 1-3 in waste water containing thallium processing.
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