CN108714413A - One Yeasts carry nano zero valence iron and application thereof - Google Patents
One Yeasts carry nano zero valence iron and application thereof Download PDFInfo
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- CN108714413A CN108714413A CN201810584848.1A CN201810584848A CN108714413A CN 108714413 A CN108714413 A CN 108714413A CN 201810584848 A CN201810584848 A CN 201810584848A CN 108714413 A CN108714413 A CN 108714413A
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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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- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
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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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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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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- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4868—Cells, spores, bacteria
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
Abstract
The present invention provides a Yeasts and carries nano zero valence iron and application thereof, it includes yeast vector or the nano zero-valence iron particle by chemically treated modified yeast bacterium carrier and its load that the saccharomycete, which carries nano zero valence iron, be by sodium borohydride or potassium borohydride by the molysite or ferrous salt in-situ reducing of yeast vector or the modified yeast bacterium carrier adsorption after chemical treatment is obtained by nano zero valence iron.It can be widely used for removing or degrading water body or the heavy metal ion in soil and organic pollution.
Description
Technical field
The present invention provides a Yeasts and carries nano zero valence iron and application thereof, is related to the culture of saccharomycete, handles and receive
The preparation method of rice Zero-valent Iron further relates to the saccharomycete and carries nano zero valence iron in removal of heavy metal ions and organic contamination
Application in object degradation.Belong to environment functional material to prepare and environment remediation technical field.
Background technology
Nano zero valence iron has stronger reducing power and excellent absorption property, is widely used in going back for halogen containing organic compound
The removal of former dehalogenation, the reduction-decolor of dyestuff and heavy metal ion is a kind of pollution law having much application potential
Control material.But nano zero valence iron there are it is oxidizable, reunite and passivation the shortcomings that, hinder its reality in pollutant process
Using.
Nano zero valence iron is loaded on carrier, the dispersibility of nano zero valence iron can not only be improved, and makes nano zero valence iron
It is easily recycled, prevents secondary pollution.
Chinese invention patent ZL200910090616.1 (preparation method and application of activated carbon loaded nano-iron material) is adopted
It uses pretreated activated carbon as support materials, under the auxiliary of argon gas and ultrasonic wave, utilizes the mushy feature of activated carbon
The nano zero-valence iron particle that reaction generates is set fully to disperse and load the activated carbon loaded nano iron material on activated carbon, obtained
Expect the pentachlorophenol in degradable water body；Chinese invention patent ZL201210447511.9 is (using montmorillonite as the nanometer zero of carrier
Valence iron and its preparation method and application) it discloses in one kind ethanol medium existing for soluble starch, using montmorillonite as carrier
The method for preparing nano zero valence iron, makes full use of between montmorillonite layer and space surface reduces the polymerization of nano zero valence iron, obtained
Nano zero valence iron activity is high, and stability is good, the significant effect when handling hexavalent chromium wastewater.
Saccharomycete has porous network structure and abundant amino, hydroxyl, carboxyl and phosphate group, is a kind of natural life
Object adsorbent.By in nano zero valence iron particulate load to saccharomycete can not weaken nano zero valence iron it is active under the premise of reduce receive
Reunion between rice zero-valent iron particle, while the suction-operated of saccharomycete and the reduction of Nanoscale Iron are played, be conducive to pollutant
Enrichment and accelerate its remove reaction rate.It yet there are no the document report that nano zero valence iron is prepared using saccharomycete as carrier.
Invention content
The deficiency that the purpose of the present invention is easily aoxidize, reunite for nano zero valence iron, using natural saccharomycete as carrier,
The strong reducing property of nano zero valence iron is combined with the excellent adsorptivity of saccharomycete, it is simple, at low cost to provide a kind of preparation process
The preparation method of honest and clean, environmental-friendly, long lifespan nano zero valence iron, and the saccharomycete prepared in this way carry nano zero-valence
Iron.
The technical principle of the present invention is to utilize the amino of saccharomycete, hydroxyl using saccharomycete as carrier, dispersant and stabilizer
The groups such as base, carboxyl and phosphoric acid adsorb Dissolvable Fe2+Or Fe3+Afterwards, in-situ reducing is Zero-valent Iron, utilizes the Double-level Reticulated of saccharomycete
Shape porous structure disperses and stablizes nano zero valence iron, and utilizes the Fe generated in saccharomycete adsorption reaction2+Or Fe3+, prevent Fe2+
Or Fe3+It is co-precipitated on nano zero-valence iron surface, maintains the reduction activation of nano zero valence iron, reduced and use nano zero valence iron when institute
The a large amount of iron cement pollution risks brought.By adjust the mass ratio of yeast vector and molysite, reductant concentration, reaction temperature,
Reaction time and stirring or hunting speed achieve the purpose that control nano zero valence iron reactivity.
Therefore, the first purpose of the invention is to provide the preparation methods that a Yeasts carry nano zero valence iron, including such as
Lower step：
(1) the saccharomycete centrifugation of gained after washing, is freeze-dried to obtain saccharomycete load by culture yeasts bacterium according to a conventional method
Body.Or centrifuge the saccharomycete of gained, after washing, it is resuspended in the chemical reagent with promotion saccharomycete self-dissolving, 40
Stirring or oscillation treatment are chemically treated for 24~48 hours at a temperature of~60 DEG C.After centrifugation, washing, freeze-drying obtains
By chemically treated modified yeast bacterium carrier；
(2) molysite or perferrite solution are added to the yeast vector or modified yeast bacterium carrier that step (1) obtains
In, in 50~200rmin-1Stirring or the oscillation lower 0.5~2h that reacts obtain being adsorbed with Fe after centrifugation, washing2+Or Fe3+'s
Saccharomycete or modified yeast bacterium；
(3) under conditions of lasting stirring or oscillation, Fe is adsorbed with toward what step (2) obtained2+Or Fe3+Saccharomycete or
Reducing agent solution is added in modified yeast bacterium, continues stirring or oscillating reactions 0.5h~2h, then is separated by solid-liquid separation, solid is with two
Secondary distillation water washing 3 times carries nano zero valence iron after freeze-drying grinding up to saccharomycete or modified yeast bacterium.
Preferably, in step (1), the saccharomycete is Saccharomyces cerevisiae or saccharomyces cerevisiae.
Preferably, in step (1), the chemical reagent is that the Tween-80 that mass percent concentration is 0.1~5% is molten
The sodium hydroxide that hydrochloric acid solution that liquid, mass percent concentration are 0.5~10%, mass percent concentration are 0.5~10% is molten
The Klorvess Liquid and matter that ethanol solution that liquid, mass percent concentration are 1~20%, mass percent concentration are 1~20%
Measure the one or more in the sodium chloride solution that percent concentration is 1~20%.
Preferably, the saccharomycete described in step (2) or modified yeast bacterium carrier quality are 0.2~8.0g, the iron
Salt or a concentration of 0.02~1.43molL of ferrous salt-1。
Preferably, the reducing agent described in step (3) is sodium borohydride or potassium borohydride, the sodium borohydride or boron hydrogen
Change a concentration of 0.04~2.80molL of potassium solution-1, the rate of addition is 0.20~1.00mLmin-1, sodium borohydride or
Potassium borohydride and Fe2+Or Fe3+Substance amount ratio be 2~10:1.
Preferably, step (3) while stirring or oscillation with 0.5~0.8mLmin-1Gas supply speed toward described molten
Lead to N in liquid2, the separation of solid and liquid is in 8000rmin-110min is centrifuged under rotating speed or is detached using magnetic method.
Second object of the present invention is to provide a Yeasts and carries nano zero valence iron, including yeast vector or processization
Learn the modified yeast bacterium carrier and nano zero-valence iron particle of processing.The wherein described nano zero valence iron particle is with sodium borohydride or boron
Hydrofining is the Fe that reducing agent adsorbs saccharomycete2+Or Fe3+In-situ reducing is obtained by Zero-valent Iron.
Third object of the present invention is to provide carry nano zero valence iron removal water body or soil using prepared saccharomycete
The method of middle heavy metal ion, wherein
In a specific embodiment, the heavy metal ion removed is Cr (VI), preferred concentration of heavy metal ion
For 10~100mgL-1。
The removal of Cr (VI) carries out in 10mL centrifuge tubes.4.50mL0.10mol is added into 10mL colorimetric cylinders successively
L-1Phosphate buffer solution (pH=6.0), 0.50mL 500mgL-1Cr (VI) solution and 10.0mg saccharomycete carry nano zero-valence
Iron shakes up and is placed in 25 DEG C of water-baths and starts timing, and timing is taken out 0.10mL and measured using 1,5- diphenyl phosphinylidyne, two hydrazine method
The removal rate of Cr (VI).
Fourth object of the present invention is to provide carries nano zero valence iron degradation water body or soil using prepared saccharomycete
The method of middle organic pollution, wherein
In a specific embodiment, the organic pollution degraded is chlorine-containing organic compounds, and involved contains
Chlorine organic compound includes chlorobenzene, chlorinated phenol, chloroacid and organic chlorine agriculture chemicals etc., preferred chlorine-containing organic compounds concentration
For 0.02~0.20mmolL-1。
The reaction that saccharomycete carries nano zero valence iron degradation chlorine-containing organic compounds carries out in 10mL glass centrifuge tubes.It will
A concentration of 0.02~0.20mmolL of 4.00mL-1Chlorine-containing organic compounds solution and 4.0~40.0mg saccharomycete carry nanometer zero
After mixing, 0.20mL is taken out in timing to valence iron, using the degradation rate of high effective liquid chromatography for measuring chlorine-containing organic compounds.
In a specific embodiment, the chlorinatedorganic degraded be 2,4,6- trichlorophenol, 2,4,6,-Ts, preferably 0.02~
0.20mmol·L-12,4,6- trichlorophenol, 2,4,6,-Ts.
In another embodiment, the chlorinatedorganic degraded be 2,4- chlorophenesic acids, preferably 0.02~
0.20mmol·L-12,4 dichloro phenol.
In another embodiment, the chlorinatedorganic degraded be 2- chlorophenols, preferably 0.02~
0.20mmol·L-12- chlorophenols.
Also in another embodiment, the chlorinatedorganic degraded be 4- chlorophenols, preferably 0.02~
0.20mmol·L-14- chlorophenols.
Technique effect
(1) it is carrier, dispersant and stabilization using stablizing and there is the saccharomycete of certain pore size structure or modified yeast bacterium
Agent prepares saccharomycete and carries nano zero valence iron, and preparation method is simple, and reaction condition is mild, uses conventional instrument just at room temperature, at a normal
It can complete.Saccharomycete load had not only increased the aerial stability of nano zero valence iron, but also effectively reduced material consumption, energy consumption, no
Secondary pollution is generated, there is considerable economic benefit and social benefit.
(2) saccharomycete prepared carries nano zero valence iron and can firmly be limited to reactant in saccharomycete, and reactant is made to reach
High concentration conditions, to accelerate reaction speed.The modified yeast bacterium of gained is than untreated ferment after chemical treatment
Female bacterium is more suitable as the carrier and stabilizer of nano zero valence iron, and the nano zero valence iron that modified yeast bacterium carries can be stable in the air
3 months, and reactivity higher.
1. saccharomycete modified yeast bacterium obtained after chemical treatment carries nano zero valence iron than unprocessed person to removal
Cr (VI) has higher reactivity.The 0.1molL for being 6 in pH-1In phosphate-buffered medium, 10mg modified yeast bacterium carry
Nano zero valence iron is in 15min to 50mgL-1The removal rate of Cr (VI) is 100%, and the saccharomycete of equivalent carries nano zero valence iron and exists
After reaction for 24 hours, the removal rate to Cr (VI) is 56.4%.Than montmorillonite-loaded nanometer disclosed in patent ZL201210447511.9
Zero-valent Iron has higher Cr (VI) removal activity：When pH is 6,1gL-1Montmorillonite-loaded nano zero valence iron is right in 40min
20mg·L-1The removal rate of Cr (VI) is 99%, and 2gL-1Modified yeast bacterium prepared by the embodiment of the present invention 9 carries nano zero-valence
Iron can be in 15min by 50mgL-1Cr (VI) is completely removed.
2. the reactivity that modified yeast bacterium carries nano zero valence iron degradation 2,4,6- trichlorophenol, 2,4,6,-Ts is slightly above unmodified yeast
The nano zero valence iron of bacterium load, the two is respectively under the same conditions 54.4% He to the degradation rate of 2,4,6- trichlorophenol, 2,4,6,-T of equivalent
50.6%.
(3) saccharomycete carries nano zero valence iron meeting automatic sedimentation after synthesis or use, convenient for recycling.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph (a, c) and EDS figures (b, d) that the saccharomycete prepared and saccharomycete carry nano zero valence iron.
Specific implementation mode
In the following, the present invention will be further detailed with embodiment, but its any for being not limited to these examples
A or similar example.
Embodiment 1：
(1) saccharomycete culture and processing：As previously mentioned, carrying out shaking flask culture yeasts bacterium, simultaneously washing thalline is then collected, it is cold
It is lyophilized dry.
(2) 1.0g saccharomycete accurately is weighed in 100mL beakers, 5.0mL 0.18molL are added-1FeSO4·7H2O
Solution is placed in 30 DEG C of water-baths with 200rmin-1Rotating speed stir 30min, in 3000rmin-110min is centrifuged under rotating speed,
It obtains being adsorbed with Fe2+Yeast vector.
(3) it is adsorbed with Fe by what step (2) obtained2+Saccharomycete be transferred in 250mL there-necked flasks, be added 5.0mL water, be placed in
With 200rmin in 30 DEG C of water-baths-1Rotating speed stir 30min, while with 0.5mLmin-1Speed be passed through N2.Persistently stirring
It mixes and stirs in logical N2Under conditions of, by constant pressure funnel with 0.8mLmin-1Speed instill 25.0mL 0.25molL-1's
NaBH4Solution.It is taken out after the reaction was continued 1h.In 8000rmin-1Under the conditions of centrifuge 10min, solid second distillation water washing 3
It is secondary, after freeze-drying grinding nano zero valence iron is carried up to saccharomycete.
Embodiment 2：
Culture, processing yeast and saccharomycete carry the preparation process of nano zero valence iron with embodiment 1, in addition to addition
FeSO4·7H2O solution concentrations are 0.36molL-1。
Embodiment 3：
Culture, processing yeast and saccharomycete carry the preparation process of nano zero valence iron with embodiment 1, in addition to addition
FeSO4·7H2O solution concentrations are 0.72molL-1, NaBH4Solution concentration is 0.69molL-1。
Embodiment 4：
Culture, processing yeast and saccharomycete carry the preparation process of nano zero valence iron with embodiment 1, in addition to addition
FeSO4·7H2O solution concentrations are 0.90molL-1, NaBH4Solution concentration is 0.69molL-1。
Embodiment 5：
Culture, processing yeast and saccharomycete carry the preparation process of nano zero valence iron with embodiment 1, in addition to addition
FeSO4·7H2O solution concentrations are 1.07molL-1, NaBH4Solution concentration is 1.72molL-1。
Embodiment 6：
Culture, processing yeast and saccharomycete carry the preparation process of nano zero valence iron with embodiment 1, in addition to addition
FeSO4·7H2O solution concentrations are 1.43molL-1, NaBH4Solution concentration is 0.58molL-1。
Embodiment 7：
Culture, processing yeast and saccharomycete carry the preparation process of nano zero valence iron with embodiment 6, in addition to the NaBH of instillation4
Solution concentration is 0.25molL-1。
Embodiment 8：
Culture, processing yeast and saccharomycete carry the preparation process of nano zero valence iron with embodiment 6, in addition to the NaBH of instillation4
Solution concentration is 0.86molL-1。
Embodiment 9：
The culture of saccharomycete and saccharomycete carry the preparation process of nano zero valence iron with embodiment 6, in addition to carrier used is
Modified yeast bacterium carrier, i.e., by conventional method culture yeasts bacterium, centrifugation, after washing, being resuspended in mass percent concentration is
In 0.5~10% sodium hydroxide solution, with 100rmin at a temperature of 40~60 DEG C-1It is small to carry out oscillation treatment 24~48
Shi Hou, after centrifugation, washing, freeze-drying obtains modified yeast bacterium carrier.
Embodiment 10：
The culture of saccharomycete and saccharomycete carry the preparation process of nano zero valence iron with embodiment 9, in addition to for quality percentage
Specific concentration is replaced the sodium hydroxide solution that mass percent concentration is 0.5~10% by 0.5~10% hydrochloric acid solution.
Embodiment 11：
The culture of saccharomycete and saccharomycete carry the preparation process of nano zero valence iron with embodiment 9, in addition to mass percent
It is 0.5~10% sodium hydroxide solution that a concentration of 1~20% sodium chloride solution, which replaces mass percent concentration,.
Embodiment 12：
The culture of saccharomycete and saccharomycete carry the preparation process of nano zero valence iron with embodiment 9, in addition to mass percent
It is 0.5~10% sodium hydroxide solution that a concentration of 1~20% Klorvess Liquid, which replaces mass percent concentration,.
Embodiment 13：
The culture of saccharomycete and saccharomycete carry the preparation process of nano zero valence iron with embodiment 9, in addition to mass percent
It is 0.5~10% sodium hydroxide solution that a concentration of 1~20% ethanol solution, which replaces mass percent concentration,.
Embodiment 14：
The culture of saccharomycete and saccharomycete carry the preparation process of nano zero valence iron with embodiment 9, in addition to mass percent
It is 0.5~10% sodium hydroxide solution that a concentration of 0.1~5% Tween-80 solution, which replaces mass percent concentration,.
Embodiment 15：
Culture, processing yeast and saccharomycete carry the preparation process of nano zero valence iron with embodiment 9, in addition to the modification ferment of addition
Female bacterium carrier is 0.3g, and addition is a concentration of 0.04molL of 16.0mL-1FeSO4·7H2O solution and 16.0mL are a concentration of
0.08mol·L-1NaBH4Solution.
Embodiment 16：
Culture, processing yeast and saccharomycete carry the preparation process of nano zero valence iron with embodiment 1, in addition to the saccharomycete of addition
Carrier is 8.0g, and addition is a concentration of 1.16molL of 25.0mL-1FeSO4·7H2O solution and 38.5mL are a concentration of
2.80mol·L-1NaBH4Solution.
Application Example 1：
Saccharomycete carries the Cr (VI) in nano zero valence iron removal water body.
The removal of Cr (VI) carries out in 10mL centrifuge tubes in water body.4.50mL is added into 10mL colorimetric cylinders successively
0.10mol·L-1Phosphate buffer solution (pH=6.0), 0.50mL 500mgL-1Cr (VI) solution and 10.0mg saccharomycete
Nano zero valence iron is carried, shakes up and is placed in 25 DEG C of water-baths and starts timing, timing takes out 0.10mL and uses 1,5- diphenyl phosphinylidynes
Two hydrazine methods measure the removal rate of Cr (VI).
When addition be that the saccharomycete that is prepared in 10.0mg embodiments 1 carries nano zero valence iron when, for 24 hours after, Cr (VI's) goes
Except rate is 10.1%.
When addition be that the saccharomycete that is prepared in 10.0mg embodiments 2 carries nano zero valence iron when, for 24 hours after, Cr (VI's) goes
Except rate is 16.4%.
When addition be that the saccharomycete that is prepared in 10.0mg embodiments 3 carries nano zero valence iron when, for 24 hours after, Cr (VI's) goes
Except rate is 30.3%.
When addition be that the saccharomycete that is prepared in 10.0mg embodiments 4 carries nano zero valence iron when, for 24 hours after, Cr (VI's) goes
Except rate is 46.0%.
When addition be that the saccharomycete that is prepared in 10.0mg embodiments 5 carries nano zero valence iron when, for 24 hours after, Cr (VI's) goes
Except rate is 90.6%.
When addition be that the saccharomycete that is prepared in 10.0mg embodiments 6 carries nano zero valence iron when, for 24 hours after, Cr (VI's) goes
Except rate is 56.4%.
When addition be that the saccharomycete that is prepared in 10.0mg embodiments 7 carries nano zero valence iron when, for 24 hours after, Cr (VI's) goes
Except rate is 50.7%.
When addition be that the saccharomycete that is prepared in 10.0mg embodiments 8 carries nano zero valence iron when, for 24 hours after, Cr (VI's) goes
Except rate is 78.3%.
When addition be that the saccharomycete that is prepared in 10.0mg embodiments 9 carries nano zero valence iron when, when 5min, 5.00mL
50mg·L-1It is 100% when being 89.0%, 15min when the removal rate of Cr (VI) is 51.3%, 10min.
When addition be 10.0mg yeast vectors when, for 24 hours after, 5.00mL 50mgL-1The removal rate of Cr (VI) is
7.7%.
When addition be modified yeast bacterium carrier used in 10.0mg embodiments 9 when, for 24 hours after, 5.00mL 50mgL-1Cr
(VI) removal rate is 15.5%.
Shown under the same conditions by comparison, modified yeast bacterium carries the reactivity of nano zero valence iron removal Cr (VI)
Higher than the nano zero valence iron of unmodified saccharomycete load, the former is in 15min to 50mgL-1The removal rate of Cr (VI) is
100%, for the latter of equivalent after reaction for 24 hours, the removal rate to Cr (VI) is 56.4%.
Application Example 2：
Saccharomycete carries nano zero valence iron degradation 2,4,6- trichlorophenol, 2,4,6,-Ts.
The reaction that saccharomycete carries nano zero valence iron degradation 2,4,6- trichlorophenol, 2,4,6,-Ts carries out in 10mL glass centrifuge tubes.It weighs
4.0~10.0mg saccharomycete carries nano zero valence iron in 10mL centrifuge tubes, and 4.00mL0.05~0.10mmolL is added-12,
4,6- trichlorophenol, 2,4,6,-T solution.It fully shakes up to be placed in 30 DEG C of air bath oscillators and be reacted.Timing takes 0.20mL supernatants
HPLC detections are carried out, the degradation rate of 2,4,6- trichlorophenol, 2,4,6,-Ts is calculated using external standard method.
When addition be that the saccharomycete that is prepared in 10.0mg embodiments 8 carries nano zero valence iron when, after reacting 9h, 4.00mL
0.10mmol·L-1The degradation rate of 2,4,6- trichlorophenol, 2,4,6,-Ts is 50.6%.
When addition be that the saccharomycete that is prepared in 10.0mg embodiments 16 carries nano zero valence iron when, after reacting 9h, 4.00mL
0.10mmol·L-1The degradation rate of 2,4,6- trichlorophenol, 2,4,6,-Ts is 50.5%.
When addition be to prepare nano zero valence iron saccharomycete in 10.0mg embodiments 9 when, react 9h after, 4.00mL
0.10mmol·L-1The degradation rate of 2,4,6- trichlorophenol, 2,4,6,-Ts is 54.4%.
When addition be to prepare nano zero valence iron saccharomycete in 4.0mg embodiments 15 when, react 12h after, 8.00mL
0.05mmol·L-1The degradation rate of 2,4,6- trichlorophenol, 2,4,6,-Ts is 28.8%.
Show that the reactivity of modified yeast bacterium load nano zero valence iron 2,4,6- trichlorophenol, 2,4,6,-Ts of degradation is slightly above by comparison
The nano zero valence iron of unmodified saccharomycete load, the two under the same conditions distinguish the degradation rate of 2,4,6- trichlorophenol, 2,4,6,-T of equivalent
For 54.4% and 50.6%.
Application Example 3：
Saccharomycete carries nano zero valence iron degradation 2,4 dichloro phenol.
Be added in 10mL glass centrifuge tubes the modified yeast bacterium prepared in 4.0mg embodiments 15 carry nano zero valence iron and
8.00mL 0.05mmol·L-12,4- chlorophenesic acid solution, fully shake up be placed in 30 DEG C of air bath oscillators carry out it is anti-
It answers.After reacting 10h, the degradation rate of 2,4- chlorophenesic acids is 18.0%.
Application Example 4：
Saccharomycete carries nano zero valence iron degradation 4- chlorophenols.
Be added in 10mL glass centrifuge tubes the modified yeast bacterium prepared in 4.0mg embodiments 15 carry nano zero valence iron and
8.00mL 0.05mmol·L-14- chlorobenzene phenol solutions, fully shake up to be placed in 30 DEG C of air bath oscillators and be reacted.Instead
After answering 16h, the degradation rate of 4- chlorophenols is 7.0%.
Application Example 5：
Saccharomycete carries nano zero valence iron degradation 2- chlorophenols.
Be added in 10mL glass centrifuge tubes the modified yeast bacterium prepared in 4.0mg embodiments 15 carry nano zero valence iron and
8.00mL 0.05mmol·L-12- chlorobenzene phenol solutions, fully shake up to be placed in 30 DEG C of air bath oscillators and be reacted.Instead
After answering 12h, the degradation rate of 2- chlorophenols is 11.0%.
Claims (9)
1. a Yeasts carry nano zero valence iron, it is characterised in that it includes yeast vector or warp that the saccharomycete, which carries nano zero valence iron,
The nano zero-valence iron particle for crossing chemically treated modified yeast bacterium carrier and its load is to prepare gained by following preparation process：
(1) bread microzyme or S. cervisiae are cultivated according to a conventional method, the saccharomycete of gained is centrifuged, and after washing, freezing is dry
It is dry to obtain yeast vector.Or centrifuge the saccharomycete of gained, after washing, it is 0.1~5% to be resuspended in mass percent concentration
Tween-80 solution, and/or mass percent concentration be 0.5~10% hydrochloric acid solution, and/or mass percent concentration be
The ethanol solution, and/or quality percentage that 0.5~10% sodium hydroxide solution, and/or mass percent concentration is 1~20%
In the sodium chloride solution that the Klorvess Liquid, and/or mass percent concentration that specific concentration is 1~20% are 1~20%, 40~
Stirring or oscillation treatment are chemically treated for 24~48 hours at a temperature of 60 DEG C.Centrifugation, washing after, freeze-drying, obtain through
Cross chemically treated modified yeast bacterium carrier.
(2) by 0.02~1.43molL-1Molysite or perferrite solution are added to the yeast vector or change that step (1) obtains
Property yeast vector in, make the mass ratio of molysite and saccharomycete be 50~400mgg-1, in 50~200rmin-1Lower stirring
Or 0.5~2h of oscillating reactions obtains being adsorbed with Fe after centrifugation, washing2+Or Fe3+Saccharomycete or modified yeast bacterium.
(3) in lasting stirring or oscillation simultaneously with 0.5~0.8mLmin-1Gas supply speed into the solution lead to N2Condition
Under, it is adsorbed with Fe toward what step (2) obtained2+Or Fe3+Saccharomycete or modified yeast bacterium in 0.20~1.00mLmin-1's
Speed instills 0.04~2.80molL-1Sodium borohydride or solution of potassium borohydride make sodium borohydride or potassium borohydride and Fe2+Or
Fe3+Substance amount ratio be 2~10:1, after continuing stirring or oscillating reactions 0.5h~2h, then it is separated by solid-liquid separation, solid water
Washing 3 times, freeze-drying carry nano zero valence iron to get the saccharomycete or modified yeast bacterium.
2. a Yeasts carry nano zero valence iron, it is characterised in that the method for removing soil or Heavy Metals in Waters pollution.
3. saccharomycete carries nano zero valence iron according to claim 2, it is characterised in that the heavy metal pollution preferably removed is six
Valence chromium ion pollutes.
4. a Yeasts carry nano zero valence iron, it is characterised in that the side for the organic pollution in degrade soil or water body
Method.
5. saccharomycete carries nano zero valence iron according to claim 4, it is characterised in that the organic pollution preferably degraded is 2,
4,6- trichlorophenol, 2,4,6,-Ts.
6. saccharomycete carries nano zero valence iron according to claim 4, it is characterised in that the organic pollution preferably degraded is 2,
4- chlorophenesic acids.
7. saccharomycete carries nano zero valence iron according to claim 4, it is characterised in that the organic pollution preferably degraded is 2-
Chlorophenol.
8. saccharomycete carries nano zero valence iron according to claim 4, it is characterised in that the organic pollution preferably degraded is 4-
Chlorophenol.
9. saccharomycete carries nano zero valence iron according to claim 4, it is characterised in that the organic pollution preferably degraded is 2,
6- chlorophenesic acids.
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| CN114854424A (en) * | 2022-04-26 | 2022-08-05 | 上海亚新城市建设有限公司 | Soil organic matter pollution repairing agent and preparation method thereof |
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