CN104624054B - A kind of preparation method of control membrane biological pollution bactericide - Google Patents
A kind of preparation method of control membrane biological pollution bactericide Download PDFInfo
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- CN104624054B CN104624054B CN201310547155.2A CN201310547155A CN104624054B CN 104624054 B CN104624054 B CN 104624054B CN 201310547155 A CN201310547155 A CN 201310547155A CN 104624054 B CN104624054 B CN 104624054B
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Abstract
The present invention relates to a kind of preparation method of control membrane biological pollution bactericide.By Bacillus acidi lactici at normal temperatures by Ag+It is reduced to Ag0Nano particle, and then realize the preparation of excellent membrane biological pollution inhibitor and cleaning agents of membrane.Bacteria suspension is made in Bacillus acidi lactici bacterium powder, mixed again with silver ammino solution after regulation basicity, 12~48h is reacted at 10~70 DEG C, obtain the mixed liquor containing microbial body and nano silver colloid, large stretch of biological residuum is removed through initial centrifugation, further biological silver sol is concentrated with ultra-filtration centrifuge tube, Na is removed+、Ag+、OH‑、NO3 ‑Deng foreign ion, biological nano silver well dispersed in aqueous is most obtained through vacuum freeze drying afterwards.The effect that this Nano Silver has good antibacterial, suppresses biomembrane and promote biofilm to come off.
Description
Technical field
The present invention relates to water process and technical field of membrane separation, such as membrane bioreactor, micro-filtration, ultrafiltration, nanofiltration and reverse osmosis
Separating technology is waited thoroughly, application field is related to sewage disposal and recycling, drink water purifying, biotechnology etc..
Background technology
Extensively, the decline yet with membrane flux caused by fouling membrane and separating property is UF membrane to application of membrane separation technology
The problem of most serious that technology is faced.Generally, fouling membrane can be divided into：Organic contamination, inorganic pollution, colloid pollution and biology are dirty
Dye.Wherein, the biological pollution caused due to biofilm formation is considered as a kind of fouling membrane most complicated, that harm is maximum.
Biomembrane refers to the microorganism that the extracellular polymeric of microbial cell and its secretion is formed after dielectric surface attachment
Aggregation.Once forming biological pollution, can not only harm be produced to public health, more can be to water treatment procedure particularly film process
Process is adversely affected.
Major measure currently for membrane biological pollution has：The disinfectant or ultraviolet irradiation of strong oxidizing property are pre-processed
And Physical Chemical Cleaning.But ripe biofilm structure is firm, has very strong resistance to cleaning process, it is difficult to go completely
Remove.In addition, frequently physics, Chemical cleaning can not only increase operating cost and can more cause irreversible broken in itself to membrane material
It is bad.Based on problem above, harm of the effective bactericide of Development of Novel to mitigate biological pollution becomes particularly important.
The superior antibiotic property of Nano Silver becomes one of most widely used nano material.Many researchs show at present,
Nano Silver can effectively suppress the formation of biomembrane, promote coming off for biofilm, therefore be expected to develop into one kind and have
The bioflm inhibiting agents or cleaning agents of membrane of effect mitigate the harm of biological pollution in membrane filtration system.
The preparation method of Nano Silver is a lot, and Physical and chemical method are obtained because experiment condition is simple, the advantages of be easy to regulation and control
To widely applying.These methods are also faced with such as nano-particle reunion, high energy consumption, severe reaction conditions, are difficult to simultaneously
The single dispersed nano silver powder end of solid, final products nano-silver powder are isolated in large-scale production and being difficult to from nano silver colloidal sol
The problems such as redispersibility is poor.It is generally acknowledged that the antibiotic property of Nano Silver is inversely proportional with particle diameter, and the Nano Silver of ordinary chemical method synthesis
Particle diameter very little or it is dense when be easy to reunite, greatly reduce the specific surface area of nano-particle, this will certainly influence
The performance of nano particle and application.
In recent years, a kind of method that biological reducing prepares Nano Silver as green has obtained increasing concern.Bacterium,
Fungi, algae and plant extracts etc. can serve as " the nanometer factory " of biological reducing.Researcher have studied several lactic acid bacterias
The ability of reduction synthesis biological nano silver.The new fresh thalli for cultivating ripe is configured to certain density bacteria suspension, basification
Reacted afterwards with certain density silver ammino solution, find Bacillus acidi lactici（Lactobacillus fermentum LMG 8900）Have
The ability of most strong reduction synthesis biological nano silver, can synthesize the about narrow granule of 11.2 nm, particle diameter distribution on cell membrane
Footpath Nano Silver.Author mainly have studied the Nano Silver for being distributed in cell surface, protection of this biological nano silver in microbial cell
Under can efficiently reduce reunion, but more cell component makes dried biological nano silver powder be difficult equal in aqueous
It is even scattered, while showing that perhaps substantial amounts of components of biomass can hinder nano-particle to the silver-colored antibacterial mechanisms research of this biological nano
With the direct contact of test bacteria, so as to reduce somewhat the anti-microbial property of Nano Silver.Equally used in the application
Bacillus acidi lactici（Lactobacillus fermentum LMG 8900）For raw material, by modifying the method having been reported
And improvement, it can obtain containing enrich, smaller particle（About 6 nm）The biological silver sol of Nano Silver.In addition, prepared by bioanalysis
Nano silver colloidal sol be also faced with the problem of subsequent concentration is purified.For example have been reported（Application number 200710008639.4）Using
Heating evaporation initial concentration nano silver colloidal sol, further adds a large amount of organic solvents (ethanol or acetone) destruction silver sol surface water
Membrane stability, makes its dehydrated precipitate, is repeatedly washed tentatively to remove foreign ion with water-containing organic solvent, then at 30-60 DEG C
Vacuum drying obtains nano-silver powder.But heating evaporation easily makes Nano Silver adherent caking of reuniting in a reservoir, can make yield significantly
Reduction；The probability of nano-particle reunion can be also increased with organic solvent washing nano-particle repeatedly.While a large amount of organic solvents
Environment is had undesirable effect using meeting.
And the application is exactly to overcome disadvantages described above to prepare, surpass there is provided a kind of cleaning, nontoxic, environment-friendly biological reducing
The small particle for purifying high degree of dispersion in aqueous is collected by centrifugation in filter（The nm of average 6）The method of biological nano silver antibacterial agent.
The content of the invention
The purpose of the present invention aims to provide a kind of preparation method of novel nanometer silver bactericide, is used as a kind of preprocess method
Or cleaning agents of membrane is applied in membrane filtration system, the stable against biological contamination performance of whole system is improved, extends the use of membrane module
Life-span.
New type bactericide of the present invention is prepared using a kind of microbial cell composition is reducing agent and protective agent
Biological nano silver powder.Obtained nano-silver powder particle diameter very little（6 nanometers of average grain diameter）, have in aqueous well again
Dispersiveness and stability.Pass through small particle Nano Silver and bacterium（Escherichia coli, pseudomonas aeruginosa）Interaction, effectively drops
The survival rate of low test bacteria, hence it is evident that reduce attachment and film-forming amount of the bacterium on membrane material surface；Biological nano silver is given birth to maturation
Biomembrane coming off from membrane material surface can be also effectively facilitated after the effect of thing film.
The preparation method of water-soluble nano silver powder of the present invention is as follows：
It will be enlarged by the Bacillus acidi lactici of culture（Lactobacillus fermentum LMG 8900）Bacterium mud is freeze-dried, and is ground
It is milled into dry bacterium powder standby；
Microorganism dry bacterium powder is configured to 1~20 g/L bacteria suspensions, NaOH regulation pH is added, makes bacteria suspension [OH]-1It is dense eventually
Spend for 0.2~0.4 mol L-1, then mix with silver ammino solution, final concentration of 1~20 g/L of silver ammino solution shakes at 10~70 DEG C
The h of shaken cultivation 12~48 in bed, obtains the mixed liquor containing microbial body and nano silver colloid；By microbial body and nano-silver colloid
The mixed liquor initial centrifugation separation of body, discards bulk microbial debris, the buff that collection supernatant is stablized to black
Biomass silver sol；Further centrifuged with ultra-filtration centrifuge tube of the molecular weight in 1000-10000 that dam in biomass silver sol
Most of moisture and Na+ 、Ag+ 、OH- 、NO3 -Plasma, obtains the biomass silver sol of highly concentrated purifying；Will be above-mentioned highly concentrated
Degree biomass silver sol is freeze-dried under a high vacuum, and grinding obtains biological nano silver powder.
Present invention process is simple, environmental protection, it is not necessary to chemical reagent of the addition in addition to silver ammino solution, sodium hydroxide,
Ultrafiltration centrifugal process can effectively in removal system heteroion and moisture content, cleaning and one step of concentration are realized.Obtained biology
Silver-colored content is 50% in Nano Silver powder（W%）More than, particle diameter distribution is uniform, has the redispersibility of height in aqueous and steady
It is qualitative.The biological nano silver powder has the effect that good antibacterial, suppression biomembrane and promotion biofilm comes off, for film
Biological pollution problem, has a good application prospect in technical field of membrane separation.
Brief description of the drawings
The TEM figures that Fig. 1 disperses for biological nano silver powder prepared by the present invention in water.Scale is 20nm in figure.
Fig. 2-1 is the full complete shaft-like shape appearance figure of Escherichia coli without biological nano silver processing；Fig. 2-2 receives for biology
There is plasmolysis to some extent, torsional deformation in the Escherichia coli figure that tem observation is arrived after rice silver processing, cell.
Embodiment
Embodiment 1：
The preparation of Bacillus acidi lactici bacteria suspension：Weigh the finely ground dry bacterium powders of 2.0 g and add 60 mL deionized waters, stirring vibration
It is well mixed standby；The preparation of silver ammino solution：15.74 g silver nitrates are weighed, appropriate amount of deionized water dissolving is added, 5% ammonia is added dropwise
Water is just disappeared until the brown precipitation of generation, and 100 mL are settled to deionized water;Prepare 2 mol L-1Sodium hydroxide
Solution.
The mL of bacteria suspension 60, the mL of NaOH solution 20, the mL of silver ammino solution 20 are mixed equal in 250 mL conical flask
Even, bacterium powder concentration is 20 g/L, Ag in end reaction system+Concentration is 20 g/L, [OH]-1Concentration is 0.4 mol L-1.Will be mixed
Liquid is closed to be placed in 30 DEG C of shaking tables（180rpm）Shaken cultivation 24h, obtains the mixed liquor containing microorganism residuum and nano silver colloidal sol；
Mixed liquor initial centrifugation is separated（7000 rpm）, thalline relic is discarded, supernatant is collected and obtains biomass silver sol.
By biomass silver sol ultra-filtration centrifuge tube（Molecular weight dam 5000）In 7000 rpm centrifugations, in centrifugation masterpiece
Under, moisture and foreign ion（Na+ 、Ag+ 、OH- 、NO3 -）Through milipore filter, biological silver is then trapped, synchronous to realize biology
The concentration and purifying of matter silver sol.Silver sol is concentrated into about 20 mL or so, is dried with high-vacuum freeze drying machine, grinding
Obtain the water-soluble nano silver powder containing biomass.
Silver-colored mass fraction is about 60% in silver powder.Nano-silver powder scattered again in water is observed under transmission electron microscope（As schemed
1）, most of Argent grain is spherical in shape, favorable dispersibility.Nano Silver picture is surveyed by Gatan Pleasanton softwares
Amount, obtains the particle diameter of each particle in picture, particle diameter distribution statistics is carried out with the softwares of SPSS 18.0, as a result shows biological silver
Average grain diameter is about 6.0nm.Escherichia coli are carried out after mixing contact with certain density biological nano silver, transmission electron microscope
（TEM）Observe visible blank control sample（Fig. 2-1）In, Bacillus coli cells are full complete, and typical rod-like structure is presented, and pass through
Cell after processing（Fig. 2-2）There is different degrees of plasmolysis, torsional deformation, part intracellular matter is lost in serious.
Although the present invention is disclosed the present invention by preferred embodiment, without departing from appended claims
In the case of the field of the invention and scope of middle restriction, many modifications, the changes and modifications of described embodiment are feasible
's.Thus, it is intended that the invention is not restricted to described embodiment, but the present invention has the language of appended claims
Mention the four corner that its equivalent is limited.
Claims (1)
1. a kind of microorganism reduction preparation method for the bactericide that can effectively control membrane biological pollution, it is characterised in that including with
Lower step：
1) preparation of the bacteria suspensions of Bacillus acidi lactici Lactobacillus fermentum LMG 8900：Weigh the finely ground dry bacterium of 2.0g
Powder adds 60mL deionized waters, and stirring vibration is well mixed standby；
2) preparation of silver ammino solution：15.74g silver nitrates are weighed, deionized water dissolving are added, the ammoniacal liquor of dropwise addition 5% is until producing
Brown precipitation just disappear, be settled to 100mL with deionized water；
3) 2mol L are prepared-1Sodium hydroxide solution；
4) bacteria suspension 60mL, NaOH solution 20mL, silver ammino solution 20mL are well mixed in 250mL conical flask, it is final anti-
It is 20g/L, Ag to answer bacterium powder concentration in system+Concentration is 20g/L, [OH]-1Concentration is 0.4mol L-1；
5) mixed liquor is placed in 30 DEG C of shaking tables with 180rpm shaken cultivation 24h, obtains molten containing microorganism residuum and Nano Silver
The mixed liquor of glue；Mixed liquor is separated with 7000rpm initial centrifugations, thalline relic is discarded, supernatant is collected and obtains biomass silver
Colloidal sol；
6) the biomass silver sol ultra-filtration centrifuge tube that molecular weight is 5000 with damming is centrifuged in 7000rpm, in centrifugal action
Under, moisture and foreign ion Na+、Ag+、OH-、NO3 -Through milipore filter, biological silver is then trapped, and synchronously realizes biomass silver sol
Concentration and purifying, silver sol is concentrated into 20mL, is dried with high-vacuum freeze drying machine, and grinding obtains the water containing biomass
Dissolubility nano-silver powder.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105344252B (en) * | 2015-10-27 | 2018-07-03 | 华中科技大学 | A kind of method and product for improving polyimide film antifouling property |
| CN105855564A (en) * | 2016-05-27 | 2016-08-17 | 厦门大学 | Method for preparing silver nanoparticles through adsorption and reduction of silver nitrate by activated sludge |
| CN106041116A (en) * | 2016-05-27 | 2016-10-26 | 厦门大学 | Method for preparing silver nanoparticles by adsorbing and reducing silver-ammonia solution through activated sludge |
| CN106621845A (en) * | 2017-03-06 | 2017-05-10 | 江苏理工学院 | Preparation method and application of combined pollution resisting type membrane material |
| CN108732151B (en) * | 2018-05-31 | 2021-01-19 | 华南理工大学 | Preparation of luminescent gold nanoparticles with high-sensitivity optical response to volatile amine and rapid analysis and detection method thereof |
| EP3686579A1 (en) * | 2019-01-28 | 2020-07-29 | Dow Global Technologies Llc | Method for visualizing and quantifying biofilm on solid surfaces |
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Non-Patent Citations (1)
| Title |
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| 《Biogenic silver nanoparticles (bio-Ag0) decrease biofouling of bio-Ag0/PES nanocomposite membranes》;Manying Zhang et.al;《Water Research》;20120131;第2077页第1段，2078页2.1、2.2部分 * |
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Effective date of registration: 20190524 Address after: 361115 W403 Breeding Center, 88 Xiangxing Road, Xiangan District, Xiamen City, Fujian Province Patentee after: In Tianjin Branch (Xiamen) Membrane Technology Co Ltd Address before: 361021 No. 1799 Jimei Avenue, Jimei District, Xiamen City, Fujian Province Patentee before: Institute of Urban Environment, Chinese Academy of Sciences |
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