CN101705359A - Method for recovering silver in silver-containing waste water by biological method - Google Patents
Method for recovering silver in silver-containing waste water by biological method Download PDFInfo
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- CN101705359A CN101705359A CN200910213078A CN200910213078A CN101705359A CN 101705359 A CN101705359 A CN 101705359A CN 200910213078 A CN200910213078 A CN 200910213078A CN 200910213078 A CN200910213078 A CN 200910213078A CN 101705359 A CN101705359 A CN 101705359A
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Abstract
The invention provides a method for recovering silver in silver-containing waste water by a biological method. The method processes the silver-containing waste water of the industries of electroplating, electronics, photography and the like by using cultured aspergillus microorganisms and synthesizes nano stage particle silver by biological catalysis, and the nano stage particle silver has very high economic value and favorable application prospect. The method comprises the following steps: firstly, after sterilizing a liquid culture medium, putting into an aseptic inoculation chamber, cooling, inoculating aspergillus proportionally and culturing the culture medium after being inoculated with the aspergillus in an oscillation way; after culturing for 6-7 days, centrifugalizing, collecting a precipitate aspergillus mixture, adding into waste liquid containing AgNO3, centrifugalizing for 10-20 minutes after mixing evenly and culturing for 6-10 days at room temperature, separating liquid from the precipitate, washing the precipitate for several times by water repeatedly and collecting silver nano particles with the particle diameter of about 15-50nm.
Description
Technical field:
The present invention relates to a kind of method that adopts the aspergillus processing environment waste water and the biosynthesizing nanometer-level silver of cultivation, can be used for handling the silver-containing waste water of industries such as plating, electronics, photograph, environment purification.
Background technology:
Aspergillus (Aspergillus) fungi, be filamentous fungus, naturally live in suddenly, in the marsh, river, especially maximum with agricultural land soil, usually colonize in plant living body or the saprophytes stubble, can seek parasitic life, also can seek saprogenesis, vitality is very strong, is the important motivating force that the nature organic substance transforms.
Common aspergillus niger (Aspergillus niger), flavus (Aspergillus flavus), Aspergillus fumigatus (Aspergillus fumigatus) etc. all are soil inhabitants, natural be present in the agricultural land soil and the pit in.On the septic straw in residual field, rubbish, the food thrown aside, be found everywhere aspergillus niger system soy sauce commonly used, fermented bean curd, wine brewing, production silage etc. in the production.Aspergillus niger, Aspergillus fumigatus etc. are also through being usually used in the experiment material of scientific research simultaneously.
The a large amount of silver-containing waste waters of the annual generation of industries such as plating, patina worker, electronics, film, photograph, serious environment pollution, the method for recycling is not too economical and practical at present.Chemical Treatment commonly used causes fierce chemical reaction, and the silver nitride precipitation thing of generation can not be recycled, owing to introduce new poisonous chemical reagent, has caused the secondary pollution environment simultaneously.
Summary of the invention:
The object of the invention is to provide a kind of biological process to reclaim the method for silver in the silver-containing waste water, this method is handled the silver-containing waste water of industries such as plating, electronics, photograph with microorganisms with expanded culture, biocatalysis synthesis of nano grade particles silver has very high economic worth and good prospects for application.
The objective of the invention is to realize by following measure:
A kind of biological process reclaims the method for silver in the silver-containing waste water, it is characterized in that:
After at first liquid nutrient medium being cultivated sterilization, be placed on the indoor cooling of aseptic inoculation, when substratum in the triangular flask is cooled to 29-32 ℃, inoculation aspergillus, the by weight/volume of aspergillus inoculum size and substratum is: 10～80mg/L, substratum behind the inoculation aspergillus is placed on shaking culture on the microorganism shaking table together with triangular flask, and oscillation frequency is 170-200rpm, and culture temperature is 35 ± 2 ℃;
After cultivating in 6～7 days, with the centrifugal 15-25 of 5000-6000rpm minute, collecting precipitation aspergillus mixture added to and contains AgNO
3Waste liquid, the aspergillus mixture and the AgNO of adding
3The by weight/volume of waste liquid is: 200-500mg/L, after mixing, at room temperature cultivate 6-10 days after, with 5000-6000rpm centrifugal treating 10-20 minute, and separating liquid and precipitation, water repetitive scrubbing precipitation is for several times, collect silver nano-grain, particle diameter is about 15-50nm.
Described aspergillus is selected aspergillus niger, flavus or Aspergillus fumigatus for use.
The making processes of described liquid nutrient medium is: add following each material configuration in every 1000mL water respectively and form, 7.5-8.5g KH is wherein arranged
2PO
4, 2.0-2.5g K
2HPO
4, 0.6-2.0g (NH
4)
2SO
4, 0.1-0.2gMgSO
4, 0.3-0.4g yeast extract, 5-10g glucose, 5-10g Semen Maydis powder, regulate pH to 6-7 with dilute hydrochloric acid and diluted sodium hydroxide solution.
The sterilising method of described liquid culture is: substratum is placed high-pressure sterilizing pot, and temperature is 120-124 ℃ in the maintenance Autoclave, and pressure is 0.12-0.8Mpa, sterilizes 20～40 minutes.
Pending contain that Silver Nitrate content is generally 100-1500mg/L in the Silver Nitrate waste water.
The present invention adopts the Aspergillus microbiological treatment to purify industry silver-containing waste waters such as plating, photograph, electronics; the protection environment; reduce and pollute; the nano-scale particle of biosynthesizing simultaneously silver; this method can not only solve the problem of environmental pollution of silver-containing waste water, the nanometer-level silver particle that can obtain having using value simultaneously, and method is easy; with low cost, the method for handling silver-containing waste water and biosynthesizing production silver nano material with aspergillus microorganism has not yet to see open report.
The present invention utilizes aspergillus can secrete some extracellular enzymes such as amylase, proteolytic enzyme, cellulase, nitrate reductase etc. in process of growth in environment.Wherein some enzyme has the catalytic reduction effect to the precious metal ion in some industrial effluent, makes silver ions be reduced the nano level silver-colored solids precipitation of formation and gets off.Biological treatment of the present invention, reaction temperature and, need not to add more poisonous chemical reagent, cost is low, and is easy and simple to handle, and most critical is can gather in the crops at last to have the nano level silver-colored particle that very big special applications is worth, therefore have lot of advantages, rising.
The present invention adopts the aspergillus biotechnology to handle these silver-containing waste waters, not only cost is low, can efficiently remove silver pollutes, what is more important, silver ions in the aspergillus excretory extracellular enzyme energy biocatalysis reduction waste liquid becomes the silver of nano-scale particle, and nano-scale particle silver is not only important precious metal, more because have the singularity of a lot of nano materials, at aspects such as photoelectric component, photoelectricity characteristics important use is arranged.Therefore, adopt Aspergillus microbiological treatment argentiferous trade effluent, not only environment purification reduces and pollutes, and can produce the nano material with property, and therefore wide application prospect is arranged.
Bacterial strains such as the aspergillus niger among the present invention, flavus, Aspergillus fumigatus can be buied from domestic any one tame colleges and universities, scientific research institution, also can be from also obtaining from Institute of Microorganism, Academia Sinica, DSMZ of the Chinese Academy of Agricultural Sciences, Shandong University, Wuhan University, Fudan University and relevant agriculture university and Nanjing Information engineering Univ.
Description of drawings:
Fig. 1 is the Electronic Speculum figure of throw out transmission electron microscope observing nanometer-level silver particle (8000 times).
Embodiment:
Below in conjunction with example, the invention will be further described.
Example one: silver nano-grain recovery method
1, adds following each material in the 2000mL water respectively: 15g KH
2PO
4, 5g K
2HPO
4, 3g (NH
4)
2SO
4, 0.2g MgSO
4, the 0.8g yeast extract, 10g glucose, the 10g Semen Maydis powder is regulated pH to 6-7 with dilute hydrochloric acid and diluted sodium hydroxide solution, makes liquid nutrient medium.After making substratum, place high-pressure sterilizing pot to sterilize substratum, sterilising conditions is 120 ℃, 0.15MPa, and the time is 30 minutes.
2, take out sterilized substratum, be placed on the indoor cooling of aseptic inoculation, when substratum in the triangular flask is cooled to 30 ℃ of left and right sides, inoculated aspergillus niger 100mg, (by weight/volume of inoculum size and liquid nutrient medium is 50mg/L), triangular flask after the inoculated aspergillus niger is placed on shaking culture on the microorganism shaking table together with substratum, and oscillation frequency is 180rpm, and culture temperature is 35 ± 2 ℃;
3, after cultivating in 7 days, centrifugal 20 minutes of 5000-6000rpm collects all precipitation aspergillus niger mixtures, gets the AgNO that 1500mg aspergillus niger mixture wherein adds to 1000mg/L
3Among the waste liquid 5000mL, mix, cultivate after 7-8 days under the room temperature, draw a small amount of supernatant liquid and do transmissioning electric mirror checking, can be observed under the Electronic Speculum has some nanometer-level silver particulate matter to produce in the solution.
4, measure the about 430mg/L of concentration of silver in the silver-containing waste water, promptly aspergillus niger has been eliminated in the waste water about 57% silver ions; 5000-6000rpm is centrifugal 15 minutes simultaneously, separating liquid and solid particulate, and collecting precipitation, the picking small amount of sample carries out transmission electron microscope observing, and result's (8000 times) is as shown in Figure 1. with pure water repetitive scrubbing precipitation for several times, get approximately 2610mg. of nano-scale particle silver
Embodiment two:
Wherein the by weight/volume of the inoculum size of aspergillus niger and substratum is: 10～80mg/L, under the situation of condition permission, in the aforementioned proportion scope, strengthen inoculum size, to promote the growth of aspergillus niger, improve the spore count and the biomass of the aspergillus niger in the unit liquid, can improve output; Aspergillus niger mixture of after cultivating, collecting and pending AgNO
3The by weight/volume of waste liquid is: 200mg/L, 300mg/L, 450mg/L, 500mg/L all can, AgNO
3Be reduced through the biocatalysis reductive action of aspergillus niger and be precipitated out, the silver nano-grain particle diameter of collecting is about 15-50nm.Other process is with embodiment one.
The pending AgNO that contains
3AgNO in the waste water
3Content is generally 100-1500mg/L, AgNO in the waste water
3The content height is different, and the aspergillus niger amount of inoculation also can be different, AgNO
3The high corresponding inoculum size of content can improve, but AgNO
3The treatment effect of too high levels is not so good, can suppress the growth of aspergillus niger, thereby influences its catalytic reduction effect; Crossing low then processing cost increases, and therefore will suitably dilute and adjust AgNO
3Concentration in above-mentioned scope so that this method reaches best effect, create greatest benefit.
Embodiment three:
With the inoculum size of flavus and the by weight/volume of substratum be: 20～80mg/L, according to circumstances suitably strengthen inoculum size, can promote the growth of flavus, improve spore count and the biomass of the flavus in the unit liquid greatly, thereby improve output; Flavus mixture of after cultivating, collecting and pending AgNO
3The by weight/volume of waste liquid is: about 350mg/L, and cultured continuously 7-10 days, AgNO
3In silver ions be reduced through the biocatalysis reductive action of flavus and be precipitated out, occur with simple substance silver ions form, the silver nano-grain particle diameter of collecting is greatly about about 15-50nm.Other process is with embodiment one.
The generally pending AgNO that contains
3AgNO in the waste water
3Content is approximately 100-1500mg/L, AgNO in the waste liquid of silverware factory
3Content is higher relatively, and AgNO in the processing waste liquid of the industry of generally taking a picture
3Relatively low.AgNO in the waste water
3The content height is different, and the flavus amount of inoculation should be made corresponding increase and decrease, AgNO
3The high corresponding inoculum size of content can improve, and simultaneously also different at the Various Seasonal treatment effect, generally summer, treatment effect was best, and winter is the poorest, mainly is because temperature just influences aspergillar growth and metabolism.
Claims (5)
1. a biological process reclaims method silver-colored in the silver-containing waste water, it is characterized in that:
At first with after the liquid nutrient medium sterilization, be placed on the indoor cooling of aseptic inoculation, when liquid nutrient medium in the triangular flask is cooled to 29-32 ℃, inoculation aspergillus, the by weight/volume of aspergillus inoculum size and liquid nutrient medium is: 10～80mg/L, substratum behind the inoculation aspergillus is placed on shaking culture on the microorganism shaking table together with triangular flask, and oscillation frequency is 170-200rpm, and culture temperature is 35 ± 2 ℃;
After cultivating in 6～7 days, with the centrifugal 15-25 of 5000-6000rpm minute, collecting precipitation aspergillus mixture added to and contains AgNO
3Waste liquid, the aspergillus mixture and the AgNO of adding
3The by weight/volume of waste liquid is: 200-500mg/L, after mixing, at room temperature cultivate 6-10 days after, with 5000-6000rpm centrifugal treating 10-20 minute, and separating liquid and precipitation, water repetitive scrubbing precipitation is collected silver-colored particle for several times.
2. biological process according to claim 1 reclaims the method for silver in the silver-containing waste water, and it is characterized in that: described aspergillus is selected aspergillus niger, flavus or Aspergillus fumigatus for use.
3. biological process according to claim 1 reclaims the method for silver in the silver-containing waste water, and it is characterized in that: the making processes of described liquid nutrient medium is: add following each material configuration in every 1000mL water respectively and form, 7.5-8.5g KH is wherein arranged
2PO
4, 2.0-2.5g K
2HPO
4, 0.6-2.0g (NH
4)
2SO
4, 0.1-0.2g MgSO
4, 0.3-0.4g yeast extract, 5-10g glucose, 5-10g Semen Maydis powder, transfer pH to 6-7.
4. biological process according to claim 3 reclaims the method for silver in the silver-containing waste water, it is characterized in that: the sterilising method of described liquid culture is: liquid nutrient medium is placed high-pressure sterilizing pot, temperature is 120-124 ℃ in the maintenance Autoclave, pressure is 0.12-0.8Mpa, sterilizes 20～40 minutes.
5. biological process according to claim 1 reclaims the method for silver in the silver-containing waste water, it is characterized in that: contain that Silver Nitrate content is 100-1500mg/L in the Silver Nitrate waste water.
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|---|---|---|---|
| CN2009102130780A CN101705359B (en) | 2009-11-10 | 2009-11-10 | Method for recovering silver in silver-containing waste water by biological method |
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|---|---|---|---|
| CN2009102130780A CN101705359B (en) | 2009-11-10 | 2009-11-10 | Method for recovering silver in silver-containing waste water by biological method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103572060A (en) * | 2013-11-26 | 2014-02-12 | 厦门大学 | Method for recycling gold ions from water solution |
| CN104312955A (en) * | 2014-10-21 | 2015-01-28 | 福州大学 | Delftia Sp. and application thereof |
| CN104404256A (en) * | 2014-12-01 | 2015-03-11 | 湖南科技大学 | Green and environment-friendly method for recycling silver in wastewater |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393898C (en) * | 2003-09-24 | 2008-06-11 | 苏州大学 | Method of recovering silver for silver-containing waste liquid |
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2009
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103572060A (en) * | 2013-11-26 | 2014-02-12 | 厦门大学 | Method for recycling gold ions from water solution |
| CN103572060B (en) * | 2013-11-26 | 2016-04-06 | 厦门大学 | A kind of method of gold recovering ion from the aqueous solution |
| CN104312955A (en) * | 2014-10-21 | 2015-01-28 | 福州大学 | Delftia Sp. and application thereof |
| CN104312955B (en) * | 2014-10-21 | 2017-07-04 | 福州大学 | One plant of Dell Ford bacterium and its application |
| CN104404256A (en) * | 2014-12-01 | 2015-03-11 | 湖南科技大学 | Green and environment-friendly method for recycling silver in wastewater |
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