CN104193012A - Method for promoting phanerochaete chrysosporium to remove heavy metal cadmium by utilizing silver nanoparticles - Google Patents
Method for promoting phanerochaete chrysosporium to remove heavy metal cadmium by utilizing silver nanoparticles Download PDFInfo
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- CN104193012A CN104193012A CN201410460566.2A CN201410460566A CN104193012A CN 104193012 A CN104193012 A CN 104193012A CN 201410460566 A CN201410460566 A CN 201410460566A CN 104193012 A CN104193012 A CN 104193012A
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- phanerochaete chrysosporium
- heavy metal
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Abstract
The invention discloses a method for promoting phanerochaete chrysosporium to remove heavy metal cadmium by utilizing silver nanoparticles. The method comprises the following steps: adding phanerochaete chrysosporium and silver nanoparticles into cadmium-containing wastewater and carrying out an oscillation adsorption reaction, thus finishing removal of the heavy metal cadmium. The method disclosed by the invention is simple to operate, is easy to carry out, is capable of effectively promoting phanerochaete chrysosporium to adsorb and remove heavy metal cadmium, can reduce the toxicity of the heavy metal cadmium to organisms in the environment and has significance in treatment of heavy metal-containing wastewater.
Description
Technical field
The present invention relates to a kind of new purposes of nano particle, relate in particular to a kind of silver nano-grain and promote Phanerochaete chrysosporium to remove the method for heavy metal in waste water cadmium.
Background technology
Containing cadmic compound widespread use in the industries such as battery, plastic cement manufacture, metallurgy, plating and tanning, thereby cause the waste water that contains in a large number Cd to drain into environment from departments such as Electroplate Factory, dye industry, mining and metallurgy process, battery production, process hides, film manufacture and automobile makings.Because cadmium has high toxicity, growing of humans and animals had to serious harm, in national standard integrated wastewater discharge standard, cadmium is classified as to first kind pollutent, European Union classifies cadmium as high harm toxic substance and can carcinogenic substance and regulated, and the waste water of therefore administering heavy metal cadmium all has great importance to the safety of human body and environment.
The method of traditional processing cadmium wastewater mainly contains ion exchange method, chemical precipitation method, membrane separation process and active carbon adsorption etc., but the shortcomings such as these method ubiquity treatment effects are bad, cost height, when especially in waste water, the content of cadmium is low.
Biosorption process is subject to people's favor because cost is low, Phanerochaete chrysosporium belongs to a kind of of white-rot fungi, because it has stronger adsorption to heavy metal, and the extremely concern of Chinese scholars in recent years.Yet utilize Phanerochaete chrysosporium adsorption treatment containing the waste water of heavy metal cadmium, when the concentration content of cadmium is low in waste water, how to improve Phanerochaete chrysosporium urgently to be resolved hurrily to the problem of the removal ability of heavy metal cadmium.
Silver nano-grain is the simple substance of a kind of particle diameter between 1～100nm silver, because its small size makes it have quantum effect and huge surface and interface effect, and has the characteristic of the physical and chemical performances such as unique optical, electrical, magnetic, heat and anti-bacteria and anti-virus.These special performances just because of it make it at aspects such as electronics, personal care articles, clothes and medical treatment, be widely used.Although silver nano-grain has the characteristics such as sterilization, yet, not yet have at present the precedent of silver nano-grain and microorganism synergy removal heavy metal.
In prior art, silver nano-grain can have the effect of killing to bacterium, virus and eukaryotic microorganisms; the present invention finds that add-on is that the silver nano-grain of 0.1mg/L～1mg/L has the effect that promotes Phanerochaete chrysosporium to remove the heavy metal cadmium in waste water first, and this derives from the overcompensation mechanism of Phanerochaete chrysosporium to silver nano-grain.When the silver nano-grain of lower concentration joins in the environment that Phanerochaete chrysosporium exists, Phanerochaete chrysosporium can be resisted the damage that silver nano-grain causes by poisonous substance generation repair mechanism to external world naturally, this repair mechanism can drive other some stress mechanism secretion more exocytosis thing (as extracellular protein), these exocytosis things are materials of good Adsorption of Heavy Metals, so, silver nano-grain has promoted Phanerochaete chrysosporium removal heavy metal cadmium in this way.
If the excessive concentration of silver nano-grain, while surpassing Phanerochaete chrysosporium to its tolerance degree, the antimicrobial effect of silver nano-grain will work gradually, the silver nano-grain of high density just can cause murder by poisoning to Phanerochaete chrysosporium, and it also no longer has promoter action to Phanerochaete chrysosporium removal heavy metal cadmium.
Compared with prior art, the invention has the advantages that:
(1) the present invention directly will directly join in the waste water containing heavy metal cadmium without transformation and pretreated Phanerochaete chrysosporium and synthetic silver nano-grain, promoter action by silver nano-grain to Phanerochaete chrysosporium, complete the Adsorption to heavy metal cadmium, removal efficiency is high, can reduce heavy metal cadmium to the biological toxicity in environment, improvement to heavy metal-containing waste water is significant, has the advantages such as simple to operate, easy to implement.
(2) preparation method of the nanometer silver that the application provides, easy and simple to handle, be applicable to suitability for industrialized production.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, provide a kind of simple, easy to implement, feasible, can effectively promote Phanerochaete chrysosporium the silver nano-grain of the Adsorption of heavy metal cadmium to be promoted to the method for Phanerochaete chrysosporium Adsorption heavy metal cadmium.
For solving above-mentioned technical problem, the technical solution used in the present invention is:
Utilize silver nano-grain to promote a method for Phanerochaete chrysosporium removal heavy metal cadmium, comprise the following steps: Phanerochaete chrysosporium bacterium ball and silver nano-grain are joined to the absorption reaction of vibrating in cadmium wastewater, complete the removal to heavy metal cadmium.In above-mentioned method, preferred, silver nano-grain is prepared by stirring by citric acid three sodium solution, sodium borohydride solution and silver nitrate solution, and whipping temp is 25 ℃, and mixing speed is 535～540r/min.
Further, the concentration of aforementioned citric acid three sodium solution is 24mmol/L, and the concentration of aforementioned sodium borohydride solution is 20mmol/L, and the concentration of aforementioned silver nitrate solution is 50mmol/L.
Further, aforementioned Phanerochaete chrysosporium bacterium ball is to prepare by following steps: Phanerochaete chrysosporium spore powder is suspended in and in sterilized water, makes spore suspension, again this spore suspension is inoculated in Kirk liquid nutrient medium, shaking culture 72h at 35 ℃～39 ℃ temperature, during cultivation, rotating speed is controlled at 140rpm～160rpm, obtains Phanerochaete chrysosporium bacterium ball after filtration.
Further, the add-on of aforementioned silver nano-grain is 0.1mg/L～1mg/L.
Further, the add-on of aforementioned Phanerochaete chrysosporium bacterium ball is 0.29g/L.
Further, the pH value of aforementioned cadmium wastewater is 6.5.
Further, in aforementioned cadmium wastewater, the concentration of cadmium is 5mg/L.
Further, the condition of aforementioned absorption reaction is: temperature is 35 ℃～39 ℃, and vibration rotating speed is 140rpm～160rpm, and sorption reaction time is 36h～84h.
Creativeness of the present invention is:
Accompanying drawing explanation
For making object, technical scheme and the advantage of the embodiment of the present invention clearer, below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out to clear, complete description.
Fig. 1 is silver nano-grain synthetic in the embodiment of the present invention 1 microtexture schematic diagram under transmission electron microscope.
Fig. 2 is the electro microscope energy spectrum schematic diagram of nano particle in the embodiment of the present invention 1.
Fig. 3 is that the silver nano-grain of different add-ons promotes the Adsorption design sketch of Phanerochaete chrysosporium to heavy metal cadmium.
Fig. 4 is the microtexture schematic diagram of Phanerochaete chrysosporium under electronic scanning Electronic Speculum before the embodiment of the present invention 2 absorption reactions.
Fig. 5 is the microtexture schematic diagram of Phanerochaete chrysosporium under electronic scanning Electronic Speculum after the embodiment of the present invention 2 absorption reactions.
Fig. 6 is the electro microscope energy spectrum schematic diagram of Phanerochaete chrysosporium surface particles in the embodiment of the present invention 2.
Embodiment
Below in conjunction with Figure of description, the invention will be further described with concrete preferred embodiment, but protection domain not thereby limiting the invention.
Embodiment 1
A method of utilizing silver nano-grain to promote Phanerochaete chrysosporium removal heavy metal cadmium of the present invention, comprises the following steps:
(1) prepare silver nano-grain: two mouthfuls of round-bottomed flasks that are added with 777ml ultrapure water are placed in to ice bath, adjustment stirring velocity is 540r/min, successively adding 22.2ml concentration is the citric acid three sodium solution of 24mmol/L and the sodium borohydride solution that 88.8ml concentration is 20mmol/L, and this solution rotating speed with 540r/min in ice bath is stirred 5 minutes; And then to add 3.6ml concentration be 50mmol/L silver nitrate solution, and at once flask is taken out from ice bath, be placed in (normal temperature temperature is generally 25 ℃) under normal temperature and, with the stirring velocity reaction 3h of 540r/min, obtain silver nano-grain.
The silver nano-grain preparing in step (1) is placed under transmission electron microscope, and it characterizes as shown in Figure 1.As can be seen from Figure 1: the nano particle preparing according to step (1) method is spherical in shape, and its particle diameter is approximately 25nm and particle diameter ratio is more even.
Nano particle in Fig. 1 is carried out to energy spectrum analysis, shown in analytical results Fig. 2, the C mainly containing in the nano particle in Fig. 1, Cu, tri-kinds of elements of Ag, wherein the weight percent of C element is 47.48%, atomic percent is 84.47%; The weight percent of Cu element is 37.12%, and atomic percent is 12.48%; The weight percent of Ag element is 15.40%, and atomic percent is 3.05%.The result of Fig. 2 shows, the nano particle in Fig. 1 is silver nano-grain, in conjunction with the result of Fig. 1 and Fig. 2, can learn and in the present invention, successfully synthesize the silver nano-grain that particle diameter is about 25nm.
(2) prepare Phanerochaete chrysosporium bacterium ball: by Phanerochaete chrysosporium BKM-F1767 (USS type culture collection deposit number be ATCC 24725, preferably adopt this bacterial strain, but be not limited to this) spore from flat board, scrape in sterilized water, (the spore amount containing is 2.0 * 10 to form spore suspension
6individual/ml); (composition of Kirk liquid nutrient medium comprises: 1.2mmol/L ammonium tartrate, 56mmol/L glucose, 20mmol/L anhydrous sodium acetate, 0.2g/L KH in 500ml Erlenmeyer flask, to add 200ml Kirk liquid nutrient medium
2pO
4, 0.05g/LMgSO
47H
2o, 0.01g/LCaCl
2, 1ml/L inorganic solution and 0.5ml/L vitamin solution; Wherein inorganic solution is by 1.5g/L nitrilotriacetic acid ester, 3g/LMgSO
47H
2o, 0.5g/LMnSO
4, 1g/LNaCl, 0.1g/LFeSO
47H
2o, 0.1g/LCoSO
4, 0.082g/LCaCl
2, 0.1g/LZnSO
4, 0.01g/LCuSO
45H
2o, 0.01g/LKAl (SO
4)
212H
2o, 0.01g/LNa
2moO
4, 0.01g/LH
3bO
3form, vitamin solution is by 2mg/L vitamin H, 2mg/L folic acid, 5mg/L vitamins B
1, 5mg/L vitamins B
2, 10mg/L vitamins B
6hydrochloride, 0.1mg/L microorganism B
12, 5mg/L nicotinic acid, 5mg/LDL-sodium pantothenate, 5mg/L para-amino benzoic acid and 5mg/L Thioctic Acid form), then 3ml Phanerochaete chrysosporium spore suspension is inoculated in Kirk liquid nutrient medium, under 37 ℃, the condition of 150rpm, in constant temperature oscillation case, cultivate 72h, obtain Phanerochaete chrysosporium bacterium ball.
(3) removal heavy metal cadmium: the Phanerochaete chrysosporium bacterium ball preparing in step (2) (add-on is 0.29g/L) is joined in the cadmium wastewater that cadmium concentration is 5mg/L, and add the silver nano-grain preparing in 0.1mg/L step (1), the pH value of adjusting waste water is 6.5, then at the temperature of 37 ℃, absorption reaction 84h vibrates on the shaking table that is 150rpm at rotating speed.Then by removing by filter the Phanerochaete chrysosporium bacterium ball in waste water, complete the Adsorption to heavy metal cadmium.
Embodiment 2
A method of utilizing silver nano-grain to promote Phanerochaete chrysosporium removal heavy metal cadmium of the present invention, comprises the following steps:
(1) prepare silver nano-grain: with embodiment 1.
(2) prepare Phanerochaete chrysosporium bacterium ball: with embodiment 1.
(3) Adsorption of heavy metal cadmium: the Phanerochaete chrysosporium bacterium ball preparing in step (2) (add-on is 0.29g/L) is joined in the cadmium wastewater that cadmium concentration is 5mg/L, and add the silver nano-grain preparing in 1mg/L step (1), the pH value of adjusting waste water is 6.5, then at the temperature of 37 ℃, absorption reaction 84h vibrates on the shaking table that is 150rpm at rotating speed.Then by removing by filter the Phanerochaete chrysosporium bacterium ball in waste water, complete the Adsorption to heavy metal cadmium.
Embodiment 3
A method of utilizing silver nano-grain to promote Phanerochaete chrysosporium removal heavy metal cadmium of the present invention, comprises the following steps:
(1) prepare silver nano-grain: with embodiment 1.
(2) prepare Phanerochaete chrysosporium bacterium ball: with embodiment 1.
(3) Adsorption of heavy metal cadmium: the Phanerochaete chrysosporium bacterium ball preparing in step (2) (add-on is 0.29g/L) is joined in the cadmium wastewater that cadmium concentration is 5mg/L, and add the silver nano-grain preparing in 5mg/L step (1), the pH value of adjusting waste water is 6.5, then at the temperature of 37 ℃, absorption reaction 84h vibrates on the shaking table that is 150rpm at rotating speed.Then by removing by filter the Phanerochaete chrysosporium bacterium ball in waste water, complete the Adsorption to heavy metal cadmium.
Comparative example 1
A method for Phanerochaete chrysosporium removal heavy metal cadmium, comprises the following steps:
(1) prepare Phanerochaete chrysosporium bacterium ball: with embodiment 1.
(2) Adsorption of heavy metal cadmium: the Phanerochaete chrysosporium bacterium ball preparing in step (2) (add-on is 0.29g/L) is joined in the cadmium wastewater that cadmium concentration is 5mg/L, the pH value of adjusting waste water is 6.5, then at the temperature of 37 ℃, absorption reaction 84h vibrates on the shaking table that is 150rpm at rotating speed.Then by removing by filter the Phanerochaete chrysosporium bacterium ball in waste water, complete the Adsorption to heavy metal cadmium.
To embodiment 1,2 and 3, comparative example 1, carries out clearance detection, and concrete detection method is: in vibration absorption reaction process, take out at set intervals the content of remaining cadmium in aliquot sample determination waste water and calculate the clearance of cadmium, its detected result is listed in table 1.
Fig. 3 is that cadmium residual concentration is with the change curve of vibration sorption reaction time.
Table 1 silver nano-grain promotes the removal effect of Phanerochaete chrysosporium to heavy metal cadmium
From Fig. 3 and as can be known from Table 1: silver nano-grain has significantly strengthened the removal efficiency of Phanerochaete chrysosporium Adsorption heavy metal cadmium, and silver nano-grain content is higher, and promoter action is stronger.When the add-on of silver nano-grain reaches 5mg/L, silver nano-grain reduces the promoter action of Phanerochaete chrysosporium.
Complete after the Adsorption step of heavy metal cadmium, by the reacted Phanerochaete chrysosporium of Adsorption filtering from solution in the pure Phanerochaete chrysosporium after cultivation 72h and embodiment 2, with ultrapure water, wash and be placed in freeze drier dry, dried two kinds of Phanerochaete chrysosporium bacterium balls are placed in to microscopy under scanning electronic microscope, and microscopy result is referring to Fig. 4 and Fig. 5.
As shown in Figure 4, the pure Phanerochaete chrysosporium mycelia surface clean of cultivating after 72h is smooth, does not have particulate material to occur.
As shown in Figure 5, the surface of mycelia is no longer smooth clean, and there is particulate material, this particulate material is carried out to energy spectrum analysis (referring to Fig. 6) to be learnt, this particulate material is the particle that the heavy metal cadmium of Phanerochaete chrysosporium Adsorption forms on its mycelia surface, illustrates that the heavy metal cadmium in waste water has obtained good removal.
Therefore, result in conjunction with comparative example 1, embodiment 1, embodiment 2 and embodiment 3 is known, in the present invention, utilize silver nano-grain to promote that the add-on of the preferred silver nano-grain of Phanerochaete chrysosporium Adsorption heavy metal cadmium is 0.1mg/L～1mg/L, and optimum is 1mg/L, under the add-on of this optimum silver nano-grain, silver nano-grain promotes that Phanerochaete chrysosporium can increase by 9.7% to the eliminating rate of absorption of heavy metal cadmium.
The above, be only preferred embodiment of the present invention, not the present invention done to any pro forma restriction.Although the present invention discloses as above with preferred embodiment, yet not in order to limit the present invention.Any those of ordinary skill in the art, in the situation that not departing from spirit of the present invention and technical scheme, all can utilize method and the technology contents of above-mentioned announcement to make many possible changes and modification to technical solution of the present invention, or be revised as the equivalent embodiment of equivalent variations.Therefore, every content that does not depart from technical solution of the present invention, according to technical spirit of the present invention to any simple modification made for any of the above embodiments, be equal to replacements, equivalence changes and modify, all still belong in the scope that technical solution of the present invention protects.
Claims (10)
1. a method of utilizing silver nano-grain to promote Phanerochaete chrysosporium removal heavy metal cadmium, it is characterized in that, comprise the following steps: Phanerochaete chrysosporium bacterium ball and silver nano-grain are joined to the absorption reaction of vibrating in cadmium wastewater, complete the removal to heavy metal cadmium.
2. method according to claim 1, is characterized in that, described silver nano-grain is prepared by stirring by citric acid three sodium solution, sodium borohydride solution and silver nitrate solution, and whipping temp is 25 ℃, and mixing speed is 535～540r/min.
3. method according to claim 2, is characterized in that, the concentration of described citric acid three sodium solution is 24mmol/L, and the concentration of described sodium borohydride solution is 20mmol/L, and the concentration of described silver nitrate solution is 50mmol/L.
4. method according to claim 1, it is characterized in that, described Phanerochaete chrysosporium bacterium ball is to prepare by following steps: Phanerochaete chrysosporium spore powder is suspended in and in sterilized water, makes spore suspension, again this spore suspension is inoculated in Kirk liquid nutrient medium, at 35 ℃～39 ℃ temperature, with 140rpm～160rpm speed oscillation, cultivates 72h and obtain Phanerochaete chrysosporium bacterium ball.
5. according to the method described in claim 1～4 any one, it is characterized in that, the add-on of described silver nano-grain is 0.1mg/L～1mg/L.
6. according to the method described in claim 1～4 any one, it is characterized in that, the add-on of described Phanerochaete chrysosporium bacterium ball is 0.29g/L.
7. according to the method described in claim 1～4 any one, it is characterized in that, the pH value of described cadmium wastewater is 6.5.
8. according to the method described in claim 1～4 any one, it is characterized in that, in described cadmium wastewater, the concentration of cadmium is 5mg/L.
9. according to the method described in claim 1～4 any one, it is characterized in that, the temperature of described vibration absorption reaction is 35 ℃～39 ℃, and vibration rotating speed is 140rpm～160rpm.
10. according to the method described in claim 1～4 any one, it is characterized in that, the time of described vibration absorption reaction is 36h～84h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105254037A (en) * | 2015-11-27 | 2016-01-20 | 湖南大学 | Method for improving activity of microorganisms in nano-silver-containing water body |
| CN105585211A (en) * | 2015-12-25 | 2016-05-18 | 湖南大学 | Method for removing nano-silver in water |
| CN107164296A (en) * | 2017-05-26 | 2017-09-15 | 湖南农业大学 | A kind of method for improving the lower Phanerochaete chrysosporium activity of heavy metal cadmium stress |
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| JP2013034993A (en) * | 2012-09-27 | 2013-02-21 | Daiichi Kankyo Kk | Water treatment apparatus |
| CN103482770A (en) * | 2013-09-09 | 2014-01-01 | 江苏大学 | Technology for degrading anthraquinone compounds in wastewater by use of phanerochaete chrysosporium |
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Patent Citations (3)
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| CN102423691A (en) * | 2011-09-08 | 2012-04-25 | 湖南大学 | Nitrogen modified nanometer titanium dioxide and Phanerochete chrysosporium composite adsorbent, and its preparation method and application |
| JP2013034993A (en) * | 2012-09-27 | 2013-02-21 | Daiichi Kankyo Kk | Water treatment apparatus |
| CN103482770A (en) * | 2013-09-09 | 2014-01-01 | 江苏大学 | Technology for degrading anthraquinone compounds in wastewater by use of phanerochaete chrysosporium |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105254037A (en) * | 2015-11-27 | 2016-01-20 | 湖南大学 | Method for improving activity of microorganisms in nano-silver-containing water body |
| CN105254037B (en) * | 2015-11-27 | 2018-09-07 | 湖南大学 | The method for improving microbial activity in water body containing nano silver |
| CN105585211A (en) * | 2015-12-25 | 2016-05-18 | 湖南大学 | Method for removing nano-silver in water |
| CN105585211B (en) * | 2015-12-25 | 2019-03-29 | 湖南大学 | The method for removing nano silver in water body |
| CN107164296A (en) * | 2017-05-26 | 2017-09-15 | 湖南农业大学 | A kind of method for improving the lower Phanerochaete chrysosporium activity of heavy metal cadmium stress |
| CN107164296B (en) * | 2017-05-26 | 2020-09-11 | 湖南农业大学 | Method for improving activity of phanerochaete chrysosporium under heavy metal cadmium stress |
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