CN103013864A - Method for performing double-layer modification on bacteria by using polyacrylamide hydrochloride, adsorbent and application of adsorbent - Google Patents
Method for performing double-layer modification on bacteria by using polyacrylamide hydrochloride, adsorbent and application of adsorbent Download PDFInfo
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- CN103013864A CN103013864A CN2012105093588A CN201210509358A CN103013864A CN 103013864 A CN103013864 A CN 103013864A CN 2012105093588 A CN2012105093588 A CN 2012105093588A CN 201210509358 A CN201210509358 A CN 201210509358A CN 103013864 A CN103013864 A CN 103013864A
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Abstract
The invention provides a method for performing double-layer modification on bacteria by using polyacrylamide hydrochloride, an adsorbent and an application of the adsorbent for the first time. According to the method, two layers of polyacrylamide hydrochloride (PAA/HCI) are connected to the surfaces of the bacteria by taking glutaraldehyde and 4-bromine butyl chloride as cross-linking agents in sequence, so that the capacity of the polyacrylamide hydrochloride for removing heavy metal is obviously improved. The maximum adsorption quantity of the heavy metal Pb <2+> by using an adsorbent LK9-G-PAA-B-PAA which is obtained by modifying bacteria LK9 by using the method disclosed by the invention is 483.19mg/g, is 406.23mg/g more than that of an unmodified adsorbent LK9 and is 213.29mg/g more than that of an adsorbent LK-9-PAA which is modified in a single layer manner; and the removal rate of the heavy metal Pb <2+> of which the concentration is less than 300mg/L by using 1g/L of the adsorbent LK9-G-PAA-B-PAA can reach 99 percent. The adsorbent has remarkable absorption capacity, is environment-friendly and has great application potentiality for treating water polluted by the heavy metal, and the microorganism modification method provides a new thought for performing two-layer or multi-layer modification on microorganisms.
Description
Technical field
The present invention relates to heavy metal water body pollution and repair the field, be specifically related to a kind of method of modifying PAH at Bacteria surface bilayer, and the thalline after will modifying the bacterial adsorption agent and the application thereof that are prepared into, this sorbent material can be removed Heavy Metals in Waters fast and efficiently.
Background technology
Heavy metal contamination refers to the environmental pollution that caused by heavy metal or its compound.Heavy metal contamination is mainly manifested in the water pollution, the main source industrial pollution, and heavy metal contamination is different from the pollution of other organic compound.Much organic compound can by the physics of nature own, chemistry or biological purification, hazardous property is reduced or releasing, and heavy metal can not be degraded, and have enriching.
In recent years, utilize biosorption process remove water pollute in heavy metal cause great concern.Utilize microbial material to have the advantages such as the source is abundant, cost is low, easy and simple to handle, quick, can reuse as heavy metal absorbent.But a large defective of natural biology sorbent material is that its adsorptive power is usually lower, and chemically modified is to solve the low effective ways of its adsorptive power.Yet bibliographical information mostly be will have functional group's material individual layer of complexing heavy metal ability connect or grafting to the microorganism surface, bilayer or multiple modification microorganism have no report, although and these individual layer modifying method of having reported can improve its adsorptive power, its removal ability to heavy metal also is not enough to the above heavy metal polluted waste water of Threshold retention 200mg/L.For example the research of this seminar is connected to the PAH individual layer on the bacterium Pseudomonas sp.LK9, and it is to Pb
2+Maximal absorptive capacity also only reaches 269.9mg/g.The present invention adopts the method for double-deck modified microorganism on the basis of existing research, provide a kind of and can significantly improve the microorganism surface modification method of processing the heavy metal effect.
Summary of the invention:
The present invention overcomes the deficiencies in the prior art, provides first method that a kind of new bilayer modifies bacterium and the sorbent material that prepared by the method and the application method of this sorbent material, and the method can significantly improve bacterium to the removal ability of heavy metal.The present invention is simple to operate, economy, safety, and can effectively process heavy metal polluted waste water.
A kind of double-deck method of modifying bacterium of polypropylene amine hydrochloride of utilizing may further comprise the steps:
1) preparation PAH solution is regulated its pH for alkalescence, and the bacterium lyophilized powder is joined in the PAH solution, adds glutaraldehyde after stirring, and continues to stir, and lyophilize obtains the PAA thalline that individual layer is modified;
2) the PAA thalline of individual layer modification, join in the chloroformic solution that contains pyridine, under agitation drip the 4-bromobutanoylchloride, obtain the acidylate thalline, at last acidylate thalline and potassium hydroxide are joined in the PAH solution, stir, centrifugal, use deionized water wash, lyophilize obtains the double-deck PAA thalline of modifying;
Described bacterium is pseudomonas Pseudomonas sp.LK9, on July 30th, 2012 in China. Wuhan. the patent preservation has been carried out at the Chinese Typical Representative culture collection center of Wuhan University, and deposit number is CCTCC M2012302.
The detailed process of step 1) is: 1g bacterium lyophilized powder adds the PAH solution that 100mL pH is 11 5g/L, stir 2h after, add the glutaraldehyde of 0.1-0.2mL25wt%, continue to stir 2h, washing, lyophilize obtain the PAA thalline that individual layer is modified to constant weight.
The addition of the PAA thalline that individual layer is modified step 2) is the 10g/L chloroform; The pyridine add-on is the PAA thalline that the 0.25mL/g individual layer is modified; 4-bromobutanoylchloride add-on is the PAA thalline that the 0.25mL/g individual layer is modified; Stirring at normal temperature 12h behind the adding 4-bromobutanoylchloride; The PAH add-on is the PAA thalline that the 1g/g individual layer is modified, and the KOH add-on is the PAA thalline that the 1g/g individual layer is modified; Temperature is controlled to be 80 ℃ after adding PAH solution; Reaction times is 8h.
A kind of microbial adsorbent of Adsorption of Heavy Metals is above-mentioned method to be modified product lyophilize to the constant weight that obtains be prepared from.
The application method of the sorbent material of above-mentioned preparation: process heavy metal in waste water Pb
2+The time waste water ph be 2-7; Be preferably 5-6(and see accompanying drawing 3).
Above-mentioned microorganism adsorption agent dose is the 1g/L heavy metal wastewater thereby; Adsorption time is 5-120min, is preferably 60-120min(and sees accompanying drawing 4).
Process the method for waste water specifically: at first regulate heavy metal polluted waste water pH, in heavy metal polluted waste water, add described microbial adsorbent, filter after the concussion or precipitate and collect sorbent material, finish the processing to heavy metal polluted waste water.
Bacterium of the present invention is Pseudomonas ss.LK9, and deposit number is CCTCC M2012302; And patent applied for, application number is: 201210295180.1.
The present invention is first at the double-deck polymkeric substance of modifying the functional group with a large amount of complexation heavy metal ions in microorganism surface; at first use glutaraldehyde as the first layer linking agent; PAH (PAA/HCl) and bacterium surface amino are connected; recycling 4-bromobutanoylchloride is as the linking agent of the second layer; after the amido functional group acidylate of bacterium surface the first layer; under alkaline condition;-C-Br again with the PAH long-chain on amino reaction; thereby at the double-deck PAA that modifies of bacterium surface; make its surface with a large amount of amido functional groups, thereby greatly improve it to the removal ability of heavy metal in the pollutant effluents.Compare with traditional sorbent material, it is remarkable that microbial adsorbent of the present invention has counterweight metal removal effect, as to heavy metal Pb
2+Maximal absorptive capacity be 483.19mg/g, this sorbent material dosage of 1g/L is to the heavy metal Pb below the 300mg/L
2+Clearance can reach 99%, to the Pb of 400mg/g
2+Clearance also can reach 96.5%.The inventive method provides the new approaches of a bilayer or multiple modification for the microorganism modifying method, and sorbent material of the present invention also has the advantages such as environmental protection, preparation process be simple in addition.
Description of drawings:
Fig. 1 is that sorbent material LK9-G-PAA of the present invention, LK9-G-PAA2, LK9-G-PAA-B-PAA are to heavy metal Pb
2+The removal effect comparison diagram;
Fig. 2 is that LK9-G-PAA-B-PAA is to heavy metal Pb
2+Clearance;
Fig. 3 is that pH is to the present invention successively sorbent material LK9-G-PAA-B-PAA Adsorption of Heavy Metals Pb
2+Affect graph of a relation;
Fig. 4 is that sorbent material LK9-G-PAA-B-PAA of the present invention is to heavy metal Pb
2+Adsorptive capacity and the graph of a relation of time;
Fig. 5 is sorbent material LK9-G-PAA-B-PAA of the present invention and LK9-G-PAA and nothing modification LK9 sorbent treatment different concns Pb
2+The effect contrast figure.
Embodiment:
Be intended to further specify the present invention below in conjunction with embodiment, and unrestricted the present invention.
Embodiment 1
1, the research of PAA multiple modification Pseudomonas sp.LK9:
Glutaraldehyde is as the research of linking agent multiple modification effect
(1) at first use a large amount of culturing plants endophyte of LB substratum Pseudomonas sp.LK912h, centrifugal collection thalline is used deionized water wash 2-3 time, obtains endophyte of plant Pseudomonas sp.LK9CCTCC M2012302 lyophilized powder with freeze-drying;
(2) 1g endophyte of plant Pseudomonas sp.LK9CCTCC M2012302 lyophilized powder is joined in the PAA/HCl solution that 100mL pH is 11 5g/L, stir 2h, the glutaraldehyde that adds 0.1-0.2mL25wt%, continue to stir 2h, deionized water wash, lyophilize is modified the individual layer of endophyte of plant Pseudomonas sp.LK9 thereby finish to constant weight; Called after LK9-G-PAA;
(3) with the process of LK9-G-PAA thalline repeating step obtained above (2), obtain the double-deck endophyte of plant Pseudomonas sp.LK9 thalline of modifying of PAA, called after LK9-G-PAA2;
(4) use successively glutaraldehyde, 4-bromobutanoylchloride as the research of linking agent modification effect
The LK9-G-PAA thalline that the individual layer of step (2) preparation is modified, join in the chloroformic solution that contains pyridine, pyridine content is the 0.25mL/gLK9-G-PAA thalline, the ratio of LK9-G-PAA thalline and chloroform is 10g thalline/L chloroform, under agitation slowly drip the 4-bromobutanoylchloride of 0.25mL/gLK9-G-PAA thalline, stir 12h under the normal temperature; Obtain the acidylate thalline; potassium hydroxide with acidylate thalline and 1g/gLK9-G-PAA thalline joins in the PAA basic solution that PAA concentration is 10g/L at last; contain 1g thalline (in the LK9-G-PAA thalline) in this solution of every 100mL; 80 ℃ of lower 8h that stir; centrifugal; deionized water wash, lyophilize obtain double-deck PAA thalline.Called after LK9-G-PAA-B-PAA.
The Pb that above-mentioned two kinds of sorbent material LK9-G-PAA2, LK9-G-PAA-B-PAA is used for absorption 260mg/L with the dosage of 1g/L
2+, the result is that the double-deck linking agent of modifying is to Pb with glutaraldehyde only as shown in Figure 1
2+Clearance obviously do not improve, and successively with glutaraldehyde, 4-bromobutanoylchloride as the double-deck sorbent material LK9-G-PAA-B-PAA that modifies gained of linking agent, it is to Pb
2+Clearance increases greatly, and the sorbent material dosage of 1g/L is lower than the Pb of 300mg/L for concentration
2+Clearance can reach 99%(and see accompanying drawing 2).
2, sorbent material LK9-G-PAA-B-PAA is to heavy metal Pb
2+Absorption research
(1) pH is to sorbent material Adsorption of Heavy Metals Pb of the present invention
2+Impact
Compound concentration is the Pb about 100mg/L
2+Solution is with the HNO of 0.1M
3Regulating pH with the NaOH of 0.1M is 2 ~ 7.Be the heavy metal Pb that the sorbent material LK9-G-PAA-B-PAA of the present invention of 1g/L adds different pH with the microbial inoculum amount
2+In the solution, at 27 ℃, absorption 1h is then with Pb in the simulated wastewater after the atomic absorption spectrometry absorption
2+Concentration.Test thus to get Pb
2+The optimum absorption of waste water pH is that 5-6(sees accompanying drawing 3).
(2) sorbent material LK9-G-PAA-B-PAA of the present invention under the different time condition to Pb
2+Absorption research
Compound concentration is the Pb of 300mg/L respectively
2+Solution is with the HNO of 0.1M
3Transfer Pb with the NaOH of 0.1M
2+Joint pH is 5-6.Be that the sorbent material LK9-G-PAA-B-PAA of the present invention of 1g/L adds heavy metal Pb with sorbent material dosage
2+In the solution, at 27 ℃ of lower absorption 5,10,20,30,45,60,120min, then with Pb in the simulated wastewater after the atomic absorption spectrometry absorption
2+Concentration.Experiment can draw thus, and the dosage of 1g/L reaches balance (accompanying drawing 4) in 60-120min.
(3) sorbent material LK9-G-PAA-B-PAA is to Pb
2+The heavy metal maximal absorptive capacity is studied
Respectively compound concentration be 50,100,150,200,300,400, the Pb of 600mg/L
2+Solution is with the HNO of 0.1M
3Regulating pH with the NaOH of 0.1M is 5-6.Be the sorbent material LK9-G-PAA-B-PAA of the present invention of 1g/L, the heavy metal Pb that LK9-G-PAA adds respectively different concns with sorbent material dosage
2+In the solution, at 27 ℃ of lower absorption 120min, then with Pb in the simulated wastewater after the atomic absorption spectrometry absorption
2+Concentration.
Sorbent material LK9-G-PAA-B-PAA of the present invention is to heavy metal Pb after optimizing
2+Maximal absorptive capacity be 483.19mg/g, increased respectively 406.23mg/g than the LK9 sorbent material of unmodified, the sorbent material LK9-G-PAA that modifies than individual layer increases 213.29mg/g(and sees accompanying drawing 5).
Claims (7)
1. one kind is utilized the double-deck method of modifying bacterium of polypropylene amine hydrochloride, it is characterized in that, may further comprise the steps:
1) preparation PAH solution is regulated its pH for alkalescence, and the bacterium lyophilized powder is joined in the PAH solution, adds glutaraldehyde after stirring, and continues to stir, and lyophilize obtains the PAA thalline that individual layer is modified;
2) the PAA thalline of individual layer modification, join in the chloroformic solution that contains pyridine, under agitation drip the 4-bromobutanoylchloride, obtain the acidylate thalline, at last acidylate thalline and potassium hydroxide are joined in the PAH solution, stir, centrifugal, use deionized water wash, lyophilize obtains the double-deck PAA thalline of modifying;
Described bacterium is Pseudomonas sp.LK9, and deposit number is CCTCC M2012302.
2. method according to claim 1, it is characterized in that, the detailed process of step 1) is: 1g bacterium lyophilized powder adds the PAH solution that 100mLpH is 11 5g/L, after stirring 2h, the glutaraldehyde that adds 0.1-0.2mL25wt% continues to stir 2h, washing, lyophilize obtains the PAA thalline that individual layer is modified to constant weight.
3. method according to claim 1 is characterized in that step 2) in the addition of the PAA thalline modified of individual layer be the 10g/L chloroform; The pyridine add-on is the PAA thalline that the 0.25mL/g individual layer is modified; 4-bromobutanoylchloride add-on is the PAA thalline that the 0.25mL/g individual layer is modified; Stirring at normal temperature 12h behind the adding 4-bromobutanoylchloride; The concentration of PAH solution is 10g/L, the PAA thalline that the add-on of acidylate thalline is modified to contain the 1g individual layer in every 100mL PAH solution, and the KOH add-on is the PAA thalline that the 1g/g individual layer is modified; Temperature is controlled to be 80 ℃ after adding PAH solution; Reaction times is 8h.
4. the microbial adsorbent of an Adsorption of Heavy Metals is characterized in that, product lyophilize to the constant weight that each described method modification of claim 1-3 is obtained is prepared from.
5. the application method of the sorbent material of preparation claimed in claim 4 is characterized in that, processes heavy metal in waste water Pb
2+The time waste water ph be 2-7.
6. the application method of the sorbent material of preparation claimed in claim 4 is characterized in that, processes heavy metal in waste water Pb
2+The time waste water ph be 5-6.
7. the application method of sorbent material according to claim 4 is characterized in that, described microorganism adsorption agent dose is the 1g/L heavy metal wastewater thereby; Adsorption time is 5-120min.
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Cited By (3)
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| CN106497194A (en) * | 2016-11-25 | 2017-03-15 | 北京建筑大学 | A kind of composite coating of preventing metal corrosion and preparation method thereof |
| CN107446862A (en) * | 2017-09-06 | 2017-12-08 | 北京双龙阿姆斯科技有限公司 | Microbial bacterial agent of degrading pesticide residues and preparation method thereof |
| CN108976362A (en) * | 2018-06-08 | 2018-12-11 | 陕西师范大学 | The method that microorganism non-genomic is transformed based on phase transition lysozyme nano thin-film |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106497194A (en) * | 2016-11-25 | 2017-03-15 | 北京建筑大学 | A kind of composite coating of preventing metal corrosion and preparation method thereof |
| CN106497194B (en) * | 2016-11-25 | 2018-10-30 | 北京建筑大学 | A kind of composite coating of preventing metal corrosion and preparation method thereof |
| CN107446862A (en) * | 2017-09-06 | 2017-12-08 | 北京双龙阿姆斯科技有限公司 | Microbial bacterial agent of degrading pesticide residues and preparation method thereof |
| CN107446862B (en) * | 2017-09-06 | 2023-12-15 | 北京双龙阿姆斯科技有限公司 | Microbial agent for degrading pesticide residues and preparation method thereof |
| CN108976362A (en) * | 2018-06-08 | 2018-12-11 | 陕西师范大学 | The method that microorganism non-genomic is transformed based on phase transition lysozyme nano thin-film |
| CN108976362B (en) * | 2018-06-08 | 2020-11-17 | 陕西师范大学 | Method for non-genetic modification of microorganisms based on phase transition lysozyme nano-film |
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Application publication date: 20130403 |