CN103159328A - Method for discoloring methylene blue by layered double hydroxide (LDH)-bacterium polymer - Google Patents
Method for discoloring methylene blue by layered double hydroxide (LDH)-bacterium polymer Download PDFInfo
- Publication number
- CN103159328A CN103159328A CN2013100753919A CN201310075391A CN103159328A CN 103159328 A CN103159328 A CN 103159328A CN 2013100753919 A CN2013100753919 A CN 2013100753919A CN 201310075391 A CN201310075391 A CN 201310075391A CN 103159328 A CN103159328 A CN 103159328A
- Authority
- CN
- China
- Prior art keywords
- ldh
- bacterium
- polymer
- methylene blue
- discoloring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention relates to a method for discoloring methylene blue by a layered double hydroxide (LDH)-bacterium polymer and belongs to the technical field of environmental protection. The method realizes combination of a LDH and microbes, utilizes the LDH-bacterium polymer to discolor methylene blue and researches a regeneration capacity of the LDH-bacterium polymer after discoloring. The LDH-bacterium polymer as an adsorption material has a strong discoloring capacity and good regenerability. After four regeneration cycles, the LDH-bacterium polymer still retains 80-90% of the adsorption capacity. Therefore, the LDH-bacterium polymer has good comprehensive discoloring adsorption characteristics, regenerability and development prospect and will become a discoloring material having a large potential.
Description
Technical field
The invention belongs to field of Environment Protection, a kind of method that relates to methylene blue decolouring, specifically with layered di-hydroxyl composite metal oxidate (Layered Double Hydroxide, LDH) and microorganism organically connect, the associated treatment waste water from dyestuff is strengthened the technology of LDH and microorganism individual curing waste water from dyestuff.
Background technology
Waste water from dyestuff complicated component, high density, high chroma, hard-degraded substance are many, and this type of waste water still with than dark shade, is difficult to qualified discharge through biochemical treatment.Therefore, decolouring is an important step for the treatment of of dyeing wastewater.Sorbent material commonly used has gac, resin, mineral, waste etc., but has that processing cost is higher, loading capacity is low, avidity is poor, is vulnerable to the impact of inorganic salt in waste water from dyestuff and adsorbs the problem of how disposing after saturated.
LDH(Layered Double Hydroxides), the layer dihydroxy compound is the lamellar structure compound that a kind of interlayer has commutative negatively charged ion.Formed by interlayer anion and the accumulation of positively charged laminate, its similar is in brucite Mg(OH)
2The composition general formula of LDH is: M
2+ 1-xM
3+ x(OH)
2(A
n-)
x/nMH
2O。M wherein
2+Represent divalent-metal ion, M
3+Represent trivalent metal ion, A
n-Represent negatively charged ion, X=M
3+/ (M
2++ M
3+), m is the number of crystal water, and along with the growth of ratio x, the number m of crystal water reduces gradually, and water molecules is present in the position of not occupied by negatively charged ion at interlayer.LDH has been widely used in a plurality of fields of environment remediation as a kind of well behaved sorbent material.LDHs class material and product of roasting thereof demonstrate extraordinary absorption property to dyestuff, and because the cost of cheapness is used widely.Due to the special laminate structure of LDH, so have some special character.The most outstanding is laminate metal ion adjustability, interlayer anion interchangeability.The adjustability of laminate metal ion refers to except the Mg in the LDH structure
2+And Al
3+Outside ion, can insert as required different metal ions.As long as the metal ion radius that inserts is with Mg
2+, Al
3+Close getting final product.The interlayer anion interchangeability refers to that the negatively charged ion of LDH interlayer can synthesize as required, and the negatively charged ion of its interlayer is tradable, these negatively charged ion are not limited only to inorganic anion, organic anion and coordination anion, biological negatively charged ion can enter equally, as long as negatively charged ion has certain electric density, not than 3.0 e nm
-2Littlely get final product too much.LDH material after absorption decolours, dries, still can continue to use after roasting.Mineral are as one of method of dye wastewater treatment using, and it can not only remove various organism, look and poison in waste water from dyestuff, have to take up an area the advantages such as little, simple to operate, effective.But it can not realize that organic degraded is the enrichment process of simple pollutent, easily cause secondary pollution, and the regenerative process running cost of sorbent material and sorbent material is higher, has therefore limited the extensive application of mineral.
Biological process is present most widely used wastewater processing technology, has that working cost is low, non-secondary pollution, safety, an advantage such as environmentally friendly, and application is more extensive in waste water containing dye is processed.At present, find many dye decolored Microbial resources that make, mainly contained fungi, bacterium and algae.The beginning of the seventies, Horitsu isolate first can degrade azo dyestuff bacterium
Bacillus subtilisIFO 3002, for microorganism decolouring dyestuff has been started new era.The bacterium of having found so far to have the azo reducing power mainly contain from Rhodopseudomonas (
Pseudomonas), Sphingomonas (
Sphingobacterium), bacillus (
BacilluS), Colibacter (
Escherichia coli), fusobacterium (
Clostridium) etc., also have simultaneously the azo reducing bacteria in many other genus, isolated a strain as people such as Kolekalr
Bacillus fusiformisKMK5, the multiple azoic dyestuff of can degrading.Biochemical treatment of dyestuff waste water has obvious shortcoming simultaneously, because microorganism active is limited by environmental factors largely, microorganism has certain requirement to conditions such as nutritive substance, pH value, temperature, be difficult to adapt to the characteristics that the waste water from dyestuff variation water quality is large, kind of dyes is many, toxicity is high, have again the difficulty of solid-liquid separation simultaneously.
Therefore, face all difficult problems that mineral and microorganism individual curing waste water from dyestuff face, attempt mineral and microorganism are organically connected, the associated treatment waste water from dyestuff, the advantage with two kinds of methods maximizes within the specific limits, the selection of a kind of wisdom of can yet be regarded as.
Summary of the invention
The objective of the invention is the actual demand of the qualified discharge that faces for dyeing waste water, the method for a kind of methylene blue efficient decolorizing in LDH-bacterium polymer structure is provided.Summary of the invention comprises that the polymeric preparation of LDH-bacterium and polymer are to the decolorizing effect of methylene blue.The present invention is a kind of with the method for LDH-bacterium polymer to the methylene blue decolouring, it is characterized in that the concrete steps of the method are:
(1) the synthetic single LDH of phase, the composition general formula of LDH is: M
2+ 1-xM
3+ x(OH)
2(A
n-)
x/nMH
2O, the present invention adopts NiFe-CO
3-LDH, granular size is 100 ~ 300 μ m;
(2) experiment adopt the gram-positive microorganism subtilis (
Bacillus subtilis) be reference culture;
(3) getting 3 ~ 10mgLDH, to be added to concentration be in 20 ~ 200mg/L Bacteria liquid, makes Ni-Fe LDH-bacterium polymer;
(4) above-mentioned middle gained LDH-bacterium polymer is joined 10 ~ 50 mg L
-1Carry out decolorization adsorption in the different concns methylene blue solution; Adsorption conditions is: 25 ± 1 ℃, and 150 r min, vibration 3 h;
(5) transferring to 10 mL centrifuge tubes after after absorption is completed, the mixed solution in Erlenmeyer flask being filtered with filter membrane detects; Experimental result can participate in adsorption process by SEM, fourier infrared bacterial detection.
The present invention has gone back research and comparison subtilis, LDH and the LDH-bacterium polymer decoloring ability to methylene blue, at ambient temperature, its decolouring amount is respectively 7.68,6.28 and 8.91 mg g-1, and obviously LDH-bacterium polymer has decoloration performance better.Therefore, comprehensive characterization of adsorption and DEVELOPMENT PROSPECT, LDH-bacterium polymer will become the decoloring material that has a high potential.
Description of drawings
Fig. 1 is the scanning electron microscopic observation figure of subtilis.
Fig. 2 is the polymeric scanning electron microscopic observation figure of LDH-bacterium.
Fig. 3 is the common photo observation figure (aseptic deionized water (A) wherein before and after bacillus subtilis bacteria suspension and ferronickel LDH absorption bacterium, bacillus subtilis bacteria suspension (B), add the bacterium liquid (C) after LDH adsorbs, LDH particle (D) before the absorption bacterium, the LDH-bacterium polymer (E) after the absorption bacterium).
Fig. 4 is the energy-spectrum scanning figure of subtilis (a) Ni-Fe LDH (b) and LDH-bacterium polymer (c).(wherein the power spectrum peak of Si comes from the glass slide of carrying bacterium).
Can see by scanning electron microscopic observation, individuality is about the subtilis of 2-3 μ m (Fig. 1) by a large amount of being adsorbed onto
Ferronickel LDH surface (Fig. 2).Muddy bacillus subtilis bacteria suspension (Fig. 3 (the B)) clear that becomes after adding LDH (Fig. 3 (C)) has confirmed the absorption of LDH to bacterium equally.And the LDH particle of absorption after bacterium the LDH particle that larger finer and close (Fig. 3 (E)) do not adsorb bacterium more open (Fig. 3 (D)) that becomes.From finding out that the peak (Fig. 4 (a)) of phosphoric on subtilis and LDH have upward all appeared on the polymeric energy of LDH-bacterium spectrogram (Fig. 4 (c)) at the peak (Fig. 4 (b)) of iron, nickel element by spectrogram.Because the characteristic peak of phosphoric and platinum element is approaching, confirm the existence of phosphoric in the LDH-polymer by phosphoric and platinum constituent content in contrast energy spectrogram.Above result has confirmed that fully ferronickel LDH has good absorption property to subtilis.
Embodiment
After now specific embodiments of the invention being described in.
The present embodiment has been narrated a kind of NiFe LDH--subtilis polymer to the method for the decolouring of methylene blue.Its concrete steps are:
(1) in two clean beakers that 250 mL deionized waters are housed, one adds 1.5 mol Ni(NO
3)
26H
2O and 0.5 mol Fe(NO
3)
39H
2O, another adds NaOH (1 M) and Na
2CO
3(2 M);
(2) then at ambient temperature, by constant flow pump, above-mentioned two kinds of solution are incorporated in the Erlenmeyer flask that fills 100 mL deionized waters, carry out vigorous stirring with magnetic stirring apparatus, keep simultaneously the pH of mixing solutions 11.0 ± 0.5, with synthetic NiFe LDH;
(3) be placed in 85 with mixed solution is airtight after after synthetic
oIn the C baking oven, ageing 4 d are to obtain better crystalline structure; Afterwards mixed solution is carried out repeatedly suction filtration, washing until the pH of filtrate near 7.0, then with solid-like Ni-Fe LDH 60
oDry under the C condition, the sample Ni-Fe LDH of oven dry is standby through grinding 200 mesh sieves;
(4) subtilis of use (
Bacillus subtilis) be reference culture, bacterial classification one ring that under aseptic condition, the picking inclined-plane is preserved, in 10 mL liquid Luria-Bertani substratum, 35
oC, 150 r min
-1Shaking culture 8 h activate;
(5) get nutrient solution 2 mL after activation, be inoculated into the same nutrient solution of 150 mL, cultivate under the same conditions 14 h.The gained culture is in 4000 r min
-1Centrifugal, collect thalline.Then with aseptic deionized water washing 3 times, remove cell surface absorption substratum and with the outer material of the part born of the same parents of the loose combination of cell.Afterwards the thalline Eddy diffusion is obtained bacterial suspension in aseptic deionized water stand-by;
(6) get 10 mgLDH and join that 6 mL concentration are housed is 45 mg L
-1Subtilis bacterium liquid in, in 25 ± 1
oC, 150 r min
-13 h that vibrate, standing 10 min leach particulate matter, use the aseptic deionized water repetitive scrubbing, remove the firmly thalline of absorption, make LDH-bacterium polymer;
(7) the above-mentioned LDH-bacterium polymers that prepare of 10 mg (LDH content is 10 mg) being put into 6 mL concentration is 30 mg L
-1Methylene blue solution in, in 25 ± 1
oC, 150 r min
-13 h vibrate; Again under aseptic condition, solid is leached afterwards, put into after rinsing with aseptic deionized water and be equipped with in the 150 sterilized LB nutrient solutions of mL, and inoculate appropriate subtilis, 35 in nutrient solution
oC, 150 r min
-110 h that vibrate leach afterwards and put into 30 mg L after solid rinses with aseptic deionized water again
-1Methylene blue solution in, carry out Decolorant Test.
The features and advantages of the invention----regenerability test
The regenerability test
The regenerability of the present invention after to LDH and LDH-bacterium polymer adsorption bleaching is studied, it is the methylene blue solution of 30 mg/L that the LDH of 10 mg is put into 6 mL concentration with the LDH-bacterium polymer for preparing (LDH content is 10 mg), in 25 ± 1 ℃, 150 r min
-13 h that vibrate under aseptic condition leach solid afterwards, put into after rinsing with aseptic deionized water and be equipped with in the 150 sterilized LB nutrient solutions of mL, and in the nutrient solution the appropriate subtilis of inoculation, 35 ℃, 150 r min
-110 h that vibrate leach afterwards and put in the methylene blue solution of 30 mg/L after solid rinses with aseptic deionized water again, carry out decolorization experiment.Repeat above-mentioned adsorption bleaching experiment, observe, measure LDH and LDH-bacterium polymer regeneration situation.
Result shows: after LDH-bacterium polymer absorption methylene blue, along with the increase of regeneration times, adsorptive capacity is descending gradually, may be due in regenerative process repeatedly, and death can occur, come off in the bacterium of LDH surface adsorption, reduces the decolouring amount; Still can keep 5.23 mg/g after 4 regeneration of LDH-bacterium polymer, still can keep 80 ~ 90% loading capacity after four regeneration of LDH-bacterium polymer, the discoloring agent loss amount is less, illustrates that LDH-bacterium polymer is a kind of reusable and easy well behaved decoloring material of regeneration.
Claims (1)
1. one kind with the method for LDH-bacterium polymer to methylene blue decolouring, it is characterized in that the concrete steps of the method are:
(1) the synthetic single LDH of phase, the composition general formula of LDH is: M
2+ 1-xM
3+ x(OH)
2(A
n-)
x/nMH
2O, the present invention adopts NiFe-CO
3-LDH, granular size is 100 ~ 300 μ m;
(2) adopt the gram-positive microorganism subtilis (
Bacillus subtilis) be reference culture;
(3) getting 3 ~ 10mgLDH, to be added to concentration be in 20 ~ 200mg/L Bacteria liquid, makes Ni-Fe LDH-bacterium polymer;
(4) above-mentioned gained LDH-bacterium polymer is joined 10 ~ 50 mg L
-1The different concns methylene blue solution (carries out decolorization adsorption in 0 ~ 50.Adsorption conditions is: 25 ± 1 ℃, and 150 r min
-1, vibration 3 h;
(5) transferring to 10 mL centrifuge tubes after after absorption is completed, the mixed solution in Erlenmeyer flask being filtered with filter membrane detects.Experimental result can participate in adsorption process by SEM, fourier infrared bacterial detection.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310075391.9A CN103159328B (en) | 2013-03-11 | 2013-03-11 | Method for discoloring methylene blue by layered double hydroxide (LDH)-bacterium polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310075391.9A CN103159328B (en) | 2013-03-11 | 2013-03-11 | Method for discoloring methylene blue by layered double hydroxide (LDH)-bacterium polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103159328A true CN103159328A (en) | 2013-06-19 |
| CN103159328B CN103159328B (en) | 2015-05-06 |
Family
ID=48582907
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310075391.9A Active CN103159328B (en) | 2013-03-11 | 2013-03-11 | Method for discoloring methylene blue by layered double hydroxide (LDH)-bacterium polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103159328B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104739655A (en) * | 2015-03-23 | 2015-07-01 | 上海源培生物科技股份有限公司 | Wet tissue |
| CN110182941A (en) * | 2019-04-30 | 2019-08-30 | 武汉理工大学 | A kind of efficient dephosphorization hydrotalcite precursor biomembrane and its preparation method and application |
| CN111001375A (en) * | 2019-12-29 | 2020-04-14 | 福建工程学院 | Preparation method of layered double-hydroxide composite adsorption material |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1843972A (en) * | 2006-04-21 | 2006-10-11 | 浙江大学 | Functional biomembrane carrier, its preparation method and use |
| CN101164688A (en) * | 2007-07-30 | 2008-04-23 | 山东大学 | Organic/inorganic substance layered composite functional material and preparation method thereof |
| BRPI0802299A2 (en) * | 2008-07-31 | 2010-03-23 | Unicamp | manufacturing process, application, recovery, reuse and final disposal of two-dimensional porous materials |
| EP2174909A1 (en) * | 2008-10-07 | 2010-04-14 | Akzo Nobel N.V. | Composition comprising a layered double hydroxide |
| CN101890329A (en) * | 2010-07-21 | 2010-11-24 | 北京化工大学 | Thiophene adsorbents and application thereof |
| CN102115722A (en) * | 2010-12-02 | 2011-07-06 | 东北林业大学 | Bacillus subtilis ls02 laccase and application thereof |
| CN102627261A (en) * | 2012-04-23 | 2012-08-08 | 上海大学 | Laminated bimetal oxide material prepared by using main laminate cation exchange way and method for preparing laminated bimetal oxide material |
-
2013
- 2013-03-11 CN CN201310075391.9A patent/CN103159328B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1843972A (en) * | 2006-04-21 | 2006-10-11 | 浙江大学 | Functional biomembrane carrier, its preparation method and use |
| CN101164688A (en) * | 2007-07-30 | 2008-04-23 | 山东大学 | Organic/inorganic substance layered composite functional material and preparation method thereof |
| BRPI0802299A2 (en) * | 2008-07-31 | 2010-03-23 | Unicamp | manufacturing process, application, recovery, reuse and final disposal of two-dimensional porous materials |
| EP2174909A1 (en) * | 2008-10-07 | 2010-04-14 | Akzo Nobel N.V. | Composition comprising a layered double hydroxide |
| CN101890329A (en) * | 2010-07-21 | 2010-11-24 | 北京化工大学 | Thiophene adsorbents and application thereof |
| CN102115722A (en) * | 2010-12-02 | 2011-07-06 | 东北林业大学 | Bacillus subtilis ls02 laccase and application thereof |
| CN102627261A (en) * | 2012-04-23 | 2012-08-08 | 上海大学 | Laminated bimetal oxide material prepared by using main laminate cation exchange way and method for preparing laminated bimetal oxide material |
Non-Patent Citations (2)
| Title |
|---|
| ALEKSEEVA 等: "Enhancing atrazine biodegradation by Pseudomonas sp strain ADP adsorption to Layered Double Hydroxide bionanocomposites", 《JOURNAL OF HAZARDOUS MATERIALS 》, vol. 191, 31 December 2011 (2011-12-31) * |
| 钱宝钢 等: "枯草芽孢杆菌产絮凝剂的发酵条件及絮凝特性研究", 《水处理技术》, vol. 37, no. 8, 31 August 2011 (2011-08-31), pages 2 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104739655A (en) * | 2015-03-23 | 2015-07-01 | 上海源培生物科技股份有限公司 | Wet tissue |
| CN110182941A (en) * | 2019-04-30 | 2019-08-30 | 武汉理工大学 | A kind of efficient dephosphorization hydrotalcite precursor biomembrane and its preparation method and application |
| CN111001375A (en) * | 2019-12-29 | 2020-04-14 | 福建工程学院 | Preparation method of layered double-hydroxide composite adsorption material |
| CN111001375B (en) * | 2019-12-29 | 2023-03-14 | 福建工程学院 | Preparation method of layered double-hydroxide composite adsorption material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103159328B (en) | 2015-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Farooq et al. | Application of magnetic graphene oxide for water purification: heavy metals removal and disinfection | |
| Haldorai et al. | An efficient removal of methyl orange dye from aqueous solution by adsorption onto chitosan/MgO composite: A novel reusable adsorbent | |
| Wang et al. | Maximizing the utilization of photo-generated electrons and holes of g-C3N4 photocatalyst for harmful algae inactivation | |
| Bustard et al. | Biosorption of textile dyes by biomass derived from Kluyveromyces marxianus IMB3 | |
| Selvakumar et al. | As (V) removal using carbonized yeast cells containing silver nanoparticles | |
| Song et al. | Biocompatible G-Fe3O4/CA nanocomposites for the removal of Methylene Blue | |
| Sun et al. | Environmental application of magnetic cellulose derived from Pennisetum sinese Roxb for efficient tetracycline removal | |
| Shanmugam et al. | Bi-model cationic dye adsorption by native and surface-modified Trichoderma asperellum BPL MBT1 biomass: from fermentation waste to value-added biosorbent | |
| CN111001375B (en) | Preparation method of layered double-hydroxide composite adsorption material | |
| Wu et al. | Decontamination of multiple heavy metals-containing effluents through microbial biotechnology | |
| CN103159328B (en) | Method for discoloring methylene blue by layered double hydroxide (LDH)-bacterium polymer | |
| Sathishkumar et al. | Two and three‐parameter isothermal modeling for liquid‐phase sorption of Procion Blue H‐B by inactive mycelial biomass of Panus fulvus | |
| CN113813921B (en) | Preparation method and application of lysine functionalized layered double hydroxide adsorbent | |
| CN103801267A (en) | Preparation method for novel magnetic chitosan composite microsphere antibiotic adsorbent | |
| Takey et al. | Bioremediation of xenobiotics: use of dead fungal biomass as biosorbent | |
| CN100363483C (en) | Heavy metal adsorbent composition | |
| CN110479226B (en) | Clay mineral/agriculture and forestry waste biomass composite sewage treatment agent, and preparation method and application thereof | |
| Angelova et al. | Magnetically modified sheaths of Leptothrix sp. as an adsorbent for Amido black 10B removal | |
| CN104258816A (en) | Preparation method of magnetic stripping type montmorillonite nanocomposite material for wastewater treatment | |
| CN105688831A (en) | Modified-nano-hydroxyapatite capable of effectively absorbing methylene blue dyes and preparation method and application of modified-nano-hydroxyapatite | |
| Saratale et al. | Decolorization and degradation of reactive azo dyes by fixed bed bioreactors containing immobilized cells of Proteus vulgaris NCIM-2027 | |
| KR101540861B1 (en) | Bacillus subtilis JB-016 strain having sorption of cationic dye and metal, and biomass using the same | |
| Zhou et al. | Coagulation enhancement of exopolysaccharide secreted by an Antarctic sea-ice bacterium on dye wastewater | |
| KR101540860B1 (en) | Bacillus thuringiensis JB-007 strain having sorption of anionic dye and metal, and biomass using the same | |
| Sachin et al. | Development of a ZnOS+ C composite as a potential adsorbent for the effective removal of fast green dye from real wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |