CN102728246A - Bacteria-immobilized hollow fiber polysulfone film for degradation of high concentration tetrachlorphenoxide, and preparation method thereof - Google Patents
Bacteria-immobilized hollow fiber polysulfone film for degradation of high concentration tetrachlorphenoxide, and preparation method thereof Download PDFInfo
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- CN102728246A CN102728246A CN2012102031359A CN201210203135A CN102728246A CN 102728246 A CN102728246 A CN 102728246A CN 2012102031359 A CN2012102031359 A CN 2012102031359A CN 201210203135 A CN201210203135 A CN 201210203135A CN 102728246 A CN102728246 A CN 102728246A
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Abstract
The invention relates to a bacteria-immobilized hollow fiber polysulfone film for degradation of high concentration tetrachlorphenoxide, and a preparation method thereof. The film has an asymmetric three-layer structure, and is divided into an outer surface layer, a middle support layer and an inner surface later from the outer to the inner, wherein active carbon particles are uniformly distributed in each layer, the particle size is less than or equal to 10 mum, the specific surface area is 1104 m<2>/g, the dead volume is 0.92 cm<3>/g, the continuous phase of the film is transparent bisphenol A type polysulfone, the molecular weight is 100000-116500, and Pseudomonas aeruginosa is fixed in the surface of the film and the middle layer. After microbial immobilization is performed, the bacteria provide increased tolerance limitation for the high concentration toxic substrates so as to continuously grow. The degradation of the high concentration matrix by the immobilized bacteria mainly depends on protective effects on the bacteria by the hollow fiber film, such that the bacteria can grow so as to degrade the matrix.
Description
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Technical field
The present invention relates to bacterium immobilization doughnut PS membrane of a kind of interpolation active carbon that is used for the degrading high concentration tetrachlorophenol and preparation method thereof.
Background technology
Along with industrial Agricultural Development; A large amount of life and industrial wastewaters enter water body; Particularly herbicide, pesticide, bacteria remover, heat exchange catalyst, insulator, lubricant; The a large amount of manufacturings and the use of these materials, wherein contained organic matter must cause soil and water pollution, even in some industrial wastewater its concentration up to 1000 mg/L.These material strong toxicities, difficult degraded, enrichment in vivo easily, thus environment is had an immense impact on.And on the other hand; Available water source of fresh water is more and more rare on the earth; The city of listing the lack of water zone in is more and more, and especially China is water quality type lack of water big country, and various places government all hopes through advanced treating and reuse to industrial wastewater; Improve the utilization rate of existing water resource, solve the difficulty of present lack of water.
(4-CP) is a kind of from the environmental contaminants in many industrial process to tetrachlorophenol.Since toxic and possible carcinogenic, extensive concern is received in its discharging.Tetrachlorophenol can be degraded through the process of the common metabolism of microorganism, and metabolism is a kind of special biodegradation mode altogether, mainly is meant this organic matter transformation that can not utilize matrix as the energy and component element of microorganism; Metabolism also is a kind of important biodegradation means altogether, usually is used to handle contaminated surface water, industrial wastewater and poisonous and harmful substance.Yet; Cometabolism process normally can not continue to carry out; The non-growth property substrate that can be degraded generally contains identical molecular structure with growth property substrate, in their degradation process, needs same enzyme to decompose substrate, so the competitiveness between these 2 kinds of materials suppresses inevitable.Come degradable organic pollutant in order to effectively utilize cometabolism process, between poisonous substrate and microorganism, need make up barrier together.Microbial immobilization is a kind of feasible technology that can reach above-mentioned requirements, and microbial immobilized technology plays important use in pharmacy in biological food conversion and some special chemical article production processes.In recent years, this technology also was used to sewage disposal, particularly in the process that promotes the degraded toxic compounds.With microbial suspension growth phase ratio, the major advantage of microbial immobilized technology is the microorganism concn that improves in the reactor, and the protection microorganism shortens hydraulic detention time, thereby improves reactor efficiency.Immobilization material commonly used has inorganic and organic two big types in this method, such as active carbon, diatomite, alginic acid pearl etc.These materials all are proved to be the fixing carrier of good microorganism.Yet when microorganism is completely fixed, its growth can inevitably slow down.This is because mass transfer limit and aeration are difficult, and another shortcoming is as time passes, and microorganism can be filtered out from fixing matrix.In sewage disposal, be applied in the biodegradation toxic organic compound, show the substrate inhibitory action, this is a kind of advantage on the contrary.
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Summary of the invention
The technical problem that solves:Matrix causes common metabolism to be difficult to carry out the problem that bacterium can not grow to the inhibitory action of bacterium when solving the degraded industrial wastewater middle and high concentration tetrachlorophenol that prior art exists.The invention provides a kind of bacterium immobilization technology, through to bacterium immobilization in having added the doughnut PS membrane reactor of active carbon, under the condition that phenol exists, bacterium can be total to the tetrachlorophenol of metabolic degradation high concentration.
Technical scheme:
Be used for the bacterium immobilization doughnut PS membrane of degrading high concentration tetrachlorophenol, this film is asymmetric three-decker, is divided into extexine, middle support layer and endosexine from outside to inside; Be uniform-distribution with activated carbon granule in every layer, grain diameter≤10 μ m, specific area 1104m
2/ g, voidage 0.92cm
3/ g, the continuous phase of film is transparent bisphenol-a polysulfone, molecular weight 100000 ~ 116500, the surface of film and intermediate layer are fixed with pseudomonas aeruginosa (Pseudomonas aeruginosa).Said activated carbon granule is processed by cocoanut shell.Said transparent bisphenol-a polysulfone is bisphenol-A and 4, and the polycondensation of 4-dichloro diphenylsulfone forms, molecular weight 100000 ~ 116500,180 ~ 190 ℃ of vitrification points, 170 ~ 175 ℃ of heat distortion tempertures, hot strength 75MPa, bending modulus 2650MPa.
The preparation method who is used for the bacterium immobilization doughnut PS membrane of degrading high concentration tetrachlorophenol; Step is: activation: pseudomonas aeruginosa (Pseudomonas aeruginosa) nutrient solution abandoning supernatant after centrifugal; Wash with physiological salt liquid again; Make bacteria suspension, transfer OD600nm=2.0; Fixing: get hollow-fibre membrane, put into container, in container, add the bacteria suspension that mixes, concussion 18h accomplishes fixing.Each centrifugal condition is 6000r/min, 10min, 4 ℃.Said hollow-fibre membrane is with transparent bisphenol-a polysulfone; Activated carbon granule and 1-methyl-2 pyrrolones mix by quality 1:4:5 ~ 1:5:5; 80 ℃ of following heating for dissolving, adopt wet type spinning technique spinning active carbon doughnut PS membrane then, the wet spinning journey is 2m; Volume flow filter 15mL/min, 80 ℃ of spinning solution temperature are extruded in spinning.
Beneficial effect:
1. carry out microbial immobilized after, bacterium strengthens the tolerance limit of the poisonous substrate of high concentration, thereby is able to continue growth.Immobilization bacterium mainly has benefited from the protective effect of hollow-fibre membrane to bacterium to the degraded of the matrix of high concentration, makes bacterium be able to growth, thus matrix degradation; With microbial suspension growth phase ratio, the major advantage of microbial immobilized technology is the microorganism concn that improves in the reactor, and the protection microorganism shortens hydraulic detention time, thereby improves reactor efficiency.
2. the adding of activated carbon granule makes membrane structure more loose, and it is big that hole becomes; In the field of biological wastewater treatment, the structures shape of film the quality of growth of microorganism environment, and big characteristics in the inner loose hole of this film; Can quantitatively hold more microbial growth; Improve the adsorption capacity of film, and improved the speed of organic matter mass transfer, thereby improved degradation efficiency; And active carbon be added in the mechanical strength that improves film the time, the pliability of film is still good, fabrication processes can make spinning solution remain on suitable temperature and viscosity, good spinning property; Active carbon doughnut film strength is big, and pliability is good, can freely support, and therefore when carrying out biological wastewater treatment, need not to increase any support object again.
3. adopted commodity polymer material polysulfones, activated carbon granule adopts cheap cocoanut shell to make, and cost of manufacture is reduced greatly.
Description of drawings
Fig. 1 is a cross-sectional structure sketch map of the present invention.
Among Fig. 1,1, fine and close extexine, 2, middle support layer, 3, loose relatively endosexine, 4, activated carbon granule, 5, bacterial clump.
Fig. 2 is a hollow-fibre membrane surface bacteria SEM sketch map of the present invention.
Fig. 3 is a hollow-fibre membrane SC SEM sketch map of the present invention.
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The specific embodiment
The following specific embodiment does not limit technical scheme of the present invention in any form, and the technical scheme that mode obtained that every employing is equal to replacement or equivalent transformation all drops on protection scope of the present invention.
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Embodiment 1:
Present embodiment is a kind of bacterium immobilization doughnut PS membrane of interpolation active carbon of the industrial wastewater middle and high concentration tetrachlorophenol that is used to degrade.Adopting macromolecule polysulfones general, with low cost is raw material, and the macromolecule polysulfones is transparent bisphenol-a polysulfone, by bisphenol-A and 4; The polycondensation of 4-dichloro diphenylsulfone forms; Molecular weight 100000 ~ 116500,180 ~ 190 ℃ of vitrification points, 170 ~ 175 ℃ of heat distortion tempertures; Hot strength 75MPa, bending modulus 2650MPa.Be aided with the activated carbon granule that cocoanut shell is processed, its average grain diameter is less than 10 μ m, specific area 1104m
2/ g, voidage 0.92cm
3/ g, 1-methyl-2 pyrrolones is a solvent, with the macromolecule polysulfones, activated carbon granule and 1-methyl-2 pyrrolones mix by quality 1:4:5.Earlier various raw materials are dissolved under 80 ℃ of temperature, adopt wet type spinning technique spinning active carbon doughnut PS membrane then; Detailed process is: spinning solution is recycled pipeline and delivers to spinning-drawing machine, through measuring pump metering, gets into spinning head through candle filter, tube connector then, and the wet spinning journey is 2m, and volume flow filter 15mL/min, 80 ℃ of spinning solution temperature are extruded in spinning.
Pseudomonas aeruginosa (Pseudomonas aeruginosa) can be fixed on the surface and the intermediate layer of film, is kept on the agar medium, and temperature is 4 ℃, and pseudomonas aeruginosa (Pseudomonas aeruginosa) nutrient solution comprises K
2HPO
43H
2O, 6.0g; KH
2PO
4, 1.0g; MgSO
47H
2O, 0.4g; (NH
4)
2SO
4, 2.5g; Distilled water, 1000mL.Bacterium carries out activation before use, cultivate 30h after, again through two times centrifugal (6000r/min, 10min, 4 ℃), abandoning supernatant, again with the physiological salt liquid flushing, centrifugal repeatedly 3 times, make bacteria suspension, transfer OD600nm=2.0, be used for degradation experiment.
After bacterium is collected, carry out its immobilization at once.Get the long doughnut PS membrane of 9cm, restraint into 1 bundle for per 9, totally 4 bundles of conical flasks of putting into 500 mL add microbial solution 35 mL that mix, and are placed on and evenly rock 18 h on the shaking table, carry out the fixing of microorganism.Subsequently, hollow fiber bundle takes out from solution, uses the sterile distilled water clean surface.Immobilization bacterium degradation of phenol and tetrachlorophenol carry out on membrane carrier, and the concentration of phenol and tetrachlorophenol is respectively 600mg/L and 120mg/L, and the experiment treatment effect is fine, and degradation rate can reach 100%.
Embodiment 2:
Present embodiment is a kind of bacterium immobilization doughnut PS membrane of interpolation active carbon of the industrial wastewater middle and high concentration tetrachlorophenol that is used to degrade.The composition of membrane material is identical with embodiment 1 with the preparation method, but has increased the dosage of granular activated carbon, and with the macromolecule polysulfones, the mass ratio of activated carbon granule and 1-methyl-2 pyrrolones is adjusted into 1:5:5.The gained tunica fibrosa is similarly three layers of dissymmetrical structure; But the outer surface of film is fine and close more; Activated carbon granule is concentrated in the inner more even distribution of film; The adsorption capacity of adding the bacterium immobilization doughnut PS membrane self of active carbon is so further strengthened, and the concentration of phenol and tetrachlorophenol is adjusted into 1000mg/L and 200mg/L during degradation experiment, and treatment effeciency also can reach 100%.
Be used for the bacterium immobilization doughnut PS membrane of degrading high concentration tetrachlorophenol, this film is asymmetric three-decker, is divided into extexine, middle support layer and endosexine from outside to inside; Be uniform-distribution with activated carbon granule in every layer, grain diameter≤10 μ m, specific area 1104m
2/ g, voidage 0.92cm
3/ g, the continuous phase of film is transparent bisphenol-a polysulfone, molecular weight 100000 ~ 116500, the surface of film and intermediate layer are fixed with pseudomonas aeruginosa (Pseudomonas aeruginosa).Said activated carbon granule is processed by cocoanut shell.Said transparent bisphenol-a polysulfone is bisphenol-A and 4, and the polycondensation of 4-dichloro diphenylsulfone forms, molecular weight 100000 ~ 116500,180 ~ 190 ℃ of vitrification points, 170 ~ 175 ℃ of heat distortion tempertures, hot strength 75MPa, bending modulus 2650MPa.
The preparation method who is used for the bacterium immobilization doughnut PS membrane of degrading high concentration tetrachlorophenol; Step is: activation: pseudomonas aeruginosa (Pseudomonas aeruginosa) nutrient solution abandoning supernatant after centrifugal; Wash with physiological salt liquid again; Make bacteria suspension, transfer OD600nm=2.0; Fixing: get hollow-fibre membrane, put into container, in container, add the bacteria suspension that mixes, concussion 18h accomplishes fixing.Each centrifugal condition is 6000r/min, 10min, 4 ℃.Said hollow-fibre membrane is with transparent bisphenol-a polysulfone; Activated carbon granule and 1-methyl-2 pyrrolones mix by quality 1:4:5 ~ 1:5:5; 80 ℃ of following heating for dissolving, adopt wet type spinning technique spinning active carbon doughnut PS membrane then, the wet spinning journey is 2m; Volume flow filter 15mL/min, 80 ℃ of spinning solution temperature are extruded in spinning.
Claims (6)
1. the bacterium immobilization doughnut PS membrane that is used for the degrading high concentration tetrachlorophenol is characterized in that this film is asymmetric three-decker, is divided into extexine, middle support layer and endosexine from outside to inside; Be uniform-distribution with activated carbon granule in every layer, grain diameter≤10 μ m, specific area 1104m
2/ g, voidage 0.92cm
3/ g, the continuous phase of film is transparent bisphenol-a polysulfone, molecular weight 100000 ~ 116500, the surface of film and intermediate layer are fixed with pseudomonas aeruginosa (Pseudomonas aeruginosa).
2. the bacterium immobilization doughnut PS membrane that is used for the degrading high concentration tetrachlorophenol according to claim 1 is characterized in that said activated carbon granule processed by cocoanut shell.
3. the bacterium immobilization doughnut PS membrane that is used for the degrading high concentration tetrachlorophenol according to claim 1; It is characterized in that said transparent bisphenol-a polysulfone is bisphenol-A and 4, the polycondensation of 4-dichloro diphenylsulfone forms, molecular weight 100000 ~ 116500; 180 ~ 190 ℃ of vitrification points; 170 ~ 175 ℃ of heat distortion tempertures, hot strength 75MPa, bending modulus 2650MPa.
4. the said preparation method who is used for the bacterium immobilization doughnut PS membrane of degrading high concentration tetrachlorophenol of above-mentioned arbitrary claim is characterized in that:
A. activation: pseudomonas aeruginosa (Pseudomonas aeruginosa) nutrient solution abandoning supernatant after centrifugal, with the physiological salt liquid flushing, make bacteria suspension again, transfer OD600nm=2.0;
B. fixing: get hollow-fibre membrane, put into container, in container, add the bacteria suspension that mixes, concussion 18h accomplishes fixing.
5. the preparation method who is used for the bacterium immobilization doughnut PS membrane of degrading high concentration tetrachlorophenol according to claim 4 is characterized in that: each centrifugal condition is 6000r/min, 10min, 4 ℃.
6. the preparation method who is used for the bacterium immobilization doughnut PS membrane of degrading high concentration tetrachlorophenol according to claim 4; It is characterized in that: said hollow-fibre membrane is with transparent bisphenol-a polysulfone, and activated carbon granule and 1-methyl-2 pyrrolones mix by quality 1:4:5 ~ 1:5:5,80 ℃ of following heating for dissolving; Adopt wet type spinning technique spinning active carbon doughnut PS membrane then; The wet spinning journey is 2m, and volume flow filter 15mL/min, 80 ℃ of spinning solution temperature are extruded in spinning.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105384243A (en) * | 2015-12-06 | 2016-03-09 | 西北农林科技大学 | Biocarbon carrier reactor |
| CN108238679A (en) * | 2016-12-27 | 2018-07-03 | 中国科学院宁波城市环境观测研究站 | A kind of water body lead ion enrichment treatment device |
| WO2018170320A1 (en) * | 2017-03-15 | 2018-09-20 | ImMutriX Therapeutics, Inc. | Compositions and methods for the treatment of metabolic disorders |
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| US20080035571A1 (en) * | 2006-08-08 | 2008-02-14 | Exxonmobil Research And Engineering Company | Integrally-layered polymeric membranes and method of use |
| CN101596420A (en) * | 2009-06-19 | 2009-12-09 | 河海大学 | Active carbon doughnut PS membrane and preparation method thereof |
| CN101857847A (en) * | 2010-05-06 | 2010-10-13 | 合肥工业大学 | Pseudomonas aeruginosa strain separating, purifying and domesticating method and use |
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2012
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| US20080035571A1 (en) * | 2006-08-08 | 2008-02-14 | Exxonmobil Research And Engineering Company | Integrally-layered polymeric membranes and method of use |
| CN101596420A (en) * | 2009-06-19 | 2009-12-09 | 河海大学 | Active carbon doughnut PS membrane and preparation method thereof |
| CN101857847A (en) * | 2010-05-06 | 2010-10-13 | 合肥工业大学 | Pseudomonas aeruginosa strain separating, purifying and domesticating method and use |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105384243A (en) * | 2015-12-06 | 2016-03-09 | 西北农林科技大学 | Biocarbon carrier reactor |
| CN108238679A (en) * | 2016-12-27 | 2018-07-03 | 中国科学院宁波城市环境观测研究站 | A kind of water body lead ion enrichment treatment device |
| WO2018170320A1 (en) * | 2017-03-15 | 2018-09-20 | ImMutriX Therapeutics, Inc. | Compositions and methods for the treatment of metabolic disorders |
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