CN101367580A - Method for accelerating biotransformation of organic matter hard-to-degrade with co-immobilized amboceptor and thalli - Google Patents
Method for accelerating biotransformation of organic matter hard-to-degrade with co-immobilized amboceptor and thalli Download PDFInfo
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- CN101367580A CN101367580A CNA2008100135164A CN200810013516A CN101367580A CN 101367580 A CN101367580 A CN 101367580A CN A2008100135164 A CNA2008100135164 A CN A2008100135164A CN 200810013516 A CN200810013516 A CN 200810013516A CN 101367580 A CN101367580 A CN 101367580A
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000036983 biotransformation Effects 0.000 title claims description 19
- 241001052560 Thallis Species 0.000 title abstract 4
- 239000005416 organic matter Substances 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000010802 sludge Substances 0.000 claims abstract description 35
- 239000012528 membrane Substances 0.000 claims abstract description 19
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 claims description 45
- 241000894006 Bacteria Species 0.000 claims description 43
- 239000000126 substance Substances 0.000 claims description 37
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 23
- 150000004056 anthraquinones Chemical group 0.000 claims description 23
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 16
- 230000009467 reduction Effects 0.000 claims description 10
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 claims description 8
- QBPFLULOKWLNNW-UHFFFAOYSA-N chrysazin Chemical compound O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O QBPFLULOKWLNNW-UHFFFAOYSA-N 0.000 claims description 8
- 239000008187 granular material Substances 0.000 claims description 7
- VBQNYYXVDQUKIU-UHFFFAOYSA-N 1,8-dichloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC(Cl)=C2C(=O)C2=C1C=CC=C2Cl VBQNYYXVDQUKIU-UHFFFAOYSA-N 0.000 claims description 4
- GJCHQJDEYFYWER-UHFFFAOYSA-N 1,8-dihydroxy-4,5-dinitroanthracene-9,10-dione Chemical compound O=C1C2=C([N+]([O-])=O)C=CC(O)=C2C(=O)C2=C1C([N+]([O-])=O)=CC=C2O GJCHQJDEYFYWER-UHFFFAOYSA-N 0.000 claims description 4
- KHUFHLFHOQVFGB-UHFFFAOYSA-N 1-aminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2N KHUFHLFHOQVFGB-UHFFFAOYSA-N 0.000 claims description 4
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 claims description 4
- YCANAXVBJKNANM-UHFFFAOYSA-N 1-nitroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2[N+](=O)[O-] YCANAXVBJKNANM-UHFFFAOYSA-N 0.000 claims description 4
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- 125000004151 quinonyl group Chemical group 0.000 claims description 2
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- POJOORKDYOPQLS-UHFFFAOYSA-L barium(2+) 5-chloro-2-[(2-hydroxynaphthalen-1-yl)diazenyl]-4-methylbenzenesulfonate Chemical compound [Ba+2].C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O.C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O POJOORKDYOPQLS-UHFFFAOYSA-L 0.000 description 8
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- 239000008363 phosphate buffer Substances 0.000 description 4
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 3
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- 238000001471 micro-filtration Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000004053 quinones Chemical class 0.000 description 2
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- 239000006228 supernatant Substances 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
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- 241001330002 Bambuseae Species 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- RZUBARUFLYGOGC-MTHOTQAESA-L acid fuchsin Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=C(N)C(C)=CC(C(=C\2C=C(C(=[NH2+])C=C/2)S([O-])(=O)=O)\C=2C=C(C(N)=CC=2)S([O-])(=O)=O)=C1 RZUBARUFLYGOGC-MTHOTQAESA-L 0.000 description 1
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- WXLFIFHRGFOVCD-UHFFFAOYSA-L azophloxine Chemical compound [Na+].[Na+].OC1=C2C(NC(=O)C)=CC(S([O-])(=O)=O)=CC2=CC(S([O-])(=O)=O)=C1N=NC1=CC=CC=C1 WXLFIFHRGFOVCD-UHFFFAOYSA-L 0.000 description 1
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- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
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Abstract
The invention provides a method of promoting refractory organics to be degraded by co-immobilized mediator and thalli, belonging to the environment engineering water treatment technical field. The method is characterized in that embedding method, membrane reactor method or grain sludge method are used to co-immobilize the thalli and water insoluble mediator in a biological reactor and promote the biological reductive conversion of the refractory organics in water, with the result that the whole biological treatment efficiency of refractory organic waste water is greatly improved. The invention has the beneficial effect that the co-immobilized water insoluble mediator and thalli has simple preparation technology, is convenient to be operated, solves the secondary pollution problem caused by the running out of the water soluble mediator with the water, and can be widely used in the biological treatment of the refractory organic waste water such as azo dyes, nitro arene, polychlorinated organic compounds and so on.
Description
Technical field
The invention belongs to the environmental engineering water-treatment technology field, relate to the method that co-immobilized amboceptor and thalline promote the hardly degraded organic substance bio-transformation.
Background technology
Along with development of industry and agriculture, produced a large amount of poisonous hardly degraded organic substances, as halo, contain azo and nitroaromatic or the like.These compounds are widely used in entering physical environment in people's production and the life and through number of ways, present characteristics such as extended residual and high toxicity.Some material wherein has teratogenesis or carcinogenesis, can be in food chain bio-accumulation, serious threat is to human life security.
The processing that contains poisonous hardly degraded organic substance waste water has the combination of physics method, chemical method, biological process and these methods.Therefore because that biological process has is simple to operate, running cost is low, the advantage of non-secondary pollution is the first-selected treatment technology of above-mentioned waste water.Biological treatment can be divided into aerobic method, anaerobic process and anaerobic-aerobic method.Wherein, anaerobic-aerobic technology (A/O) is to handle the most effectual way of this class waste water.Because azo bond, nitro etc. have extremely strong sucting electronic effect, make it directly to be difficult to obtain degraded by oxidative pathway.And these hardly degraded organic substances as hydrolysis, product methane, denitrification, reversal of cure etc., often can improve its follow-up aerobic biochemical through anaerobic biological treatment.But the anaerobion metabolic rate is slow, especially to some intractable organic pollutants.Therefore, the bottleneck of the normally above-mentioned hardly degraded organic substance complete biodegradable of anaerobic treatment.
There are some researches show, some humic acid or quinones, as 2,6-disulfonic acid anthraquinone (AQDS), but as the transmission of redox mediators accelerated electron between electron donor and acceptor, thereby increase substantially the chemistry and the bio-transformation efficient of pollutent.Its action principle is as follows: in the presence of suitable electron donor, AQDS can be a quinhydrones by biological reducing, but the latter reduces chemical compound lot as electron donor non-selectivity ground, as halo and nitrogenous aromatic compound etc., and finishes the regeneration of AQDS.This biological-chemical combination mechanism has special advantages in mixing the hardly degraded organic substance processing, especially this reaction can be carried out outside born of the same parents, enter intracellular high polarity or baroque organism, poisonous hardly degraded organic substance etc. for being difficult to, can increase substantially its biodegradation rate.
Though the anaerobe that some water-soluble quinoness such as AQDS can the catalytic intensification hardly degraded organic substance transforms, its drawback is these quinones costlinesses in water treatment system, and can run off with water outlet, causes secondary pollution.
Van der Zee etc. has found that gac can and can be used as redox mediators by biological reducing, and its active group is considered to quinone/carbonyl.But it is much lower that gac is accepted the energy force rate micromolecular compound AQDS of electronics, and the latter is the former 6.1 times.And gac quinone/carbonyl that have and that oxidation modification generates itself is positioned at the micropore place of aperture less than 2nm mostly, and microorganism is difficult to touch micropore usually greater than 0.2 μ m, and therefore, the katalysis that quinone/carbonyl wherein plays is limited.This laboratory once used calcium-alginate-immobilized anthraquinone as amboceptor, found that it can make the biological decolouring speed of several azoic dyestuffs improve 1.5-2 doubly.But owing to the contact restriction of thalline, so the catalytic activity of this immobilization anthraquinone awaits further raising with amboceptor.
Summary of the invention
The objective of the invention is thalline and redox mediators co-immobilization in a reactor, solve water soluble oxidized reduction amboceptor and run off with water outlet and cause the technical problem of secondary pollution, the biological reducing of strengthening hardly degraded organic substance transforms.
Technical solution of the present invention is: select water-insoluble anthraquinone analog compound as amboceptor, utilize three kinds of immobilization technologies (entrapping method, membrane reactor method or granule sludge method), realize the co-immobilization of water-insoluble amboceptor and thalline, and in anaerobic biological reactor, quicken the biological reducing conversion of hardly degraded organic substance, thereby the whole biological treatment efficient of organic wastewater with difficult degradation thereby is greatly improved.
Particular content is as follows:
One, its step of bio-transformation of hardly degraded organic substance is as follows in entrapping method co-immobilized amboceptor and the thalline acceleration water:
1, the selection of thalline and cultivation
Used thalline is quinone reduction flora, active sludge or the two combination by enrichment obtained.Wherein, the enrichment of quinone reduction flora and cultivation are as follows:
Enrichment medium consists of (g.L
-1): NH
4Cl, 1.0; KH
2PO
4, 0.5; K
2HPO
4, 0.6; MgCl
26H
2O, 0.2; CaCl
22H
2O, 0.05; Na
2S9H
2O, 0.037; PH7.0; AQDS 0.15g.L
-1, glucose 0.5g.L
-1
Pack in the serum bottle active sludge of above-mentioned enrichment medium and 1～10% (v/v) fills up serum bottle with enrichment medium, the sealing of recycle silicon plug, put 30 ℃ of incubators and leave standstill cultivation, 1～7d is an enrichment cycle, behind each end cycle, bacterium liquid is transferred in the fresh enrichment medium.After enrichment finishes, this flora is forwarded to carries out enlarged culturing in the enrichment medium.Place 30 ℃ of anaerobism incubators to cultivate, centrifugal when reaching logarithmic phase, abandoning supernatant uses the phosphate buffer soln of 0.1M pH7.0 to wash three times, the thalline after centrifugal is mixed with phosphate buffer soln concentrates bacterium liquid at last.
2, the selection of amboceptor
Water-insoluble amboceptor is anthraquinone, 1-nitroanthraquinone, 1-aminoanthraquinone, 1,8-dihydroxyanthraquinone, 1-chloroanthraquinone, 1,2-dihydroxyanthraquinone, 1,4-dihydroxyanthraquinone, 1,8-dihydroxyl-4,5-dinitroanthraquinone, 1,8-dichloroanthraquinone, 1-amino-2, in the 4-dibromo-anthraquinone one or more, its structural formula is as shown in table 1.
The water-insoluble amboceptor of table 1
3, the preparation of entrapping method co-immobilization bacterium ball/bacterium piece:
The embedding carrier is some natural or synthesising macromolecule copolymers, as one or more of alginates, agar, carrageenin, polyvinyl alcohol etc.The preparation process of co-immobilization bacterium ball or bacterium piece is as follows:
Step 1. makes the embedding carrier water-soluble by heater means;
Step 3. makes the said mixture gelation by adding additive or reducing temperature;
Step 4. is processed into above-mentioned gel spherical or block.
4, co-immobilized amboceptor and thalline quicken the bio-transformation of hardly degraded organic substance in the water
Co-immobilization bacterium ball/bacterium piece is added in the anaerobic biological reactor, and water inlet consists of hardly degraded organic substance, cosubstrate, (NH
4)
2SO
4, Na
2HPO
4, KH
2PO
4, micro-CaCl
2, MgSO
4, FeCl
3, COD:N:P=100:5:1.
Reactor intermittently or continuously moves.Biological reducing according to hardly degraded organic substance transforms situation, adjusts hydraulic load, COD load and hardly degraded organic substance load, hydraulic detention time.During the reactor whole service, temperature remains on 10-60 ℃, dissolved oxygen＜0.5mg/L, and water inlet pH value is 6-9.
Two, its step of bio-transformation of hardly degraded organic substance is as follows in membrane reactor co-immobilized amboceptor and the thalline acceleration water:
1, the selection of thalline
Select active sludge as seed sludge.
2, the selection of amboceptor
Water-insoluble amboceptor is anthraquinone, 1-nitroanthraquinone, 1-aminoanthraquinone, 1,8-dihydroxyanthraquinone, 1-chloroanthraquinone, 1,2-dihydroxyanthraquinone, 1,4-dihydroxyanthraquinone, 1,8-dihydroxyl-4,5-dinitroanthraquinone, 1,8-dichloroanthraquinone, 1-amino-2, one or more in the 4-dibromo-anthraquinone.
3, the bio-transformation of hardly degraded organic substance in membrane reactor co-immobilized amboceptor and thalline and the acceleration water thereof
Membrane reactor adopts integral type or separate film reactor, and the crown_interception by membrane module is fixed on water-insoluble amboceptor and mud in the reactor altogether.It is tubular fibre, tubular type or the dull and stereotyped microfiltration membrane of 0.1-0.4 μ m that membrane module adopts the aperture.
Seed sludge adds in the membrane reactor, and its concentration is 1-30g/L in reactor; Water-insoluble amboceptor adds in the mud, and its concentration is 1-30g/L in reactor.
Water inlet is formed: easily biodegradable organics, hardly degraded organic substance, (NH
4)
2SO
4, Na
2HPO
4, KH
2PO
4, micro-CaCl
2, MgSO
4, FeCl
3, COD:N:P=100:5:1.
During reactor start-up, move with intermittent mode earlier.When target hardly degraded organic substance clearance reaches 80% when above, reactor begins continuous operation.Remove and the aerogenesis situation according to hardly degraded organic substance, COD, little by little increase progressively COD load and hardly degraded organic substance load, shorten hydraulic detention time, with the startup of accelerating reactor.
In order to make mud further directly contact water-insoluble amboceptor, improve the biological reducing speed of amboceptor, also in order further to improve the mud flocculence, alleviate the film pollution simultaneously, when reactor start-up, can suitably add some flocculation agents, divalent-metal ion etc.
After reactor steady running, the target hardly degraded organic substance is transformed by the quick bio reduction.
During the reactor whole service, spoil disposal not, temperature remains on 10-60 ℃, dissolved oxygen＜0.5mg/L, water inlet pH value is 6-9.
Three, its step of bio-transformation of hardly degraded organic substance is as follows in granule sludge method co-immobilized amboceptor and the thalline acceleration water:
1, the selection of thalline
Select cotton-shaped active sludge as seed sludge.
2, the selection of amboceptor
Water-insoluble amboceptor is anthraquinone, 1-nitroanthraquinone, 1-aminoanthraquinone, 1,8-dihydroxyanthraquinone, 1-chloroanthraquinone, 1,2-dihydroxyanthraquinone, 1,4-dihydroxyanthraquinone, 1,8-dihydroxyl-4,5-dinitroanthraquinone, 1,8-dichloroanthraquinone, 1-amino-2, one or more in the 4-dibromo-anthraquinone.
3, the bio-transformation of hardly degraded organic substance in granule sludge method co-immobilized amboceptor and thalline and the acceleration water thereof
The reactor that adopts is for cultivating the bio-reactor of anaerobic grain sludge, as upflow anaerobic sludge blanket process (UASB), anaerobic expanded granular sludge bed (EGSB), inner circulation reactor (IC), upflow anaerobic sludge blanket process strainer (UBF) or anaerobic baffle reactor (ABR).
Seed sludge adds in the reactor, its concentration 5-80g/L in reactor; Water-insoluble amboceptor adds in the mud, concentration 1-80g/L in reactor.
Water inlet is formed: easily biodegradable organics, hardly degraded organic substance, (NH
4)
2SO
4, Na
2HPO
4, KH
2PO
4, micro-CaCl
2, MgSO
4, FeCl
3, COD:N:P=100:5:1.
During reactor start-up, at first intermittent water inflow reflux cycle operation.When the hardly degraded organic substance clearance reach more than 80%, when sludge settling property makes moderate progress, reactor begins continuous operation.Remove and the aerogenesis situation according to hardly degraded organic substance, COD, increase progressively hydraulic load, COD load and hardly degraded organic substance load in time, shorten hydraulic detention time, the formation that contains water-insoluble amboceptor anaerobic grain sludge with the startup and the promotion of accelerating reactor.
In addition, in order further to quicken anaerobic sludge granulating process, when reactor start-up, can suitably add some flocculation agents, divalent-metal ion etc.
After reactor steady running, the target hardly degraded organic substance is transformed by the quick bio reduction.
During the reactor whole service, temperature remains on 10-60 ℃, dissolved oxygen＜0.5mg/L, and water inlet pH value is 6-9.
Effect of the present invention and benefit are:
(1) preparation technology of amboceptor and thalline co-immobilization is simple, easy to operate.
(2) with thalline and water-insoluble amboceptor co-immobilization in a reactor, solved the technology bottle footpath that water soluble oxidized reduction amboceptor runs off and causes secondary pollution with water outlet in the water treatment system.
(3) accelerating effect of co-immobilized amboceptor and thalline has broad spectrum, can increase substantially the anaerobe conversion rate of hardly degraded organic substances such as azoic dyestuff in the water, nitro-aromatic or many chlorine organics, thereby promote the whole biological treatment efficient of organic wastewater with difficult degradation thereby.
Description of drawings
Fig. 1 is co-immobilized amboceptor provided by the invention and the biological decolouring figure of thalline to different azoic dyestuffs.Ordinate zou is represented percent of decolourization among the figure, and unit is %; X-coordinate is represented different azoic dyestuffs.1 represents Acid Red B; 2 represent acid fuchsin 6b; 3 represent acid bright red 3r; 4 represent the bamboo water pipe dish red; 5 represent reactive red X-3B; 6 represent reactive brilliant red k-2g; 7 represent reactive brilliant red KE-7B; 8 represent Reactive Brilliant Red K-2BP; 9 represent direct fast blue B2RL; 10 represent direct fast black GF.-■-represent co-immobilization bacterium ball;--represent the immobilized bacterium ball, it does not contain anthraquinone, and other are with co-immobilization bacterium ball.Fig. 1 shows that with respect to the immobilized bacterium ball, co-immobilization bacterium ball improves 2-5 doubly to the biological decolouring speed of 10 kinds of different structure azoic dyestuffs.
Fig. 2 is co-immobilized amboceptor provided by the invention and the thalline bio-transformation graphic representation to nitro-aromatic.Ordinate zou is represented nitro-aromatic concentration among the figure, and unit is mg/L; X-coordinate is represented the time, and unit is hour.-◇-represent immobilized bacterium ball+oil of mirbane;--immobilized bacterium ball+2, the 6-dinitrotoluene (DNT);-△-immobilized bacterium ball+2, the 4-dinitrotoluene (DNT);-◆-represent co-immobilization bacterium ball+oil of mirbane;-■-co-immobilization bacterium ball+2, the 6-dinitrotoluene (DNT);-▲-co-immobilization bacterium ball+2, the 4-dinitrotoluene (DNT).The immobilized bacterium ball is meant and does not contain anthraquinone that other are with co-immobilization bacterium ball.Fig. 2 shows, with respect to the immobilized bacterium ball, and co-immobilization bacterium ball p-nitrophenyl, 2,4-dinitrotoluene (DNT) and 2, the biological reducing of 6-dinitrotoluene (DNT) transforms all has obvious booster action.
Fig. 3 is co-immobilized amboceptor provided by the invention and the thalline bio-transformation figure to many chlorine organics.Ordinate zou is represented dechlorination rate among the figure, and unit is %; X-coordinate is represented many chlorine organics.The ratio calculation of chlorine element theory content obtains in the amount of chloride ions that dechlorination rate is measured by experiment and the many chlorine organics.1 represents trieline; 2 represent Pentachlorophenol.-■-represent co-immobilization bacterium ball;--represent the immobilized bacterium ball, it does not contain anthraquinone, and other are with co-immobilization bacterium ball.Fig. 3 shows that with respect to the immobilized bacterium ball, co-immobilization bacterium ball has improved 2.5-3 doubly to the anaerobism dechlorination rate of trieline and Pentachlorophenol.
Fig. 4 is the graphic representation that membrane reactor co-immobilized amboceptor provided by the invention and thalline quicken reactive brilliant red KE-7B biological decolouring.Ordinate zou is represented percent of decolourization among the figure, and unit is %; X-coordinate is represented the time, and unit is the sky.-■-represent to add anthraquinone in the mud;-▲-represents and do not add anthraquinone in the mud.Fig. 4 shows that the adding of anthraquinone has not only been shortened the start time of membrane reactor significantly, and has improved reactive brilliant red KE-7B biological decolouring speed.
Embodiment
The invention will be further described below in conjunction with technical scheme and accompanying drawing, but the wood invention is not limited to following embodiment.
Embodiment 1
Alginate calcium co-immobilized amboceptor and thalline promote the biological decolouring of azoic dyestuff
[1] enrichment and the cultivation of quinone reduction flora
Enrichment medium consists of (g.L
-1): NH
4Cl, 1.0; KH
2PO
4, 0.5; K
2HPO
4, 0.6; MgCl
26H
2O, 0.2; CaCl
22H
2O, 0.05; Na
2S9H
2O, 0.037; PH7.0; AQDS 0.15g.L
-1, glucose 0.5g.L
-1Minimal medium is not for containing the enrichment medium of glucose and AQDS.
In the 135mL serum bottle, pack into above-mentioned enrichment medium of 100mL and 10mL active sludge, enrichment medium fills up serum bottle, seals with silica gel plug, put 30 ℃ of incubators and leave standstill cultivation, 2～3d is an enrichment cycle, behind each end cycle, bacterium liquid is transferred in the fresh enrichment medium.8 all after date enrichments finish.This flora is forwarded to carries out enlarged culturing in the enrichment medium.Place 30 ℃ of anaerobism incubators to cultivate, when reaching logarithmic phase at 8000r.min
-1Following centrifugal 10min, abandoning supernatant, with the phosphate buffer soln washing of 0.1M pH7.0, recentrifuge, so repetitive scrubbing is three times, the thalline after centrifugal is mixed with phosphate buffer soln concentrates bacterium liquid at last.
[2] selection of amboceptor
Select anthraquinone as water-insoluble amboceptor.
[3] preparation of co-immobilization bacterium ball
1. the heating of 1.1g sodium alginate is dissolved in the 20mL deionized water, and is cooled to 30 ℃;
2. sodium alginate-the water mixture in inciting somebody to action 1. mixes with the bacteria suspension with volume, and adds the 1g anthraquinone, stirs;
3. with syringe 2. middle mixture is splashed into 5%CaCl
2In the solution, make bead, use normal saline flushing 2 times, crosslinked 4h in 4 ℃ of refrigerators, standby.
[4] co-immobilized amboceptor and thalline promote the azoic dyestuff biological decolouring
In the 135mL serum bottle, carry out.In the anaerobism incubator, listed azoic dyestuff in co-immobilization bacterium ball or immobilized bacterium ball, glucose, the table 2 is joined in the serum bottle, be full of with minimal medium.Final bacterium ball concentration is 120g.L
-1, glucose concn is 0.5g.L
-1, azoic dyestuff concentration is 180mg.L
-1Use the rubber stopper seal bottleneck, leave standstill in 30 ℃ of anaerobism incubators and cultivate 12h.
The used azoic dyestuff of table 2
Alginate calcium co-immobilized amboceptor and thalline promote the bio-transformation of nitro-aromatic
[1] presses embodiment 1 enrichment and cultivation quinone reduction flora
[2] select anthraquinone as water-insoluble amboceptor
[3] press embodiment 1 preparation co-immobilized amboceptor and thalline
[4] co-immobilized amboceptor and thalline quicken the bio-transformation of nitro-aromatic
In the 135mL serum bottle, carry out.In the anaerobism incubator, co-immobilization bacterium ball or immobilized bacterium ball, glucose, the nitro-aromatic that is dissolved in the acetone are joined in the serum bottle, be full of with minimal medium.Final bacterium ball concentration is 120g.L
-1, glucose concn is 0.5g.L
-1, nitro-aromatic concentration is 100mg.L
-1Use the rubber stopper seal bottleneck, leave standstill in 30 ℃ of anaerobism incubators and cultivated 3 days.
Embodiment 3
Alginate calcium co-immobilized amboceptor and thalline promote the biological dechlorination of many chlorine organics
[1] presses embodiment 1 enrichment and cultivation quinone reduction flora
[2] select anthraquinone as water-insoluble amboceptor
[3] press embodiment 1 preparation co-immobilized amboceptor and thalline
[4] co-immobilized amboceptor and thalline promote the biological dechlorination of many chlorine organics
In the 135mL serum bottle, carry out.In the anaerobism incubator, co-immobilization bacterium ball or immobilized bacterium ball, glucose, many chlorine organics are joined in the serum bottle, be full of with minimal medium.Final bacterium ball concentration is 120g.L
-1, glucose concn is 0.5g.L
-1, many chlorine organics concentration is 50mg.L
-1Use the rubber stopper seal bottleneck, leave standstill in 30 ℃ of anaerobism incubators and cultivated 4 days.
Embodiment 4
Membrane reactor co-immobilized amboceptor and thalline quicken the biological decolouring of azoic dyestuff reactive brilliant red KE-7B
[1] select active sludge as seed sludge
[2] select anthraquinone as water-insoluble amboceptor
[3] biological decolouring of membrane reactor co-immobilized amboceptor and thalline and acceleration reactive brilliant red KE-7B thereof
Adopt the integral type film reactor.Reactor material is a synthetic glass, is of a size of: 150mm * 250mm * 350mm, and useful volume is 10L; Used membrane module is the hollow fiber microfiltration membrane of polypropylene material, and the aperture is 0.2 μ m, and effective filtration area is 0.2m
2
Seed sludge adds in the membrane reactor, and concentration is 5g/L; Anthraquinone adds in the mud, and concentration is 2g/L.
Water inlet consists of (g.L
-1): NH4Cl, 1.0; KH
2PO
4, 0.5; K
2HPO
4, 0.6; MgCl
26H
2O, 0.2; CaCl
22H
2O, 0.05; Na
2S9H
2O, 0.037; Reactive brilliant red KE-7B, 0.2; Glucose, 0.5g.L
-1PH7.0.
The artificial distribution sends into bio-reactor by intake pump from the bottom; The film water outlet is discharged under the negative pressure-pumping effect of peristaltic pump, and each suction period is 10min, promptly aspirates 8min, stops 2min.During reactor start-up, move with intermittent mode earlier.When reactive brilliant red KE-7B percent of decolourization reached 80%, reactor began continuous operation.The reactor run duration is provided with magnetic agitation, not spoil disposal.Temperature controller maintains the temperature at 30 ± 1 ℃, dissolved oxygen＜0.5mg/L, and hydraulic detention time was 24h after startup was finished.With the membrane reactor that does not add anthraquinone is contrast.
Embodiment 5
Granule sludge method co-immobilized amboceptor and thalline quicken 2, the bio-transformation of 4-dinitrotoluene (DNT)
[1] select cotton-shaped active sludge as seed sludge
[2] select anthraquinone as water-insoluble amboceptor
[3] granule sludge method co-immobilized amboceptor and thalline and quicken 2, the bio-transformation of 4-dinitrotoluene (DNT)
Reactor adopts upflow anaerobic sludge blanket process (UASB).Reactor material is a synthetic glass, and internal diameter is 50mm; High 600mm, useful volume is 1L.
Seed sludge adds in the reactor, and concentration is 20TSSg/L; Anthraquinone adds in the mud, and concentration is 15g/L; The cationic polyacrylamide that adds 10mg/L simultaneously.
Water inlet consists of (g.L
-1): NH
4Cl, 1.0; KH
2PO
4, 0.5; K
2HPO
4, 0.6; MgCl
26H
2O, 0.2; CaCl
22H
2O, 0.1; Na
2S9H
2O, 0.037; 2,4-dinitrotoluene (DNT), 0.03-0.15; Glucose, 1.2g.L
-1PH7.0.
The artificial distribution sends into reactor by intake pump from the bottom, regulates upflow velocity by reflux pump.During reactor start-up, in the water inlet 2,4-dinitrotoluene (DNT) starting point concentration is 30mg/L, intermittent operation.When 2,4-dinitrotoluene (DNT) clearance reaches more than 80%, when sludge settling property makes moderate progress, and reactor begins continuous operation.According to 2,4-dinitrotoluene (DNT), COD are removed and the aerogenesis situation, shorten hydraulic detention time in time and increase progressively in the water 2, and 4-dinitrotoluene (DNT) concentration is until 150mg/L.Reactor run duration, temperature controller maintain the temperature at 30 ± 1 ℃, dissolved oxygen＜0.5mg/L, and upflow velocity 0.15-0.25m/h, hydraulic detention time was 36h after startup was finished.
Claims (3)
1. co-immobilized amboceptor and thalline promote the method for hardly degraded organic substance bio-transformation, may further comprise the steps:
(1) selection of thalline, (2) selection of amboceptor, (3) adopt entrapping method, membrane reactor method or granule sludge method with thalline and water-insoluble amboceptor co-immobilization in a bio-reactor, (4) biological reducing that is used for the water hardly degraded organic substance transforms, and it is characterized in that: the mass ratio of water-insoluble amboceptor and thalline is 0.1-10 in entrapping method co-immobilization bacterium ball or the bacterium piece; The mass ratio of water-insoluble amboceptor and inoculation of activated-sludge is 0.033-30 in the membrane reactor; Water-insoluble amboceptor is 0.013-16 with the mass ratio of the cotton-shaped active sludge of inoculation in the granule sludge method.
2. co-immobilized amboceptor according to claim 1 and thalline promote the method for hardly degraded organic substance bio-transformation, it is characterized in that: water-insoluble amboceptor is anthraquinone, 1-nitroanthraquinone, 1-aminoanthraquinone, 1,8-dihydroxyanthraquinone, 1-chloroanthraquinone, 1,2-dihydroxyanthraquinone, 1,4-dihydroxyanthraquinone, 1,8-dihydroxyl-4,5-dinitroanthraquinone, 1,8-dichloroanthraquinone, 1-amino-2, one or more in the 4-dibromo-anthraquinone.
3. co-immobilized amboceptor according to claim 1 and thalline promote the method for hardly degraded organic substance bio-transformation, it is characterized in that: thalline is quinone reduction flora, active sludge or the two combination that obtains by enrichment.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103952445A (en) * | 2014-04-14 | 2014-07-30 | 杭州电子科技大学 | Method for promoting production of fermentation acid from remaining sludge by utilizing redox mediator |
| CN104478084A (en) * | 2014-12-08 | 2015-04-01 | 天津城建大学 | Method for enhancing biological denitrification and denitrification of low-temperature sewage in winter |
| CN110054277A (en) * | 2018-12-07 | 2019-07-26 | 南京林业大学 | A method of waste water from dyestuff is handled using vanillic aldehyde selective paraffin oxidation product |
| CN111943351A (en) * | 2020-08-17 | 2020-11-17 | 河北科技大学 | Biological filler embedded with anthraquinone and thiobacillus denitrificans and sulfur autotrophic denitrification method |
-
2008
- 2008-09-30 CN CNA2008100135164A patent/CN101367580A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103952445A (en) * | 2014-04-14 | 2014-07-30 | 杭州电子科技大学 | Method for promoting production of fermentation acid from remaining sludge by utilizing redox mediator |
| CN104478084A (en) * | 2014-12-08 | 2015-04-01 | 天津城建大学 | Method for enhancing biological denitrification and denitrification of low-temperature sewage in winter |
| CN104478084B (en) * | 2014-12-08 | 2016-02-17 | 天津城建大学 | A kind of method improving winter low temperature saprobia denitrification denitrogenation |
| CN110054277A (en) * | 2018-12-07 | 2019-07-26 | 南京林业大学 | A method of waste water from dyestuff is handled using vanillic aldehyde selective paraffin oxidation product |
| CN110054277B (en) * | 2018-12-07 | 2021-09-14 | 南京林业大学 | Method for treating dye wastewater by utilizing vanillin directional oxidation product |
| CN111943351A (en) * | 2020-08-17 | 2020-11-17 | 河北科技大学 | Biological filler embedded with anthraquinone and thiobacillus denitrificans and sulfur autotrophic denitrification method |
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