CN1724413A - Process for degrading high chlorodioxin kinds pollutant by combined biological ecological system - Google Patents
Process for degrading high chlorodioxin kinds pollutant by combined biological ecological system Download PDFInfo
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- CN1724413A CN1724413A CN 200510035388 CN200510035388A CN1724413A CN 1724413 A CN1724413 A CN 1724413A CN 200510035388 CN200510035388 CN 200510035388 CN 200510035388 A CN200510035388 A CN 200510035388A CN 1724413 A CN1724413 A CN 1724413A
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- evil
- dechlorination
- coccus
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Abstract
A method for de-gradating the perchlordioxin pollutant in soil or sewage by use of microbial composition includes such steps as naturalizing the white rot and dis-chlorococcus able to de-gradate dioxin pollutants, choosing the perchloro-dioxin pollutant, adding the nutritive factors to make said white rot and dis-chlorococcus to generate de-gradate enzyme, inoculating white rot and dis-chlorococcus, reduction reaction for removing chlorine, and oxidizing degradation reaction.
Description
Technical field
The present invention relates to a kind of method with combination microbial ecological system's degraded agricultural soil and other media environment such as the high chlorine of trade effluent generation two Evil pollutants.
Background technology
Er Evil is the general name of two compounds, and a class is polychlorinated dibenzo-2 Er Evil (Polychlorinateddibenzo-p-dioxin is called for short PCDD), and another kind of is polychlorinated dibenzo (Polychlorinateddibenzofuran is called for short PCDF).Because to replace the quantity of chlorine atom different with the position, each have 75 and 135 isomer of the same clan among PCDD and the PCDF (PCDD/Fs), its chemical structure is similar.In addition, the analogue that also has 209 kinds of polychlorobiphenyl Wei Er Evil .
Er Evil is one of toxic compound of tool known to up to now, and its carcinogenic toxicity is higher 10 times than known flavacin, than 3, and the taller several times of 4-benzopyrene and polychlorobiphenyl.Position and quantity that the toxicity of Er Evil and chlorine atom replace are closely related, and the 17 Zhong Er Evil English toxicity that wherein have the chlorine atom to replace on 2-, 3-, 7-and the 8-position are the strongest, for example, 2,3,7,8-TCDD and 2,3,7,8-TCDF, but the toxicity of these compounds is also variant, as 2,3,7, malicious 1000 times of 8-TCDD than OCDD.
The chemical stability height of Er Evil class material, all inoperative with acid or alkali, be difficult for decomposing, nonflammable, be insoluble in water, enter in the organism and drained hardly, but directly accumulate in liver and the fat.Er Evil compounds is mainly by agricultural soil pollution fish, meat, egg and milk preparation.As the top of food chain in the earth ecology circle, the pollution condition of human Shou Er Evil class material is quite serious, and at present, some cities partly fatty tissue, blood and the breast milk of resident's human body detect Er Evil class material sometimes.
Studies show that Er Evil is mainly from the comings and goingses such as Human's production, main source has: (1). when being burned, chlorinated organics forms, as waste incineration, industrial combustion (smelting furnace), family's coal bavin burning and fuel for motor vehicles burning etc., especially incomplete combustion or under lower temperature burning more easily produce Er Evil , these two Evil are discharged in the atmosphere with the flue dust form, fall on the face of land particularly agricultural soil and other media environment such as trade effluent at last.(2). the organic chemistry production, the normal You Er of especially chloride phenolate drug production process Evil compounds generates as its byproduct, production process as wood preservative, weedicide, Pentachlorophenol agrochemical all can produce Er Evil class material, they usually are drained in the atmosphere with the form of sol particle, are deposited to then on the face of land particularly in the agricultural soil.(3). also can produce two Evil in the chlorine bleaching process of paper pulp, during chlorination in the paper pulp DD and DF (deriving from defoamer, log itself and lignin degradation product or other small molecules aromatics) can be transformed into PCDD and PCDF, and along with trade effluent is discharged into rivers and lakes and agricultural soil.
In the Zai Er Evil pollutant, it is stable especially to contain above high substitution value compound (the high chlorine Dai Er Evil ) character of 4 chlorine atoms.At present, still find to degrade the separately microorganism of high chlorine Dai Er Evil pollutant.Therefore, how eliminating high chlorine Dai Er Evil class material pollution effectively is society and the urgent requirement of the public.
Summary of the invention
The object of the present invention is to provide a kind of method with the high chlorine Dai Er Evil pollutant of combination microbial ecological system's degraded.The combination microbial ecological system that the present invention proposes promptly is at specific agricultural soil and other media environment such as trade effluent, is made of the ecosystem of degraded whiterot fungi and reduction dechlorination bacterium.In this ecosystem, the dechlorination coccus is transformed into low chlorine Dai Er Evil class material with high chlorine Dai Er Evil class material reduction dechlorination, by the metabolism of whiterot fungi oxidative degradation, is transformed into CO immediately
2And water.Thereby realize effective removal to high chlorine Dai Er Evil class material.
For achieving the above object, the present invention has taked following technical scheme:
The method of the high chlorine Dai Er Evil pollutant of combination microbial ecological system's degraded, form by following steps:
(1) has the whiterot fungi bacterial strain of degraded Er Evil pollutant ability and the adaptability domestication of dechlorination coccus; Whiterot fungi is for penetrating arteries and veins side bacterium Phlebia radiate; The dechlorination coccus is Dehalococcoides sp, and both all are microorganisms of public use.
The whiterot fungi bacterial strain is that dote from forest is through isolation and selection substratum (Han Er Evil pollutant) screening obtains, and further pass through ultraviolet radiation mutagenesis, by the hereditary and selection in 3～10 generations, the bacterial strain that filters out carries out the adaptability domestication before the use.
The coccus screening of dechlorination coccus from physical environments such as rice field, wheatland, forest land, orcharding, vegetable plot, and use Co
60The width of cloth is according to 1～30min or 40Wt uviolizing 1～5min; Bacterial strain through obtaining behind succeeding transfer culture based selective cultivation 10～18 generation hereditary and selection that contains two Evil pollutants uses the domestication of previous crops adaptability.
(2) whiterot fungi produce degrading enzyme nutritional factor (add-on: 1: 1000,000～10,000,000, nutritive salt/soil, w/w): Li Lu alcohol: 0.0001～0.1mol/L; Xitix: 0.01～0.1mol/L; Nutritional factor: 0.1～10g/L K
2HPO
4, 0.1～10g/L KH
2PO
4, 0.1～10g/L MgSO
4, 0.1～10g/LCaCl
2, 0.01～0.1g/L NaCl, 0.1～10g/L FeSO
47H
2O
2, 0.01～1g/L ZnSO
47H
2O
2, 0.01～1g/L CuSO
45H
2O
2, 0.01～1g/L MnSO
4H
2O
2, 0.01～1g/L CoCl
2, 0.01～1g/L pyridoxine hydrochloride and 1～10g/L ammonium tartrate; PH2～6, temperature are 18～39 ℃;
(3) nutritional factor of the generation degrading enzyme of dechlorination coccus (add-on: 1: 1000,000～10,000,000, nutritive salt/soil, w/w): 0.01～1gMgSO
4, 0.1～1g K
2HPO
4, 0.2～2g (NH4)
2SO
4, pH nature; Temperature is 12～30 ℃;
(4) can be to the agricultural soil or the inoculation of universal industrial waste water reactor of similar half anaerobic reaction system to dechlorination coccus (anaerobic bacterium) bacterial strain of high chlorine Dai Er Evil pollutant generation reduction dechlorination reaction with to hanging down whiterot fungi (aerobic fungi) bacterial strain of chlorine Dai Er Evil pollutant generation oxidative degradation, inoculum size is 1: 1000,000～1000,000,000 (weight ratio, w/w);
(5), dechlorination coccus etc. (4 the above) Er of chlorine atom Evil carry out the reduction dechlorination reaction to high chloro;
(6), (4 the following) Er of chlorine atom Evil carry out oxidative degradation to the low chloro of whiterot fungi after to reduction dechlorination.
Total dechlorination rate is that the following low chlorine Dai Er Evil pollutant production rate of 15～95%, 4 chlorine atoms is 40～95% to the dechlorination coccus in 3～12 days in order to cultivate to high chlorine Dai Er Evil pollutant generation reduction dechlorination reaction; Whiterot fungi is that degradation rate is 35～95% in 3～12 days to low chlorine Dai Er Evil pollutant generation oxidative degradation reaction, CO
2Transformation efficiency is 10～65%.
Compared with the prior art, the present invention has following beneficial effect:
Be combined to form microecosystem by whiterot fungi and dechlorination coccus, the use of uniting by whiterot fungi and dechlorination coccus, the high chlorine generation two Evil pollutant generation reduction dechlorinations reaction of ortho states is gone back in realization to height, be transformed into low chlorine Dai Er Evil pollutant, and can realize degraded to highly toxic low chlorine generation two Evil pollutants, thereby new technology and novel method are provided for the two Evil pollutants of thoroughly eliminating the big earth of agricultural and other media environment such as trade effluent thereupon.
Embodiment
The present invention is further illustrated below in conjunction with specific embodiment:
Embodiment 1
Whiterot fungi is for penetrating arteries and veins side bacterium Phlebia radiate; The dechlorination coccus is Dehalococcoides sp.Inoculation soil: rice field; Eight Lv Er Evil pollutant content: 1: 10,000,000 (w/w); Add nutritional factor (by per 10 tons of soil): 0.1g K
2HPO
4, 1g KH
2PO
4, 0.24g MgSO
4, 0.1g CaCl
2, 0.01g NaCl, 0.1gFeSO
47H
2O
2, 0.01g ZnSO
47H
2O
2, 0.02g CuSO
45H
2O
2, 0.08g MnSO
4H
2O
2, 0.01gCoCl
2, 0.01g pyridoxine hydrochloride, pH6.2, temperature be the soil natural temperature; Inoculum size 1: 2000,000 (the heavy or bacterial biomass weight/soil of whiterot fungi mycelia, w/w).Degradation effect to eight Lv Er Evil under the above-mentioned condition sees Table 1:
Table 1.
| Days post inoculation (d) | Total dechlorination rate (%) | 4 low chlorine Dai Er Evil production rates (%) that the chlorine atom is following | 4 low chlorine Dai Er Evil degradation rates (%) that the chlorine atom is following | Total CO 2Transformation efficiency (%) |
| 3 5 7 9 12 | 23.9 33.8 52.4 82.6 93.1 | 44.6 75.8 78.9 91.4 97.8 | 18.0 35.2 64.2 84.4 93.1 | 3.5 13.4 23.6 35.7 37.2 |
Embodiment 1
Whiterot fungi is for penetrating arteries and veins side bacterium Phlebia radiate; The dechlorination coccus is Dehalococcoides sp.Inoculation soil: lichee orchard; Liu Lv Er Evil content: 1: 20,000,000 (w/w); Add nutritional factor (by per 10 tons of soil): 0.2g K
2HPO
4, 2g KH
2PO
4, 0.48g MgSO
4, 0.2g CaCl
2, 0.02g NaCl, 0.2gFeSO
47H
2O
2, 0.02g ZnSO
47H
2O
2, 0.04g CuSO
45H
2O
20,0.16g MnSO
4H
2O
2, 0.04gCoCl
2, 0.04g pyridoxine hydrochloride, pH6.5, temperature be the soil natural temperature; Inoculum size 1: 4000,000 (the heavy or bacterial biomass weight/soil of whiterot fungi mycelia, w/w).Degradation effect to Liu Lv Er Evil under the above-mentioned condition sees Table 2:
Table 2.
| Days post inoculation (d) | Total dechlorination rate (%) | 4 high chlorine Dai Er Evil production rates (%) that the chlorine atom is following | 4 low chlorine Dai Er Evil degradation rates (%) that the chlorine atom is following | Total CO 2Transformation efficiency (%) |
| 3 5 7 9 12 | 24.3 38.8 62.7 73.5 81.7 | 35.7 56.9 67.4 82.3 86.5 | 23.7 49.2 78.2 87.9 96.8 | 12.1 32.6 43.7 48.2 58.5 |
Embodiment 3
Whiterot fungi is for penetrating arteries and veins side bacterium Phlebia radiate; The dechlorination coccus is Dehalococcoides sp.Inoculated medium environment: Eucalyptus sulfate pulp CEH bleaching effluent biochemical reactor; Liu Lv Er Evil content: 1/40,000,000 (w/w) in the bleaching effluent; Add nutritional factor (by per 10 tons of soil): 0.5g/L K
2HPO
4, 0.3g/LKH
2PO
4, 0.4g/L MgSO
4, 0.6g/L CaCl
2, 0.05g/L NaCl, 0.3g/L FeSO
47H
2O
2, 0.02g/L ZnSO
47H
2O
2, 0.03g/LCuSO
45H
2O
2, 0.01g/L MnSO
4H
2O
2, 0.04g/L CoCl
2, 0.03g/L pyridoxine hydrochloride and 2g/L ammonium tartrate; PH6.6, temperature are natural room temperature; Inoculum size 1: 2500,000 (the heavy or bacterial biomass weight/soil of whiterot fungi mycelia, w/w).Degradation effect to Liu Lv Er Evil under the above-mentioned condition sees Table 2:
Table 2.
| Days post inoculation (d) | Total dechlorination rate (%) | 4 high chlorine Dai Er Evil production rates (%) that the chlorine atom is following | 4 low chlorine Dai Er Evil degradation rates (%) that the chlorine atom is following | Total CO 2Transformation efficiency (%) |
| 3 5 7 9 12 | 32.2 35.7 58.9 69.8 79.3 | 32.4 52.7 63.5 78.5 85.7 | 22.1 51.1 65.3 79.5 91.2 | 15.2 27.5 38.6 45.2 53.7 |
Claims (5)
1, with the method for the high chlorine Dai Er Evil pollutant of combination microbial ecological system's degraded, it is characterized in that comprising the steps:
(1) has the whiterot fungi bacterial strain of degraded Er Evil pollutant ability and the adaptability domestication of dechlorination coccus;
(2) selection of high chlorine Dai Er Evil pollutant: high chlorine Dai Er Evil pollutant is that the content that is present in agricultural soil or trade effluent is 1: 1, four the above De Er of chlorine atom substitution value Evil pollutants of 000,000～100,000,000 (w/w);
(3) by nutritive salt: soil or trade effluent reactor are 1: 1000, and 000～10,000,000 weight ratio adds the nutritional factor that makes whiterot fungi generation degrading enzyme to scholar's earth or trade effluent reactor; The adding condition is that pH2～6, temperature are 18～39 ℃;
(4) by nutritive salt: soil or trade effluent reactor are 1: 1000, and 000～10,000,000 weight ratio adds the nutritional factor that makes dechlorination coccus generation degrading enzyme to soil or trade effluent reactor; The adding condition is the pH nature; Temperature is 12～30 ℃;
(5) to agricultural soil or universal industrial waste water reactor inoculation dechlorination coccus bacterial strain and whiterot fungi bacterial strain, form combination microbial ecological system, by weight, inoculum size was respectively 1: 1000, and 000～1000,000,000;
(6) the dechlorination coccus carries out the reduction dechlorination reaction to high chlorine Dai Er Evil pollutant; The dechlorination coccus occurs in inoculation back 3～12 days to high chlorine Dai Er Evil pollutant generation reduction dechlorination reaction;
(7) whiterot fungi carries out oxidative degradation to the low chlorine Dai Er Evil pollutant behind reduction dechlorination, and whiterot fungi occurs in inoculation back 3～12 days to low chlorine Dai Er Evil pollutant generation oxidative degradation reaction.
2, the method with the high chlorine Dai Er Evil pollutant of combination microbial ecological system degraded according to claim 1 is characterized in that the described whiterot fungi bacterial strain of step (1) is that screening obtains through the isolation and selection substratum penetrates arteries and veins side bacterium for dote from forest; Further pass through adaptability mutagenesis, by the hereditary and selection in 3～10 generations, the new bacterial strain that filters out.
3, the method with the high chlorine Dai Er Evil pollutant of combination microbial ecological system's degraded according to claim 1, the screening that it is characterized in that the described dechlorination coccus of step (1) is the screening of the coccus from rice field, wheatland, forest land, orcharding or vegetable plot physical environment, and uses Co
60The width of cloth is according to 1～30min or 40Wt uviolizing 1～5min; Through the dechlorination coccus that obtains behind succeeding transfer culture based selective cultivation 10～18 generation hereditary and selection that contains two Evil pollutants be.
4, the method with the high chlorine of combination microbial ecological system degraded generation two Evil pollutants according to claim 1 is characterized in that the described nutritional factor that makes whiterot fungi produce degrading enzyme of step (3) is: Li Lu alcohol: 0.0001～0.1mol/L; Xitix: 0.01～0.1mol/L; Nutritional factor: 0.1～10g/L K
2HPO
4, 0.1～10g/L KH
2PO
4, 0.1～10g/L MgSO
4, 0.1～10g/LCaCl
2, 0.01～0.1g/LNaCl, 0.1～10g/LFeSO
47H
2O
2, 0.01～1g/LZnSO
47H
2O
2, 0.01～1g/LCuSO
45H
2O
2, 0.01～1g/LMnSO
4H2O
2, 0.01～1g/L CoCl
2, 0.01～1g/L pyridoxine hydrochloride and 1～10g/L ammonium tartrate.
5, the method with the high chlorine Dai Er Evil pollutant of combination microbial ecological system's degraded according to claim 1 is characterized in that the described nutritional factor of the generation degrading enzyme of dechlorination coccus that makes of step (3) is: 0.01～1g MgSO
4, 0.1～1g K
2HPO
4, 0.2～2g (NH
4)
2SO
4
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