CN1699220A - Method and apparatus for immobilizing cells to treat wastewater - Google Patents
Method and apparatus for immobilizing cells to treat wastewater Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 29
- 230000003100 immobilizing effect Effects 0.000 title abstract description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 241000233866 Fungi Species 0.000 claims abstract description 13
- 241000894006 Bacteria Species 0.000 claims abstract description 10
- 230000015556 catabolic process Effects 0.000 claims abstract description 9
- 238000006731 degradation reaction Methods 0.000 claims abstract description 9
- 102000004190 Enzymes Human genes 0.000 claims abstract description 8
- 108090000790 Enzymes Proteins 0.000 claims abstract description 8
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 4
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- 239000002699 waste material Substances 0.000 claims description 18
- 241000222355 Trametes versicolor Species 0.000 claims description 9
- 230000001580 bacterial effect Effects 0.000 claims description 9
- 241001138370 Pleurotus pulmonarius Species 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 241000222393 Phanerochaete chrysosporium Species 0.000 claims description 4
- 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 claims description 3
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- 229920001661 Chitosan Polymers 0.000 claims description 2
- 241000187654 Nocardia Species 0.000 claims description 2
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- 241000589516 Pseudomonas Species 0.000 claims 1
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- 239000003795 chemical substances by application Substances 0.000 abstract 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
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- 238000004519 manufacturing process Methods 0.000 description 7
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- 238000007796 conventional method Methods 0.000 description 6
- 229960000355 copper sulfate Drugs 0.000 description 6
- 229910000365 copper sulfate Inorganic materials 0.000 description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
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- 239000011347 resin Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000012138 yeast extract Substances 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- 241000228257 Aspergillus sp. Species 0.000 description 1
- 241001480537 Fomitopsis Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000007836 KH2PO4 Substances 0.000 description 1
- 241000108664 Nitrobacteria Species 0.000 description 1
- 241000605121 Nitrosomonas europaea Species 0.000 description 1
- 241000143395 Nitrosomonas sp. Species 0.000 description 1
- 241000222397 Phlebia radiata Species 0.000 description 1
- 241000589540 Pseudomonas fluorescens Species 0.000 description 1
- 241000589774 Pseudomonas sp. Species 0.000 description 1
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- 238000003723 Smelting Methods 0.000 description 1
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- 241001557886 Trichoderma sp. Species 0.000 description 1
- 241000223261 Trichoderma viride Species 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
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- 238000010170 biological method Methods 0.000 description 1
- 230000036983 biotransformation Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229940041514 candida albicans extract Drugs 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
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- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
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- 235000013373 food additive Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
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- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 235000013575 mashed potatoes Nutrition 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
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Abstract
The invention discloses a method and apparatus for immobilizing cells to treat wastewater wherein abandoned mycelium is used as a carrying agent for co-immobilization of white-rot fungi and bacteria, the enzyme system in the bacterium group is employed for coupled catalytic degradation of heterocyclic compounds and phenol in the waste water at the presence of oxygen supply. The device includes a reactor with moving sieving board and an oxygen supplying device.
Description
Technical Field
The invention belongs to the field of wastewater treatment, and relates to a method for treating wastewater containing high-concentration phenol and an organic solvent by using immobilized cells, and a device used by the method.
Background
At present, the waste water discharged in the production of phenol-containing resin and plasticizer has complex components, high COD and phenol contents and high organic solvent content. The waste water organisms cannot (easily) survive in the waste water organisms, so that most of the waste water organisms are extracted by using an organic solvent, the content of phenol is lower than 200mg/L, and the phenol is treated by using a biological method, but the phenol recovered by the extraction method has many impurities, cannot be directly recycled, has high operation cost, and causes the problem of secondary pollution to the waste water. The phenol-containing waste water is treated by using the immobilized large edible fungus mycelium, but the content of phenol in the treated waste water is only less than 600mg/L, and when the content of phenol in the waste water is higher than 600mg/L, the phenol removing effect is poor, and the continuous use time is not provided. In summary, various microorganisms have been used to treat wastewater in a synergistic manner, but the selection of microbial flora is a problem, and the technology of immobilized cells is also suitable for various bacterial strains, so that the wastewater is difficult to treat.
Disclosure of Invention
The invention aims to provide a method for treating wastewater containing high-concentration phenol and organic solvent by using immobilized cells, which has the advantages of low cost, good effect and no secondary pollution.
It is a further object of the present invention to provide an apparatus for use in the above method.
The technical scheme of the invention is designed according to the following principle:
the wastewater containing the heterocyclic ring and the phenolic compound passes through the immobilized cell layer and is aerated with compressed air, and the following biological reactions occur:
heterocyclic compound and phenol
If the landfill leachate passes through immobilized cells, in addition to the above reaction, an ammonium salt oxidation reaction may also occur:
the reaction needs oxygen, so compressed air needs to be introduced (the air cost is low), and 70-100m of oxygen needs to be supplied for treating each ton of wastewater3Air.
The aim of the invention is achieved by the following measures:
a process for treating waste water features that the waste mycelium is used as carrier, white-rot fungus and bacteria are co-immobilized, and the enzyme system of bacterial colony is used to couple and catalytically degrade heterocyclic compound and phenol in waste water under the condition of supplying oxygen.
The method, wherein the waste mycelium is waste Rhizopus (Rhizopus sp.), Aspergillus (Aspergillus sp.) or Trichoderma (Trichoderma sp.).
The method, wherein the immobilized white rot fungi is one or more of Phanerochaete chrysosporium (Phanerochaete chrysosporium), Coriolus versicolor (Polyporus versicolor), Trametes versicolor (Trametes versicolor), Phlebia radiata, Pleurotus pulmonarius (Pleurotus pulmonarius), and Fomitopsis cinnabarinus (Pyrnoporus cingularis).
The method described, wherein the bacteria to be immobilizedare Pseudomonas sp, Nocardia sp or Nitrosomonas sp.
The method, wherein the coating immobilization reagent for immobilizing the cells is polyvinyl alcohol, sodium alginate or chitosan.
The method is characterized in that the temperature of catalytic degradation is 15-35 ℃, and the action time is 20-26 hours.
The method comprises introducing oxygen-containing gas (air or pure oxygen), wherein the amount of air introduced is 70-100m3air/T waste water, the amount of pure oxygen introduced is 21% of the air amount.
The apparatus for treating waste water is composed of reactor with movable sieve plate and oxygen supplying unit.
The device is characterized in that the reactor is provided with a bracket for adjusting the movable sieve plate; the co-immobilized bacteria and white rot fungi with waste hypha as carriers are placed on a movable sieve plate in the reactor.
The apparatus according to (1), wherein the reactor is a column reactor.
The device, wherein the oxygen supply device is an air compression device or an oxygen bottle.
The invention has the beneficial effects that:
1. the invention utilizes the waste natural products, low-cost immobilized cells, treats plasticizer and phenol-containing resin production wastewater with complex components, and comprehensively removes COD, phenol and organic solvent, so that the wastewater which is difficult to treat is purified to achieve the quality allowed by environmental water.
The invention continuously tests 50 tons of phenol-containing wastewater (COD5000mg/L, phenol 700mg/L) by the methodAnd after 15 days, the volatile phenol in the effluent is less than 0.5mg/L, and the COD is less than 480 mg/L. 30 tons of landfill leachate, COD 6500mg/L and NH are treated3460mg/L, continuously running the experiment for 12 days, leading the COD of the effluent to be less than 400mg/L and leading the NH to be3Less than 60 mg/L. The dephenolizing efficiency of the invention exceeds 90 percent, when the COD of the inlet water is less than or equal to 5000mg/L, the phenol is less than or equal to 700mg/L, the removal rate of the COD and the phenol reaches 99 percent, and the outlet water can reach the following indexes: COD is less than 500mg/L, and phenol is less than 0.5 mg/L.
The available degradation of a microorganism is limited. Some of them are absorbed and utilized as raw materials required for cell growth, and some of them are degraded by enzyme-biocatalyst catalyzed reaction secreted by the aged microorganisms. These enzymes are not always expressed dominantly and require substrate induction, thus presenting acclimatization problems. When it is desired to degrade a compound with a microorganism which may have a certain degrading enzyme, it is common to first culture the microorganism in such a way that the content of the compound in the culture medium is gradually increased for one generation, the tolerance of the microorganism to the compound is gradually increased, and the amount of the enzyme which is expressed dominantly and secretly degrades the compound is increased, which is called acclimatization. This is useful in industry. For example, copper sulfate is a commonly used bactericide, and generally, the content of 5mg/L in water has obvious bactericidal effect, but the content of copper sulfate in a culture solution is gradually increased by one generation in the culture process of thiobacillus ferrogenes, and the thiobacillus ferrogenes can tolerate the copper sulfate of up to 60mg/L to normally grow. In the metallurgical industry, copper sulfide in sulfide ore is directly corroded and converted into copper sulfate by the copper sulfate, then a coppersulfate solution is extracted and directly electrolyzed to obtain a high-purity copper plate, and the process of ore dressing and smelting high energy consumption is omitted, so that the technology for directly producing electrolytic copper by using the low-cost bacteria metallurgy is a technology for directly producing the electrolytic copper. The ability of the white rot fungi for degrading the plasticizer wastewater is poor, and the ability of degrading the plasticizer wastewater is greatly increased after half a month of domestication by increasing the content of the plasticizer wastewater in the culture solution.
The components of the landfill leachate are different from those of plasticizer wastewater, the landfill leachate also contains high heavy metal ions, and the landfill leachate is domesticated by adopting a method of increasing the content of the landfill leachate in a culture solution by generations, so that the tolerance and the degradation capability of the landfill leachate are gradually improved. The invention can effectively treat the garbage percolate by utilizing the immobilized and domesticated white rot fungi and nitrobacteria, and the removal rate of COD and ammonia nitrogen of the effluent is as high as 90 percent.
2. The invention has the advantages of low investment, small occupied area, low operating cost, reliable operation and no secondary pollution.
3. The device provided by the invention has the advantages of simple structure, good effect and low cost.
4. The multi-strain combination and the waste hypha as the carrier have the advantages that: the chemical wastewater has complex components, the types of enzymes which can be secreted and leaked by one microorganism are limited, only a few substrates can be degraded and utilized, and the multiple strains are combined to coordinate metabolism and complement defects, so that certain mixed chemical wastewater can be effectively degraded. The combination of fungi and bacteria is adjusted in a proper proportion according to the components of the wastewater, and the fungi are more and less. The degradation of the phenol-containing wastewater is a biological oxidation process, except the special enzyme action secreted by thalli, waste hypha is used as a carrier to immobilize cells, and the hypha balls are of a grid structure, so that the contact area of oxygen is greatly increased, and the oxidation reaction rate is effectively improved. The waste hyphae are low in cost, degradable natural substances, and can not increase secondary pollution to the environment, so that the waste is treated by waste.
Drawings
FIG. 1 is a system diagram of a wastewater treatment plant according to the present invention.
Wherein 1 is a waste water storage tank, 2 is an air compressor, 3 is a pump, 4 is air bubbles, 5 is immobilized cells, 6 is a tower reactor, 7 is an overflow pipe, and 8 is an effluent storage tank.
Detailed Description
The invention is further illustrated by the following examples.
General description: the waste mycelium refers to mycelium which is inactivated after the mould obtained by fermentation culture is used for producing medical intermediates by biotransformation and is ready to be discarded. Other moulds for bioconversion production of food additives or pharmaceuticals may be used with mycelium that has been inactivated and is ready for disposal.
Example 1
The method of increasing the content of plasticizer production wastewater in a culture solution is adopted for domestication, so that the tolerance and the degradation capability of white rot fungus coriolus versicolor (Polyporus versicolor NG04010) are gradually improved. Culturing white rot fungus Coriolus versicolor NG04010 for 7 days to collect mycelium, wherein the culture method is conventional method, and the culture medium is potato mash mixed with wheat bran.
Culturing Pseudomonas fluorescens ATCC11172 for 3 days, centrifuging, collecting bacterial sludge, culturing by conventional method, and culturing in culture medium (malic acid 10 g/L), (NH)4)2SO42g/L and yeast extract 1 g/L.
Mixing the collected mycelia and the bacterial mud according to the ratio of 5: 1 to obtain a mixture, mixing the mixture with about 50 times (weight ratio to the mixture) of waste Rhizopus stolonifer (Rhizomus stolonifer ATCC14037) mycelia, fully mixing, adding 10% polyvinyl alcohol (PVA) solution with the same weight as the mycelia, stirring uniformly, dripping into a saturated boric acid solution to solidify the gel balls to obtain solidified beads containing the mixed mycelia, and packing the beads into a column to obtain the immobilized cells.
As shown in figure 1, plasticizer production wastewater (COD5000mg/L, phenol 700mg/L) is continuously and slowly injected into the bottom of a tower reactor 6 from a wastewater storage tank 1 by a chemical pump 3, and simultaneously compressed air is blown into the tower from the bottom of the tower by an air compressor 2, wherein the compressed air is 70m3air/T waste water, the retention time of the waste water in the tower is 25h, the waste water reacts with the immobilized cells 5 placed on the movable sieve plate, and the reaction temperature isThe bubbles 4 can provide oxygen required by the reaction at 25 ℃, the wastewater after the reaction flows out from an overflow pipe 7 at the top of a tower reactor 6 and enters the next-stage tower reactor for the same reaction, and finally the treated water enters an effluent storage tank for storage, wherein the effluent phenol is less than 0.5mg/L and the COD is less than 500 mg/L.
Example 2
The method of increasing the content of the landfill leachate in the culture solution is adopted for acclimatization, and the tolerance and the degradation capability of the white-rot fungus phoenix mushroom (Pleurotus pulmonarius NG 0412) are gradually improved. Culturing domesticated white rot fungus Pleurotus pulmonarius NG 0412 for 7 days to collect mycelium, and culturing with conventional method in culture medium of mashed potato mixed with testa Tritici.
Culturing nitrosobacteria (Nitrosomonas europaea IFO14298) for 7 days, centrifuging, collecting bacterial mud, and culturing by conventional method in culture medium containing NaCl0.3g and MgSO 0 in water per liter4·7H2O 0.14g,FeSO4·7H2O 0.03g,(NH4)2SO40.6g,KH2PO42g。
Mixing the collected mycelia and bacterial mud at a ratio of 3: 1 to obtain a mixture, mixing the mixture with about 50-100 times (by weight) of waste Trichoderma viride AS 3.1044 mycelia, adding sodium alginate solution with the same weight AS the mycelia, stirring, and dripping into saturated CaCl2The gel beads were solidified in the solution to obtain solidified small beads containing mixed mycelia, and the small beads were packed into a column.
As shown in figure 1, landfill leachate (COD 6500mg/L, NH) is pumped by a chemical pump 33460mg/L) is continuously and slowly injected into the bottom of the tower reactor 6 from the waste water storage tank 1, and simultaneously compressed air is blown into the tower from the bottom of the tower through an air compressor 2, wherein the compressed air has the compression capacity of 100m3air/T waste water, the retention time of the waste water in the tower is 20h, the waste water is reacted through the immobilized cells 5, the reaction temperature is 35 ℃, the bubbles 4 can provide oxygen required by the reaction, the reacted waste water flows out from an overflow pipe 7 at the top of the tower reactor 6 and enters the next-stage tower reactor for the same reactionThe reaction of the sample, the water after final treatment enters an effluent storage tank for storage, the COD of the effluent is less than 400mg/L, and NH is added3<60mg/L。
Example 3
The method of increasing the content of the phenolic resin production wastewater in the culture solution by generations is adopted for domestication, and the tolerance and the degradation capability of the white-rot fungus Phanerochaete Chrysosporium ME-446 are gradually improved. Culturing white rot fungi (PChrysosporium ME-446) for 7 days by conventional method in the presence of testa Tritici mixed with potato mash as culture medium.
Culturing Rhodococcus erythropolis (Rhodococcus erythropolis NG0402) for 3 days, centrifuging, and collecting bacterial sludge by conventional method with culture medium of glucose 20 g.L-120 g.L. protein-1Yeast extract 10 g.L-1,K2HPO42g·L-1,MgSO4·7H2O 0.5g·L-1,pH7.0-7.2。
Mixing the collected mycelia and the bacterial sludge according to a ratio of 7: 1 to obtain a mixture, stirring the mixture into waste Aspergillus ochraceus (Aspergillus ochraceus NG0401) mycelia which is 50-100 times (by weight) of the mixture, fully mixing, adding 10% PVA solution which is equal to the mycelia in weight, uniformly stirring, dripping into a saturated boric acid solution to solidify thegel balls to obtain solidified small beads containing the mixed mycelia, and filling the small beads into a column to prepare the immobilized cells.
As shown in figure 1, phenolic resin production wastewater (COD5000mg/L, phenol 780mg/L) is continuously and slowly injected into the bottom of a tower reactor 6 from a wastewater storage tank 1 by a peristaltic pump 3, and simultaneously compressed air is blown into the tower from the bottom of the tower by an air compressor 2, wherein the compressed air is 70m3air/T waste water, the retention time of the waste water in the tower is 25h, the waste water is reacted through the immobilized cells 5, the reaction temperature is 35 ℃, the bubbles 4 can provide oxygen required by the reaction, the reacted waste water flows out from an overflow pipe 7 at the top of the tower reactor 6 and enters the next-stage tower reactor for the same reaction, finally, the treated water enters an effluent storage tank for storage, the effluent phenol is less than 0.5mg/L, and the COD is 480 mg/L.
Claims (12)
1. A process for treating waste water features that the waste mycelium is used as carrier to co-immobilize white-rot fungus and bacteria, and the enzyme system of bacterial colony is used to couple and catalytically degrade heterocyclic compound and phenol in waste water under the condition of supplying oxygen.
2. The method according to claim 1, wherein the waste mycelia are waste mycelia of rhizopus, aspergillus or trichoderma.
3. The method of claim 1, wherein the immobilized white rot fungi is one or more of Phanerochaete chrysosporium, Coriolus versicolor, trametes versicolor, Phlebia, Pleurotus pulmonarius, and Fomitopsis pinicola.
4. The method according to claim 1, wherein the immobilized bacteria is Pseudomonas, Nocardia or Nitrosclerobacteria.
5. The method of claim 1, wherein the encapsulating agent used to immobilize the cells is polyvinyl alcohol, sodium alginate or chitosan.
6. The method according to claim 1, characterized in that the temperature of the catalytic degradation is 15-35 ℃ and the duration of action is 20-26 hours.
7. The method of claim 1, wherein the oxygen supply means comprises supplying an oxygen-containing gas, the oxygen-containing gas being air or pure oxygen, wherein the amount of air supplied is 70 to 100m3air/T waste water, the amount of pure oxygen introduced is 21% of the air amount.
8. An apparatus for treating wastewater according to the method of claim 1, wherein the apparatus comprises a reactor having a movable sieve plate and an oxygen supply apparatus.
9. An apparatus according to claim 8, characterized in that the reactor is provided with a holder for adjusting the movable screen.
10. The apparatus as claimed in claim 8, wherein the co-immobilized bacteria and white rot fungi, which are waste hyphae, are placed on the movable sieve plate in the reactor.
11. An apparatus according to claim 8, 9 or 10, characterized in that the reactor is a column reactor.
12. The apparatus of claim 8, wherein the oxygen supply device is an air compression device or an oxygen cylinder.
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CNB2005100401417A CN100384761C (en) | 2005-05-23 | 2005-05-23 | Method and apparatus for immobilizing cells to treat wastewater |
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