CN102659220B - Method for removing ferric phosphate film and ferrous phosphate passivating film from filler surface layer in iron-carbon microelectrolysis reactor - Google Patents
Method for removing ferric phosphate film and ferrous phosphate passivating film from filler surface layer in iron-carbon microelectrolysis reactor Download PDFInfo
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- 239000000945 filler Substances 0.000 title claims abstract description 74
- 229940116007 ferrous phosphate Drugs 0.000 title claims abstract description 52
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 52
- 229910000155 iron(II) phosphate Inorganic materials 0.000 title claims abstract description 52
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 29
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 title abstract description 15
- 239000005955 Ferric phosphate Substances 0.000 title abstract 3
- 229940032958 ferric phosphate Drugs 0.000 title abstract 3
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title abstract 3
- 239000002344 surface layer Substances 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000010802 sludge Substances 0.000 claims abstract description 40
- 239000010865 sewage Substances 0.000 claims abstract description 27
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 230000004060 metabolic process Effects 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 129
- 238000005868 electrolysis reaction Methods 0.000 claims description 63
- 229910052742 iron Inorganic materials 0.000 claims description 62
- 239000003610 charcoal Substances 0.000 claims description 59
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 49
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 16
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 14
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 8
- 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 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 8
- 239000001110 calcium chloride Substances 0.000 claims description 8
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- 238000006424 Flood reaction Methods 0.000 claims description 7
- 244000005700 microbiome Species 0.000 claims description 7
- 229920002472 Starch Polymers 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- 159000000007 calcium salts Chemical class 0.000 claims description 6
- 159000000003 magnesium salts Chemical class 0.000 claims description 6
- 239000001103 potassium chloride Substances 0.000 claims description 6
- 235000011164 potassium chloride Nutrition 0.000 claims description 6
- 239000008107 starch Substances 0.000 claims description 6
- 235000019698 starch Nutrition 0.000 claims description 6
- 230000000050 nutritive effect Effects 0.000 claims description 5
- 239000008399 tap water Substances 0.000 claims description 4
- 235000020679 tap water Nutrition 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 238000007599 discharging Methods 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 235000015097 nutrients Nutrition 0.000 abstract 1
- 239000000463 material Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 5
- 239000002362 mulch Substances 0.000 description 5
- 230000002906 microbiologic effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000001727 glucose Nutrition 0.000 description 2
- 239000010841 municipal wastewater Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- CQPFMGBJSMSXLP-ZAGWXBKKSA-M Acid orange 7 Chemical compound OC1=C(C2=CC=CC=C2C=C1)/N=N/C1=CC=C(C=C1)S(=O)(=O)[O-].[Na+] CQPFMGBJSMSXLP-ZAGWXBKKSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZGBSOTLWHZQNLH-UHFFFAOYSA-N [Mg].S(O)(O)(=O)=O Chemical compound [Mg].S(O)(O)(=O)=O ZGBSOTLWHZQNLH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
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Abstract
The invention relates to a method for removing a ferric phosphate film and a ferrous phosphate passivating film from filler surface layer in an iron-carbon microelectrolysis reactor. The method comprises the following steps of: (1) adding anaerobic sludge or aerobic sludge and sewage or self-prepared water for providing nutrient substances for the growth metabolism of microbes into a reaction tank, in which fillers are hardened, of the iron-carbon microelectrolysis reactor, standing in the reaction tank of the iron-carbon microelectrolysis reactor for at least 30 minutes; and (2) when the standing time in the step (1) expires, introducing the sewage or the self-prepared water into the reaction tank continuously while discharging a mixed solution out of the reaction tank continuously, and continuously operating according to the mode until the ferric phosphate film and the ferrous phosphate passivating film on the filler surface layer in the reactor tank of the iron-carbon microelectrolysis reactor are decomposed completely, wherein the hydraulic retention time of the sewage or the self-prepared water in the reaction tank is 4 to 10 hours.
Description
Technical field
The invention belongs to the method that removes filler top layer passive film in micro-electrolysis reactor, particularly a kind of method that removes filler top layer tertiary iron phosphate and ferrous phosphate passive film in iron charcoal micro-electrolysis reactor.
Background technology
Iron-carbon micro-electrolysis is based on the corrosion electrochemistry principle of iron, by two kinds of iron with Different electrodes current potential with together with carbon is in direct contact with, be immersed in conductive electrolyte solution, battery effect occurs and form countless small corrosion galvanic cells, comprise the technology of macroscopical battery and microcosmic battery.Metal anode easily is corroded and consumes, and simultaneous electrochemical corrosion has caused again a series of related synergies, thus iron charcoal micro-electrolysis method there is flocculation, absorption, bridge formation, roll up sweep, the combined effect of the multiple effects such as coprecipitated, galvanic deposit, electrochemical reduction.
Iron charcoal micro electrolysis tech has efficient Effect of Pretreatment to poisonous and harmful trade effluents such as petrochemical complex, printing and dyeing, pharmacy and plating, poisonous difficult degradation pollutent in can decomposition and inversion waste water, improve the biodegradability of waste water, there is the advantages such as working cost is low, management easy to operate simultaneously.But the problem that iron charcoal micro electrolysis tech exists easy generation iron-carbon filling material to harden in actual applications, especially in the treating processes of phosphorus-containing acid ion trade effluent, the Fe that phosphate radical can generate with iron rot
2+and Fe
3+ion is fast in conjunction with generating ferrous phosphate and tertiary iron phosphate, and ferrous phosphate and tertiary iron phosphate can cover with the form of crystal the surface of iron-carbon filling material particle, form the passive film of one deck densification, cause iron-carbon filling material to lose activity.
Remove iron-carbon filling material top layer tertiary iron phosphate and ferrous phosphate passive film, prior art (is shown in Liu H N, Li G T, Qu J H, et al. Degradation of azo dye Acid Orange 7 in water by Fe to common employing intensified by ultrasonic wave method
0/ granular activated carbon system in the presence of ultrasound[J]. Journal of Hazardous Materials, 2007,144 (1-2): 180-186.) and mechanical mixing method (Qu Jiuhui, Liu Haining. a kind of rotary drum type reaction apparatus for waste water treatment by micro-electrolysis [P]. CN:1789155A, 2006), described method exists energy consumption height and the high problem of running cost.Therefore, remove tertiary iron phosphate and the ferrous phosphate passive film on iron-carbon filling material top layer in the urgent need to a kind of method of economical and efficient, to recover the activity of iron-carbon filling material.
Summary of the invention
The purpose of this invention is to provide a kind of method that removes filler top layer tertiary iron phosphate and ferrous phosphate passive film in iron charcoal micro-electrolysis reactor, this kind of method can not only remove tertiary iron phosphate and the ferrous phosphate passive film on iron-carbon filling material top layer efficiently, and cost is low, simple to operate.
Technical scheme of the present invention: occur inoculation anaerobion or aerobic microbiological in the micro-electrolysis reactor of tertiary iron phosphate and ferrous phosphate passive film to the iron-carbon filling material top layer, add the sewage that biodegradability is high simultaneously or provide nutritive substance from water distribution for microorganism, decomposing tertiary iron phosphate and the ferrous phosphate passive film on iron-carbon filling material top layer by the dephosphorizing of microorganism.
The method that removes filler top layer tertiary iron phosphate and ferrous phosphate passive film in iron charcoal micro-electrolysis reactor of the present invention, processing step is as follows:
(1) to adding anaerobic sludge or aerobic sludge in the reaction tank that the iron charcoal micro-electrolysis reactor that filler hardens occurs and for the microorganism growth metabolism provides the sewage of nutritive substance or from water distribution, and in the reaction tank of described iron charcoal micro-electrolysis reactor parked at least 30min;
(2) after the described holding time of step (1) expires, to passing into continuously described sewage in described reaction tank or from water distribution, meanwhile make the mixed solution in reaction tank discharge continuously, operation continuously in a manner described, until in the reaction tank of iron charcoal micro-electrolysis reactor, the tertiary iron phosphate on filler top layer and ferrous phosphate passive film decompose fully, described sewage or the hydraulic detention time in reaction tank is 4～10 h from water distribution.
In aforesaid method, described anaerobic sludge and aerobic sludge derive from the active sludge of municipal wastewater treatment plant or industrial sewage treatment plant anaerobic treatment unit and aerobic processing unit.
In aforesaid method, the add-on of the described anaerobic sludge of step (1) or aerobic sludge is: in the reaction tank of anaerobic sludge or aerobic sludge and iron charcoal micro-electrolysis reactor, the volume ratio of filler is 1:60～1:20, described sewage or be limited with the filler in the reaction tank that floods iron charcoal micro-electrolysis reactor and anaerobic sludge or aerobic sludge from the add-on of water distribution.
In aforesaid method, described sewage or be 300～2000 mg/L from the COD of water distribution concentration, BOD
5/ COD value>0.4.
In aforesaid method, the water temperature in the reaction tank of described iron charcoal micro-electrolysis reactor is controlled at 20～45 ℃.
In aforesaid method, described formulated by readily biodegradable organism, ammonium salt, sylvite, magnesium salts, calcium salt and water from water distribution, in water distribution, the organic concentration of readily biodegradable is 300～2000 mg/L, the concentration of ammonium salt is 60 ~ 450 mg/L, the concentration of sylvite is 5～30 mg/L, and the concentration of magnesium salts is 5～30 mg/L, and the concentration of calcium salt is 5～30 mg/L.
In aforesaid method, the preferred glucose of described readily biodegradable organism is or/and Zulkovsky starch, and described ammonium salt preferably sulfuric acid ammonium is or/and ammonium chloride, the preferred Repone K of described sylvite, described magnesium salts preferably sulfuric acid magnesium, described calcium salt preferably calcium chloride, described water is tap water or middle water.
The method of the invention utilizes the metabolism of microorganism that the tertiary iron phosphate on filler top layer and ferrous phosphate passive film are decomposed into to Fe
3+, Fe
2+, PO
4 3-, the above-mentioned ion quilt soluble in water discharged is discharged iron charcoal micro-electrolysis reactor continuously.
The present invention has following beneficial effect:
1, using anaerobic sludge or aerobic sludge and be inoculated in the reaction tank of iron charcoal micro-electrolysis reactor as anaerobion or aerobic microbiological source due to the method for the invention, take sewage or provide nutritive substance as the microorganism growth metabolism from water distribution, thus with low cost.
2, experiment shows (seeing each embodiment), after inoculating anaerobion or aerobic microbiological in the reaction tank of the iron charcoal micro-electrolysis reactor hardened to the generation filler, operation can make the tertiary iron phosphate on filler top layer and ferrous phosphate passive film decompose fully in 10 ~ 15 days continuously, shows that the method for the invention can remove tertiary iron phosphate and the ferrous phosphate passive film on filler top layer efficiently.
3, after the method for the invention is inoculated anaerobion or aerobic microbiological in the reaction tank of the iron charcoal micro-electrolysis reactor hardened to the generation filler, only need pass into continuously and provide the sewage of nutritive substance or from water distribution for the microorganism growth metabolism, and discharge continuously the mixed solution in reaction tank, thereby simple to operate, energy consumption is low.
The accompanying drawing explanation
Fig. 1 is the structural representation of iron charcoal micro-electrolysis reactor, 1-tank wherein, 2-intake pump, 3-reaction tank.
Fig. 2 is scanning electron microscope (SEM) photo of filler in iron charcoal micro-electrolysis reactor, magnification is 50, wherein, (a) being the photo before filler top layer tertiary iron phosphate and ferrous phosphate passive film remove, is (e) photo after filler top layer tertiary iron phosphate and ferrous phosphate passive film remove.
Fig. 3 is scanning electron microscope (SEM) photo of filler in iron charcoal micro-electrolysis reactor, magnification is 300, wherein, (b) being the photo before filler top layer tertiary iron phosphate and ferrous phosphate passive film remove, is (f) photo after filler top layer tertiary iron phosphate and ferrous phosphate passive film remove.
Fig. 4 is scanning electron microscope (SEM) photo of filler in iron charcoal micro-electrolysis reactor, magnification is 1000, wherein, (c) being the photo before filler top layer tertiary iron phosphate and ferrous phosphate passive film remove, is (g) photo after filler top layer tertiary iron phosphate and ferrous phosphate passive film remove.
Fig. 5 is scanning electron microscope (SEM) photo of filler in iron charcoal micro-electrolysis reactor, magnification is 5000, wherein, (d) being the photo before filler top layer tertiary iron phosphate and ferrous phosphate passive film remove, is (h) photo after filler top layer tertiary iron phosphate and ferrous phosphate passive film remove.
Embodiment
Remove the method for filler top layer tertiary iron phosphate and ferrous phosphate passive film in iron charcoal micro-electrolysis reactor and be described further of the present invention below by embodiment.In following embodiment, the structure of described iron charcoal micro-electrolysis reactor as shown in Figure 1; Described anaerobic sludge and aerobic sludge are respectively the mud of municipal wastewater treatment plant anaerobic treatment unit and the mud of aerobic processing unit.
The filler hardened in the reaction tank 3 of iron charcoal micro-electrolysis reactor is as shown in the photo (b) in the photo in Fig. 2 (a), Fig. 3, photo (c) in Fig. 4, photo (d) in Fig. 5, its Surface mulch has fine and close tertiary iron phosphate and ferrous phosphate passive film, and the present embodiment adopts following processing step to remove tertiary iron phosphate and the ferrous phosphate passive film on filler top layer:
(1) in the reaction tank 3 of the iron charcoal micro-electrolysis reactor hardened to the generation filler, add anaerobic sludge and sanitary sewage, in the reaction tank of anaerobic sludge and iron charcoal micro-electrolysis reactor, the volume ratio of filler is 1:40, the add-on of sanitary sewage is limited with the filler in the reaction tank that floods iron charcoal micro-electrolysis reactor and anaerobic sludge, the COD concentration of described sanitary sewage is 300 mg/L, BOD
5/ COD value>0.4, be controlled at 30 ℃ by the water temperature in described reaction tank 3, parked 100 min;
(2) after the described holding time of step (1) expires, pass into continuously described sanitary sewage and maintain water temperature at 30 ℃ in described reaction tank 3, meanwhile make the mixed solution in reaction tank 3 discharge continuously, the hydraulic detention time of described sanitary sewage in the reaction tank 3 of iron charcoal micro-electrolysis reactor is 4 h, move continuously in a manner described 15 days, the tertiary iron phosphate on filler top layer and ferrous phosphate passive film decompose fully, the PO of generation
4 3-ion is discharged from reaction tank 3.Remove filler after tertiary iron phosphate and ferrous phosphate passive film and see photo (e) in Fig. 2, the photo (f) in Fig. 3, the photo (g) in Fig. 4, the photo (h) in Fig. 5.
Embodiment 2
The filler hardened in the reaction tank 3 of iron charcoal micro-electrolysis reactor is as shown in the photo (b) in the photo in Fig. 2 (a), Fig. 3, photo (c) in Fig. 4, photo (d) in Fig. 5, its Surface mulch has fine and close tertiary iron phosphate and ferrous phosphate passive film, and the present embodiment adopts following processing step to remove tertiary iron phosphate and the ferrous phosphate passive film on filler top layer:
(1) in the reaction tank 3 of the iron charcoal micro-electrolysis reactor hardened to the generation filler, add aerobic sludge and sanitary sewage, in the reaction tank of aerobic sludge and iron charcoal micro-electrolysis reactor, the volume ratio of filler is 1:60, the add-on of sanitary sewage is limited with the filler in the reaction tank that floods iron charcoal micro-electrolysis reactor and aerobic sludge, the COD concentration of described sanitary sewage is 400 mg/L, BOD
5/ COD value>0.4, be controlled at 20 ℃ by the water temperature in described reaction tank 3, parked 120min;
(2) after the described holding time of step (1) expires, pass into continuously described sanitary sewage and maintain water temperature at 20 ℃ in described reaction tank 3, meanwhile make the mixed solution in reaction tank 3 discharge continuously, the hydraulic detention time of described sanitary sewage in the reaction tank 3 of iron charcoal micro-electrolysis reactor is 6h, move continuously in a manner described 14 days, the tertiary iron phosphate on filler top layer and ferrous phosphate passive film decompose fully, the PO of generation
4 3-ion is discharged from reaction tank 3.Remove filler after tertiary iron phosphate and ferrous phosphate passive film and see photo (e) in Fig. 2, the photo (f) in Fig. 3, the photo (g) in Fig. 4, the photo (h) in Fig. 5.
The filler hardened in the reaction tank 3 of iron charcoal micro-electrolysis reactor is as shown in the photo (b) in the photo in Fig. 2 (a), Fig. 3, photo (c) in Fig. 4, photo (d) in Fig. 5, its Surface mulch has fine and close tertiary iron phosphate and ferrous phosphate passive film, and the present embodiment adopts following processing step to remove tertiary iron phosphate and the ferrous phosphate passive film on filler top layer:
(1) to adding anaerobic sludge in the reaction tank 3 that the iron charcoal micro-electrolysis reactor that filler hardens occurs and from water distribution, in the reaction tank of anaerobic sludge and iron charcoal micro-electrolysis reactor, the volume ratio of filler is 1:20, add-on from water distribution is limited with the filler in the reaction tank that floods iron charcoal micro-electrolysis reactor and anaerobic sludge, water temperature in described reaction tank 3 is controlled to 35 ℃, parked 60min, described from water distribution by glucose, ammonium chloride, Repone K, calcium chloride, sal epsom and tap water are formulated, in water distribution, the concentration of glucose is 800 mg/L, the concentration of ammonium chloride is 160 mg/L, the concentration of Repone K is 30 mg/L, the concentration of calcium chloride and sal epsom is 5 mg/L, this kind is about 2000 mg/L from the COD of water distribution concentration, BOD
5/ COD value>0.5,
(2) after the described holding time of step (1) expires, described from water distribution and maintain water temperature at 35 ℃ to passing into continuously in described reaction tank 3, meanwhile make the mixed solution in reaction tank 3 discharge continuously, it is described that from water distribution, the hydraulic detention time in the reaction tank 3 of iron charcoal micro-electrolysis reactor is 7h, move continuously in a manner described 12 days, the tertiary iron phosphate on filler top layer and ferrous phosphate passive film decompose fully, the PO of generation
4 3-ion is discharged from reaction tank 3.Remove filler after tertiary iron phosphate and ferrous phosphate passive film and see photo (e) in Fig. 2, the photo (f) in Fig. 3, the photo (g) in Fig. 4, the photo (h) in Fig. 5.
Embodiment 4
The filler hardened in the reaction tank 3 of iron charcoal micro-electrolysis reactor is as shown in the photo (b) in the photo in Fig. 2 (a), Fig. 3, photo (c) in Fig. 4, photo (d) in Fig. 5, its Surface mulch has fine and close tertiary iron phosphate and ferrous phosphate passive film, and the present embodiment adopts following processing step to remove tertiary iron phosphate and the ferrous phosphate passive film on filler top layer:
(1) to adding anaerobic sludge in the reaction tank 3 that the iron charcoal micro-electrolysis reactor that filler hardens occurs and from water distribution, in the reaction tank of anaerobic sludge and iron charcoal micro-electrolysis reactor, the volume ratio of filler is 1:30, add-on from water distribution is limited with the filler in the reaction tank that floods iron charcoal micro-electrolysis reactor and anaerobic sludge, water temperature in described reaction tank 3 is controlled to 40 ℃, parked 40min, described from water distribution by Zulkovsky starch, glucose, ammonium sulfate, ammonium chloride, Repone K, calcium chloride, sal epsom and middle water are formulated, in water distribution, the concentration of Zulkovsky starch is 500 mg/L, the concentration of glucose is 1500 mg/L, the concentration of ammonium sulfate is 100 mg/L, the concentration of ammonium chloride is 350 mg/L, the concentration of Repone K is 15mg/L, the concentration of calcium chloride is 15mg/L, the concentration of sal epsom is 30 mg/L, this kind is about 1000 mg/L from the COD of water distribution concentration, BOD
5/ COD value>0.5,
(2) after the described holding time of step (1) expires, described from water distribution and maintain water temperature at 40 ℃ to passing into continuously in described reaction tank 3, meanwhile make the mixed solution in reaction tank 3 discharge continuously, it is described that from water distribution, the hydraulic detention time in the reaction tank 3 of iron charcoal micro-electrolysis reactor is 8h, move continuously in a manner described 10 days, the tertiary iron phosphate on filler top layer and ferrous phosphate passive film decompose fully, the PO of generation
4 3-ion is discharged from reaction tank 3.Remove filler after tertiary iron phosphate and ferrous phosphate passive film and see photo (e) in Fig. 2, the photo (f) in Fig. 3, the photo (g) in Fig. 4, the photo (h) in Fig. 5.
Embodiment 5
The filler hardened in the reaction tank 3 of iron charcoal micro-electrolysis reactor is as shown in the photo (b) in the photo in Fig. 2 (a), Fig. 3, photo (c) in Fig. 4, photo (d) in Fig. 5, its Surface mulch has fine and close tertiary iron phosphate and ferrous phosphate passive film, and the present embodiment adopts following processing step to remove tertiary iron phosphate and the ferrous phosphate passive film on filler top layer:
(1) to adding aerobic sludge in the reaction tank 3 that the iron charcoal micro-electrolysis reactor that filler hardens occurs and from water distribution, in the reaction tank of aerobic sludge and iron charcoal micro-electrolysis reactor, the volume ratio of filler is 1:50, add-on from water distribution is limited with the filler in the reaction tank that floods iron charcoal micro-electrolysis reactor and aerobic sludge, water temperature in described reaction tank 3 is controlled to 45 ℃, parked 30min, described from water distribution by Zulkovsky starch, glucose, ammonium chloride, Repone K, calcium chloride, sal epsom and tap water are formulated, in water distribution, the concentration of Zulkovsky starch is 100 mg/L, the concentration of glucose is 200 mg/L, the concentration of ammonium chloride is 60 mg/L, the concentration of Repone K is 5mg/L, the concentration of calcium chloride is 30mg/L, the concentration of sal epsom is 20 mg/L, this kind is about 300mg/L from the COD of water distribution concentration, BOD
5/ COD value>0.5,
(2) after the described holding time of step (1) expires, described from water distribution and maintain water temperature at 45 ℃ to passing into continuously in described reaction tank 3, meanwhile make the mixed solution in reaction tank 3 discharge continuously, it is described that from water distribution, the hydraulic detention time in the reaction tank 3 of iron charcoal micro-electrolysis reactor is 10h, move continuously in a manner described 15 days, the tertiary iron phosphate on filler top layer and ferrous phosphate passive film decompose fully, the PO of generation
4 3-ion is discharged from reaction tank 3.Remove filler after tertiary iron phosphate and ferrous phosphate passive film and see photo (e) in Fig. 2, the photo (f) in Fig. 3, the photo (g) in Fig. 4, the photo (h) in Fig. 5.
Claims (4)
1. a method that removes filler top layer tertiary iron phosphate and ferrous phosphate passive film in iron charcoal micro-electrolysis reactor is characterized in that processing step is as follows:
(1) to adding anaerobic sludge or aerobic sludge in the reaction tank that the iron charcoal micro-electrolysis reactor that filler hardens occurs and providing the sewage of nutritive substance or from water distribution for the microorganism growth metabolism, and in the reaction tank of described iron charcoal micro-electrolysis reactor parked at least 30min
The add-on of described anaerobic sludge or aerobic sludge is: in the reaction tank of anaerobic sludge or aerobic sludge and iron charcoal micro-electrolysis reactor, the volume ratio of filler is 1:60～1:20, described sewage or be limited with the filler in the reaction tank that floods iron charcoal micro-electrolysis reactor and anaerobic sludge or aerobic sludge from the add-on of water distribution;
(2) after the described holding time of step (1) expires, to passing into continuously described sewage in described reaction tank or from water distribution, meanwhile make the mixed solution in reaction tank discharge continuously, operation continuously in a manner described, until in the reaction tank of iron charcoal micro-electrolysis reactor, the tertiary iron phosphate on filler top layer and ferrous phosphate passive film decompose fully, described sewage or the hydraulic detention time in reaction tank is 4～10h from water distribution;
Described sewage or be 300～2000mg/L from the COD of water distribution concentration, BOD
5/ COD value>0.4.
2. remove according to claim 1 the method for filler top layer tertiary iron phosphate and ferrous phosphate passive film in iron charcoal micro-electrolysis reactor, it is characterized in that the water temperature in the reaction tank of described iron charcoal micro-electrolysis reactor is controlled at 20～45 ℃.
3. according to the described method that removes filler top layer tertiary iron phosphate and ferrous phosphate passive film in iron charcoal micro-electrolysis reactor of claim 1 or 2, it is characterized in that described formulated by readily biodegradable organism, ammonium salt, sylvite, magnesium salts, calcium salt and water from water distribution, in water distribution, the organic concentration of readily biodegradable is 300～2000mg/L, the concentration of ammonium salt is 60～450mg/L, the concentration of sylvite is 5～30mg/L, and the concentration of magnesium salts is 5～30mg/L, and the concentration of calcium salt is 5～30mg/L.
4. remove according to claim 3 the method for filler top layer tertiary iron phosphate and ferrous phosphate passive film in iron charcoal micro-electrolysis reactor, it is characterized in that described readily biodegradable organism is that glucose is or/and Zulkovsky starch, described ammonium salt is that ammonium sulfate is or/and ammonium chloride, described sylvite is Repone K, described magnesium salts is sal epsom, described calcium salt is calcium chloride, and described water is tap water or middle water.
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