CN102659219B - Method for removing ferrous sulfide passivating film from filler surface layer in iron-carbon microelectrolysis reactor - Google Patents
Method for removing ferrous sulfide 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
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 42
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 title abstract description 14
- 239000002344 surface layer Substances 0.000 title abstract 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 86
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 81
- 241000894006 Bacteria Species 0.000 claims abstract description 66
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 59
- 239000011593 sulfur Substances 0.000 claims abstract description 59
- 230000001590 oxidative effect Effects 0.000 claims abstract description 54
- 238000005273 aeration Methods 0.000 claims abstract description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- 230000004060 metabolic process Effects 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 131
- 238000005868 electrolysis reaction Methods 0.000 claims description 65
- 229910052742 iron Inorganic materials 0.000 claims description 65
- 230000009849 deactivation Effects 0.000 claims description 63
- 239000003610 charcoal Substances 0.000 claims description 61
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 25
- 239000001103 potassium chloride Substances 0.000 claims description 13
- 235000011164 potassium chloride Nutrition 0.000 claims description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 12
- 229910002651 NO3 Inorganic materials 0.000 claims description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 12
- 150000003863 ammonium salts Chemical class 0.000 claims description 12
- 239000001110 calcium chloride Substances 0.000 claims description 12
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 12
- 159000000007 calcium salts Chemical class 0.000 claims description 12
- 159000000003 magnesium salts Chemical class 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical group [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 238000006424 Flood reaction Methods 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical group [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 6
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 6
- 239000008399 tap water Substances 0.000 claims description 5
- 235000020679 tap water Nutrition 0.000 claims description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 4
- 230000000050 nutritive effect Effects 0.000 claims description 4
- 229940001516 sodium nitrate Drugs 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 235000015097 nutrients Nutrition 0.000 abstract description 6
- 239000010802 sludge Substances 0.000 abstract description 2
- 230000001580 bacterial effect Effects 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 abstract 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000011049 filling Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 230000001954 sterilising effect Effects 0.000 description 6
- 241000605118 Thiobacillus Species 0.000 description 5
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- 238000004659 sterilization and disinfection Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010183 spectrum analysis Methods 0.000 description 3
- 241000605272 Acidithiobacillus thiooxidans Species 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- -1 distilled water compound Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
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- 238000000386 microscopy Methods 0.000 description 2
- 235000016709 nutrition Nutrition 0.000 description 2
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- 239000007787 solid Substances 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 2
- 238000012549 training Methods 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
- 241000605222 Acidithiobacillus ferrooxidans Species 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 238000003794 Gram staining Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 241001052560 Thallis Species 0.000 description 1
- 108010021006 Tyrothricin Proteins 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
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- GSXRBRIWJGAPDU-BBVRJQLQSA-N tyrocidine A Chemical group C([C@H]1C(=O)N[C@H](C(=O)N[C@@H](CCCN)C(=O)N[C@H](C(N[C@H](CC=2C=CC=CC=2)C(=O)N2CCC[C@H]2C(=O)N[C@@H](CC=2C=CC=CC=2)C(=O)N[C@H](CC=2C=CC=CC=2)C(=O)N[C@@H](CC(N)=O)C(=O)N[C@@H](CCC(N)=O)C(=O)N1)=O)CC(C)C)C(C)C)C1=CC=C(O)C=C1 GSXRBRIWJGAPDU-BBVRJQLQSA-N 0.000 description 1
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- Micro-Organisms Or Cultivation Processes Thereof (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
The invention relates to a method for removing a ferrous sulfide passivating film from a filler surface layer in an iron-carbon microelectrolysis reactor. The method comprises the following steps of: (1) adding bacterial sludge of sulfur oxidizing bacteria and self-prepared water for providing nutrient substances for the growth metabolism of the sulfur oxidizing bacteria into a reaction tank, in which the ferrous sulfide passivating film occurs on the filler surface layer, of the iron-carbon microelectrolysis reactor, standing in the reaction tank of the iron-carbon microelectrolysis reactor for at least 30 minutes, and aerating during standing; and (2) when the standing time in the step (1) expires, introducing the self-prepared water into the reaction tank continuously while discharging a mixed solution out of the reaction tank continuously, performing aeration to provide dissolved oxygen for the metabolism of the sulfur oxidizing bacteria, and operating continuously according to the mode until the ferrous sulfide passivating film on the filler surface layer in the reaction tank of the iron-carbon microelectrolysis reactor is decomposed completely, wherein the hydraulic retention time of 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 the micro-electrolysis reactor, particularly a kind of method that removes filler top layer ferrous sulfide deactivation film in the iron charcoal micro-electrolysis reactor.
Background technology
Iron-carbon micro-electrolysis technology is based on the corrosion electrochemistry principle of iron, two kinds of iron and carbon with different electropotentials are in direct contact with together, be immersed in the conductive electrolyte solution, battery effect takes place and form countless small corrosion galvanic cells, comprise macroscopical battery and microcosmic battery.Metal anode easily is corroded and consumes, and galvanic corrosion has simultaneously caused a series of related synergies again, thus iron charcoal micro-electrolysis method have flocculation, absorption, bridge formation, roll up sweep, the combined effect of multiple effects such as coprecipitated, galvanic deposit, electrochemical reduction.
Iron charcoal micro electrolysis tech has pre-treatment effect efficiently to poisonous and harmful trade effluents such as petrochemical complex, printing and dyeing, pharmacy and plating, poisonous difficult degradation feature pollutent in can decomposition and inversion waste water, improve the biodegradability of waste water, have advantages such as the low and management easy to operate of working cost 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 to sulfur-bearing acid group salt, thiosulphate and sulfide trade effluent, the strong reducing action of little electrolytic system can cause forming Iron sulfuret at iron charcoal particle surface, the Iron sulfuret that is distributed in the filler particles top layer constitutes the passive film of one deck densification, causes iron-carbon filling material to lose activity.
Remove iron-carbon filling material top layer ferrous sulfide deactivation film, prior art (is seen 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), there is the high and high problem of running cost of energy consumption in described method.Therefore, the method that presses for a kind of economical and efficient is removed the ferrous sulfide deactivation film on iron-carbon filling material top layer, 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 ferrous sulfide deactivation film in the iron charcoal micro-electrolysis reactor, this kind method can not only remove the ferrous sulfide deactivation film on iron-carbon filling material top layer efficiently, and cost is low, and is simple to operate.
Technical scheme of the present invention: occur to the iron-carbon filling material top layer inoculating sulfur oxidizing bacterium (Sulfur-Oxidizing Bacteria in the micro-electrolysis reactor of ferrous sulfide deactivation film, SOB), add simultaneously biodegradability high provide nitrogenous source and inorganic nutrient substance from water distribution for sulfur oxidizing bacterium, aeration provides oxygen and carbon source to sulfur oxidizing bacterium, utilizes sulfur oxidizing bacterium to the oxygenizement oxygenolysis iron-carbon filling material top layer ferrous sulfide deactivation film of lower valency sulphur.
Described sulfur oxidizing bacterium (Sulfur-Oxidizing Bacteria, SOB) be warm, aerobic in the class, have a liking for acid, chemoautotrophic microorganism, can obtain the energy of vital movement by reductibilities such as oxidation elementary sulfur, sulfide, thiosulphate and sulfurous acid sulfuration thing, produce a class bacterium of meta-bolites sulfuric acid simultaneously.Common sulfur oxidizing bacterium has grate sulfur thiobacillus (Thiobacillus thloparus), thiobacillus thiooxidans (Thiobacillus thiooxidans) and the thiobacillus ferrooxidant (Thiobacillus ferrooxidans) in the Thiobacillus (Thiobacillus).
The method that removes filler top layer ferrous sulfide deactivation film in the iron charcoal micro-electrolysis reactor of the present invention, processing step is as follows:
(1) add in the reaction tank of iron charcoal micro-electrolysis reactor of ferrous sulfide deactivation film occurring to the filler top layer sulfur oxidizing bacterium bacterium mud and to the sulfur oxidizing bacterium growth metabolism provide nutritive substance from water distribution, and in the reaction tank of described iron charcoal micro-electrolysis reactor parked 30min at least, carry out aeration during parked, for the sulfur oxidizing bacterium metabolism provides dissolved oxygen;
(2) after the described holding time of step (1) expires, feeding is described from water distribution continuously in described reaction tank, mixed solution in the reaction tank is discharged continuously, in this process, carry out aeration, for the sulfur oxidizing bacterium metabolism provides dissolved oxygen, operation continuously in a manner described, till the ferrous sulfide deactivation film on filler top layer decomposed fully in the reaction tank of iron charcoal micro-electrolysis reactor, described was 4～10 h from the hydraulic detention time of water distribution in reaction tank.
In the aforesaid method, described sulfur oxidizing bacterium bacterium mud extracts purifying and cultivates acquisition from sewage sludge, and it extracts purification cultivation method and sees: the screening of a strain sulfur oxidizing bacterium and sign [J]., Qiu Lina etc., University of Science ﹠ Technology, Beijing's journal, 2007,29 (supplementary issue 2): 212-215; Have a liking for separation and the application in the sludge organism detoxification [J] thereof of sour sulfur oxidizing bacterium strain., Zhou Shungui etc., Research of Environmental Sciences, 2003,16 (5): 41-45.
In the aforesaid method, the add-on of described sulfur oxidizing bacterium bacterium mud is: every liter of filler 0.5～2.5g sulfur oxidizing bacterium bacterium mud, described add-on from water distribution is limited with the filler in the reaction tank that floods iron charcoal micro-electrolysis reactor and sulfur oxidizing bacterium bacterium mud.
In the aforesaid method, the water temperature control in the described micro-electrolysis reactor is at 20～45 ℃.Described aeration rate reaches 0.5～3.0 mg/L with dissolved oxygen concentration in the reaction tank and is limited.
In the aforesaid method, described formulated by ammonium salt or nitrate, carbonate, sylvite, calcium salt, magnesium salts and water from water distribution, the control of pH value is 3.0～8.0, the concentration of described ammonium salt or nitrate is 100～400 mg/L, the concentration of described carbonate is 10～50 mg/L, the concentration of described sylvite is 5～30 mg/L, and the concentration of described calcium salt is 5～30 mg/L, and the concentration of described magnesium salts is 5～30 mg/L.
In the aforesaid method, the preferred ammonium chloride of described ammonium salt is or/and ammonium sulfate, the preferred SODIUMNITRATE of described nitrate or ammonium nitrate, the preferred sodium bicarbonate of described carbonate, the preferred Repone K of described sylvite, described calcium salt preferably calcium chloride, described magnesium salts preferably sulfuric acid magnesium, described water are tap water or middle water.
The method of the invention utilizes sulfur oxidizing bacterium to the oxygenizement oxygenolysis ferrous sulfide deactivation film of lower valency reducible sulfur, the meta-bolites SO of generation
4 2-Ion is soluble in water, and discharges along with the continuous discharge of the mixed solution in the reaction tank of iron charcoal micro-electrolysis reactor.
The present invention has following beneficial effect:
1, because the method for the invention is inoculated in the reaction tank of iron charcoal micro-electrolysis reactor as the sulfur oxidizing bacterium source with sulfur oxidizing bacterium bacterium mud, being that the sulfur oxidizing bacterium growth metabolism provides nutritive substance from water distribution, provide dissolved oxygen by aeration for the sulfur oxidizing bacterium metabolism, thus with low cost.
2, experiment shows (seeing each embodiment), occur to the filler top layer in the reaction tank of iron charcoal micro-electrolysis reactor of ferrous sulfide deactivation film behind the inoculation sulfur oxidizing bacterium, operation can make the ferrous sulfide deactivation film on filler top layer decompose fully in 10 ~ 15 days continuously, showed that the method for the invention can remove the ferrous sulfide deactivation film on filler top layer efficiently.
3, after the method for the invention is inoculated sulfur oxidizing bacterium in the reaction tank of the iron charcoal micro-electrolysis reactor that occurs the ferrous sulfide deactivation film to the filler top layer, only need to feed continuously for the sulfur oxidizing bacterium growth metabolism provide nutritive substance from water distribution and aeration, discharge the mixed solution in the reaction tank simultaneously continuously, thereby simple to operate, energy consumption is low.
Description of drawings
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 the iron charcoal micro-electrolysis reactor, wherein, is that filler top layer ferrous sulfide deactivation film removes preceding photo (a), (b) is the photo after filler top layer ferrous sulfide deactivation film removes.
Fig. 3 is the energy spectrum analysis spectrogram of filler in the iron charcoal micro-electrolysis reactor, wherein, (c) being that filler top layer ferrous sulfide deactivation film removes preceding energy spectrum analysis (EDS) spectrogram, (d) is energy spectrum analysis (EDS) spectrogram after filler top layer ferrous sulfide deactivation film removes.
Embodiment
Below by embodiment the method that removes filler top layer ferrous sulfide deactivation film in the iron charcoal micro-electrolysis reactor of the present invention is described further.Among the following embodiment, the structure of described iron charcoal micro-electrolysis reactor as shown in Figure 1.Described sulfur oxidizing bacterium bacterium mud extracts purifying and cultivates from mud, step is as follows:
(1) preparation of substratum
Liquid nutrient medium: utilize the distilled water preparation, in the liquid training nutrition base, (NH
4)
2SO
4Concentration be 0.4 g/L, KH
2PO
4Concentration be 3.0 g/L, MgSO
47H
2The concentration of O is 0.5 g/L, CaCl
22H
2The concentration of O is 0.25 g/L, adopts moist heat sterilization; The sulphur powder that adds tyndallization provides energy for sulfur oxidizing bacterium, and the addition of sulphur powder is every liter of liquid training nutrition base 10 g.
Solid medium: A liquid: utilize the distilled water preparation, (NH in the solution
4)
2SO
4Concentration be 4 g/L, the concentration of KCl is 0.2 g/L, K
2HPO
4Concentration be 0.5 g/L, MgSO
47H
2The concentration of O is 0.5 g/L, Ca (NO
3)
24H
2The concentration of O is 0.02 g/L, and with the H of concentration 5 mol/L
2SO
4The pH of regulator solution is 3.0, moist heat sterilization; B liquid: be the Na of 70 g/L with the distilled water compound concentration
2S
2O
35H
2O solution, moist heat sterilization; C liquid: be 150 g/L agar powder solution with the distilled water compound concentration, moist heat sterilization.A behind B and the C liquid difference moist heat sterilization, is cooled to 60 ℃, and the flat board that falls at once after the three is mixed forms solid medium.
(2) single bacterium colony isolation and purification
Inhale the mud of 20 mL sulfur-bearing oxidation bacterium in the substratum of sterilising liq of 200 mL steps (1) preparation, in 28 ℃ of shaking tables, cultivate (180 r/min) and drop to below 2.0 until the pH of nutrient solution; Get 1 mL nutrient solution then and add the test tube that 9 mL sterilized waters are housed, so doubling dilution to 10
-9, obtain 10
-4, 10
-5, 10
-6, 10
-7, 10
-8, 10
-9Six dilution diluents; Get 10
-4～10
-9Dilution diluent is coating cultivation (3 repetitions of each extent of dilution) respectively on flat board, occur the faint yellow bacterium colony of 1～3 mm behind cultivation 10～15 d at flat board, and the adularescent bacterium colony occurs simultaneously.Microscopy finds in the faint yellow bacterium colony it mainly is tyrothricin.The faint yellow bacterium colony of picking is made bacteria suspension and is done to dilute separation by last method, gets different dilution diluents and does dull and stereotyped coating and cultivation under 28 ℃.So repeat on flat board, only to have faint yellow bacterium colony after 2 times, by smear, gramstaining and microscopy, the consistence of observation thalli morphology finally obtains the sulfur oxidizing bacterium strain.
(3) autotrophy is cultivated
The sulfur oxidizing bacterium strain of purifying is inoculated in the liquid nutrient medium of step (1) preparation, carries out multiplication culture, utilize supercentrifuge to separate after cultivation is finished, obtain wet bacterium mud, it is standby that lyophilize obtains sulfur oxidizing bacterium bacterium mud then.
Reaction tank 3 mesexine of iron charcoal micro-electrolysis reactor the filler of ferrous sulfide deactivation film occurs shown in the photo among Fig. 2 (a), can see Fig. 3 (c) by spectrogram, its top layer is coated with fine and close ferrous sulfide deactivation film, and present embodiment adopts following processing step to remove the ferrous sulfide deactivation film on filler top layer:
(1) adds sulfur oxidizing bacterium bacterium mud in the reaction tank of iron charcoal micro-electrolysis reactor of ferrous sulfide deactivation film occurring to the filler top layer and from water distribution, the add-on of sulfur oxidizing bacterium bacterium mud is every liter of filler 2.5 g, add-on from water distribution is limited with the filler in the reaction tank that floods iron charcoal micro-electrolysis reactor and sulfur oxidizing bacterium bacterium mud, water temperature in the described reaction tank 3 is controlled at 20 ℃, parked 120 min, aeration during parked, aeration rate reaches 3.0 mg/L with dissolved oxygen concentration in the reaction tank and is limited, described from water distribution by ammonium chloride, sodium bicarbonate, Repone K, calcium chloride, sal epsom and tap water are formulated, in water distribution, the concentration of ammonium chloride is 100 mg/L, the concentration of sodium bicarbonate is 10 mg/L, Repone K, the concentration of calcium chloride and sal epsom is 5 mg/L, and regulating from water distribution pH value with volumetric concentration 20% sulfuric acid is 3;
(2) after the described holding time of step (1) expires, feed in the described reaction tank described from water distribution and keep water temperature at 20 ℃ continuously, mixed solution in the reaction tank is discharged continuously, in this process, carry out aeration, aeration rate reaches 3.0 mg/L with dissolved oxygen concentration in the reaction tank and is limited, described is 4 h from the hydraulic detention time of water distribution in the reaction tank 3 of iron charcoal micro-electrolysis reactor, move 10 days in a manner described continuously, the ferrous sulfide deactivation film on filler top layer namely decomposes fully in the reaction tank of iron charcoal micro-electrolysis reactor, the SO that metabolism produces
4 2-Ion is discharged from reaction tank 3.Remove filler behind the ferrous sulfide deactivation film and see photo (b) among Fig. 2, can see Fig. 3 (d) by spectrogram.
Embodiment 2
Reaction tank 3 mesexine of iron charcoal micro-electrolysis reactor the filler of ferrous sulfide deactivation film occurs shown in the photo among Fig. 2 (a), can see Fig. 3 (c) by spectrogram, its top layer is coated with fine and close ferrous sulfide deactivation film, and present embodiment adopts following processing step to remove the ferrous sulfide deactivation film on filler top layer:
(1) adds sulfur oxidizing bacterium bacterium mud in the reaction tank of iron charcoal micro-electrolysis reactor of ferrous sulfide deactivation film occurring to the filler top layer and from water distribution, the add-on of sulfur oxidizing bacterium bacterium mud is every liter of filler 1 g, add-on from water distribution is limited with the filler in the reaction tank that floods iron charcoal micro-electrolysis reactor and sulfur oxidizing bacterium bacterium mud, water temperature in the described reaction tank 3 is controlled at 30 ℃, parked 100 min, aeration during parked, aeration rate reaches 2 mg/L with dissolved oxygen concentration in the reaction tank and is limited, described from water distribution by ammonium sulfate, sodium bicarbonate, Repone K, calcium chloride, sal epsom and tap water are formulated, in water distribution, the concentration of ammonium sulfate is 400 mg/L, the concentration of sodium bicarbonate is 20 mg/L, Repone K, the concentration of calcium chloride and sal epsom is 10 mg/L, and regulating from water distribution pH value with volumetric concentration 20% sulfuric acid is 5;
(2) after the described holding time of step (1) expires, feed in the described reaction tank described from water distribution and keep water temperature at 30 ℃ continuously, mixed solution in the reaction tank is discharged continuously, in this process, carry out aeration, aeration rate reaches 2 mg/L with dissolved oxygen concentration in the reaction tank and is limited, described is 5 h from the hydraulic detention time of water distribution in the reaction tank 3 of iron charcoal micro-electrolysis reactor, move 15 days in a manner described continuously, the ferrous sulfide deactivation film on filler top layer namely decomposes fully in the reaction tank of iron charcoal micro-electrolysis reactor, the SO that metabolism produces
4 2-Ion is discharged from reaction tank 3.Remove filler behind the ferrous sulfide deactivation film and see photo (b) among Fig. 2, can see Fig. 3 (d) by spectrogram.
Embodiment 3
Reaction tank 3 mesexine of iron charcoal micro-electrolysis reactor the filler of ferrous sulfide deactivation film occurs shown in the photo among Fig. 2 (a), can see Fig. 3 (c) by spectrogram, its top layer is coated with fine and close ferrous sulfide deactivation film, and present embodiment adopts following processing step to remove the ferrous sulfide deactivation film on filler top layer:
(1) adds sulfur oxidizing bacterium bacterium mud in the reaction tank of iron charcoal micro-electrolysis reactor of ferrous sulfide deactivation film occurring to the filler top layer and from water distribution, the add-on of sulfur oxidizing bacterium bacterium mud is every liter of filler 2 g, add-on from water distribution is limited with the filler in the reaction tank that floods iron charcoal micro-electrolysis reactor and sulfur oxidizing bacterium bacterium mud, water temperature in the described reaction tank 3 is controlled at 35 ℃, parked 80 min, aeration during parked, aeration rate reaches 1.5 mg/L with dissolved oxygen concentration in the reaction tank and is limited, described from water distribution by ammonium nitrate, sodium bicarbonate, Repone K, calcium chloride, sal epsom and middle water are formulated, in water distribution, the concentration of ammonium nitrate is 200 mg/L, the concentration of sodium bicarbonate is 30 mg/L, Repone K, the concentration of calcium chloride and sal epsom is 20 mg/L, and regulating from water distribution pH value with volumetric concentration 20% sulfuric acid is 6;
(2) after the described holding time of step (1) expires, feed in the described reaction tank described from water distribution and keep water temperature at 35 ℃ continuously, mixed solution in the reaction tank is discharged continuously, in this process, carry out aeration, aeration rate reaches 1.5 mg/L with dissolved oxygen concentration in the reaction tank and is limited, described is 8 h from the hydraulic detention time of water distribution in the reaction tank 3 of iron charcoal micro-electrolysis reactor, move 12 days in a manner described continuously, the ferrous sulfide deactivation film on filler top layer namely decomposes fully in the reaction tank of iron charcoal micro-electrolysis reactor, the SO that metabolism produces
4 2-Ion is discharged from reaction tank 3.Remove filler behind the ferrous sulfide deactivation film and see photo (b) among Fig. 2, can see Fig. 3 (d) by spectrogram.
Embodiment 4
Reaction tank 3 mesexine of iron charcoal micro-electrolysis reactor the filler of ferrous sulfide deactivation film occurs shown in the photo among Fig. 2 (a), can see Fig. 3 (c) by spectrogram, its top layer is coated with fine and close ferrous sulfide deactivation film, and present embodiment adopts following processing step to remove the ferrous sulfide deactivation film on filler top layer:
(1) adds sulfur oxidizing bacterium bacterium mud in the reaction tank of iron charcoal micro-electrolysis reactor of ferrous sulfide deactivation film occurring to the filler top layer and from water distribution, the add-on of sulfur oxidizing bacterium bacterium mud is every liter of filler 1.5 g, add-on from water distribution is limited with the filler in the reaction tank that floods iron charcoal micro-electrolysis reactor and sulfur oxidizing bacterium bacterium mud, water temperature in the described reaction tank 3 is controlled at 40 ℃, parked 50 min, aeration during parked, aeration rate reaches 1 mg/L with dissolved oxygen concentration in the reaction tank and is limited, described from water distribution by SODIUMNITRATE, sodium bicarbonate, Repone K, calcium chloride, sal epsom and middle water are formulated, in water distribution, the concentration of SODIUMNITRATE is 150 mg/L, the concentration of sodium bicarbonate is 40 mg/L, Repone K, the concentration of calcium chloride and sal epsom is 25mg/L, and regulating from water distribution pH value with the sodium hydroxide solution of concentration 2 mol/L is 8;
(2) after the described holding time of step (1) expires, feed in the described reaction tank described from water distribution and keep water temperature at 40 ℃ continuously, mixed solution in the reaction tank is discharged continuously, in this process, carry out aeration, aeration rate reaches 1 mg/L with dissolved oxygen concentration in the reaction tank and is limited, described is 9 h from the hydraulic detention time of water distribution in the reaction tank 3 of iron charcoal micro-electrolysis reactor, move 14 days in a manner described continuously, the ferrous sulfide deactivation film on filler top layer namely decomposes fully in the reaction tank of iron charcoal micro-electrolysis reactor, the SO that metabolism produces
4 2-Ion is discharged from reaction tank 3.Remove filler behind the ferrous sulfide deactivation film and see photo (b) among Fig. 2, can see Fig. 3 (d) by spectrogram.
Reaction tank 3 mesexine of iron charcoal micro-electrolysis reactor the filler of ferrous sulfide deactivation film occurs shown in the photo among Fig. 2 (a), can see Fig. 3 (c) by spectrogram, its top layer is coated with fine and close ferrous sulfide deactivation film, and present embodiment adopts following processing step to remove the ferrous sulfide deactivation film on filler top layer:
(1) adds sulfur oxidizing bacterium bacterium mud in the reaction tank of iron charcoal micro-electrolysis reactor of ferrous sulfide deactivation film occurring to the filler top layer and from water distribution, the add-on of sulfur oxidizing bacterium bacterium mud is every liter of filler 0.5 g, add-on from water distribution is limited with the filler in the reaction tank that floods iron charcoal micro-electrolysis reactor and sulfur oxidizing bacterium bacterium mud, water temperature in the described reaction tank 3 is controlled at 45 ℃, parked 30 min, aeration during parked, aeration rate reaches 0.5 mg/L with dissolved oxygen concentration in the reaction tank and is limited, described from water distribution by ammonium chloride, ammonium sulfate, sodium bicarbonate, Repone K, calcium chloride, sal epsom and tap water are formulated, in water distribution, ammonium chloride, the concentration of ammonium sulfate is 100 mg/L, the concentration of sodium bicarbonate is 50 mg/L, Repone K, the concentration of calcium chloride and sal epsom is 30 mg/L, and regulating from water distribution pH value with the sodium hydroxide solution of concentration 2 mol/L is 4;
(2) after the described holding time of step (1) expires, feed in the described reaction tank described from water distribution and keep water temperature at 45 ℃ continuously, mixed solution in the reaction tank is discharged continuously, in this process, carry out aeration, aeration rate reaches 0.5 mg/L with dissolved oxygen concentration in the reaction tank and is limited, described is 10 h from the hydraulic detention time of water distribution in the reaction tank 3 of iron charcoal micro-electrolysis reactor, move 11 days in a manner described continuously, the ferrous sulfide deactivation film on filler top layer namely decomposes fully in the reaction tank of iron charcoal micro-electrolysis reactor, the SO that metabolism produces
4 2-Ion is discharged from reaction tank 3.Remove filler behind the ferrous sulfide deactivation film and see photo (b) among Fig. 2, can see Fig. 3 (d) by spectrogram.
Claims (10)
1. method that removes filler top layer ferrous sulfide deactivation film in the iron charcoal micro-electrolysis reactor is characterized in that processing step is as follows:
(1) add in the reaction tank of iron charcoal micro-electrolysis reactor of ferrous sulfide deactivation film occurring to the filler top layer sulfur oxidizing bacterium bacterium mud and to the sulfur oxidizing bacterium growth metabolism provide nutritive substance from water distribution, and in the reaction tank of described iron charcoal micro-electrolysis reactor parked 30min at least, carry out aeration during parked, for the sulfur oxidizing bacterium metabolism provides dissolved oxygen;
(2) after the described holding time of step (1) expires, feeding is described from water distribution continuously in described reaction tank, mixed solution in the reaction tank is discharged continuously, in this process, carry out aeration, for the sulfur oxidizing bacterium metabolism provides dissolved oxygen, operation continuously in a manner described, till the ferrous sulfide deactivation film on filler top layer decomposed fully in the reaction tank of iron charcoal micro-electrolysis reactor, described was 4～10 h from the hydraulic detention time of water distribution in reaction tank.
2. according to the described method that removes filler top layer ferrous sulfide deactivation film in the iron charcoal micro-electrolysis reactor of claim 1, the add-on that it is characterized in that described sulfur oxidizing bacterium bacterium mud is: every liter of filler 0.5～2.5g sulfur oxidizing bacterium bacterium mud, described add-on from water distribution is limited with the filler in the reaction tank that floods iron charcoal micro-electrolysis reactor and sulfur oxidizing bacterium bacterium mud.
3. according to claim 1 or the 2 described methods that remove filler top layer ferrous sulfide deactivation film in the iron charcoal micro-electrolysis reactor, it is characterized in that water temperature control in the reaction tank of described iron charcoal micro-electrolysis reactor is at 20～45 ℃.
4. according to claim 1 or the 2 described methods that remove filler top layer ferrous sulfide deactivation film in the iron charcoal micro-electrolysis reactor, it is characterized in that aeration rate reaches 0.5～3.0 mg/L with dissolved oxygen concentration in the reaction tank and is limited.
5. according to the described method that removes filler top layer ferrous sulfide deactivation film in the iron charcoal micro-electrolysis reactor of claim 3, it is characterized in that aeration rate reaches 0.5～3.0 mg/L with dissolved oxygen concentration in the reaction tank and is limited.
6. according to claim 1 or the 2 described methods that remove filler top layer ferrous sulfide deactivation film in the iron charcoal micro-electrolysis reactor, it is characterized in that described formulated by ammonium salt or nitrate, carbonate, sylvite, calcium salt, magnesium salts and water from water distribution, the control of pH value is 3.0～8.0, the concentration of described ammonium salt or nitrate is 100～400 mg/L, the concentration of described carbonate is 10～50 mg/L, the concentration of described sylvite is 5～30 mg/L, the concentration of described calcium salt is 5～30 mg/L, and the concentration of described magnesium salts is 5～30 mg/L.
7. according to the described method that removes filler top layer ferrous sulfide deactivation film in the iron charcoal micro-electrolysis reactor of claim 3, it is characterized in that described formulated by ammonium salt or nitrate, carbonate, sylvite, calcium salt, magnesium salts and water from water distribution, the control of pH value is 3.0～8.0, the concentration of described ammonium salt or nitrate is 100～400 mg/L, the concentration of described carbonate is 10～50 mg/L, the concentration of described sylvite is 5～30 mg/L, the concentration of described calcium salt is 5～30 mg/L, and the concentration of described magnesium salts is 5～30 mg/L.
8. according to the described method that removes filler top layer ferrous sulfide deactivation film in the iron charcoal micro-electrolysis reactor of claim 4, it is characterized in that described formulated by ammonium salt or nitrate, carbonate, sylvite, calcium salt, magnesium salts and water from water distribution, the control of pH value is 3.0～8.0, the concentration of described ammonium salt or nitrate is 100～400 mg/L, the concentration of described carbonate is 10～50 mg/L, the concentration of described sylvite is 5～30 mg/L, the concentration of described calcium salt is 5～30 mg/L, and the concentration of described magnesium salts is 5～30 mg/L.
9. according to the described method that removes filler top layer ferrous sulfide deactivation film in the iron charcoal micro-electrolysis reactor of claim 5, it is characterized in that described formulated by ammonium salt or nitrate, carbonate, sylvite, calcium salt, magnesium salts and water from water distribution, the control of pH value is 3.0～8.0, the concentration of described ammonium salt or nitrate is 100～400 mg/L, the concentration of described carbonate is 10～50 mg/L, the concentration of described sylvite is 5～30 mg/L, the concentration of described calcium salt is 5～30 mg/L, and the concentration of described magnesium salts is 5～30 mg/L.
10. according to the described method that removes filler top layer ferrous sulfide deactivation film in the iron charcoal micro-electrolysis reactor of claim 6, it is characterized in that described ammonium salt is that ammonium chloride is or/and ammonium sulfate, described nitrate is SODIUMNITRATE or ammonium nitrate, described carbonate is sodium bicarbonate, described sylvite is Repone K, described calcium salt is calcium chloride, and described magnesium salts is sal epsom, and described water is tap water or middle water.
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