CN1375553A - Ferrous oxide theobacillus and sludge heavy-metal eliminating method therewith - Google Patents
Ferrous oxide theobacillus and sludge heavy-metal eliminating method therewith Download PDFInfo
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- CN1375553A CN1375553A CN02112924A CN02112924A CN1375553A CN 1375553 A CN1375553 A CN 1375553A CN 02112924 A CN02112924 A CN 02112924A CN 02112924 A CN02112924 A CN 02112924A CN 1375553 A CN1375553 A CN 1375553A
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- mud
- heavy metal
- sludge
- thiobacillus ferrooxidant
- alkaline matter
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Links
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000010802 sludge Substances 0.000 title claims abstract description 36
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 45
- 239000011593 sulfur Substances 0.000 claims abstract description 42
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 16
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 16
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 16
- 230000001580 bacterial effect Effects 0.000 claims abstract description 11
- 238000004321 preservation Methods 0.000 claims abstract description 8
- 239000007790 solid phase Substances 0.000 claims abstract description 8
- 238000012258 culturing Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- 241000605118 Thiobacillus Species 0.000 claims description 49
- 241000894006 Bacteria Species 0.000 claims description 20
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 238000012545 processing Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000292 calcium oxide Substances 0.000 claims description 9
- 235000012255 calcium oxide Nutrition 0.000 claims description 9
- 239000003337 fertilizer Substances 0.000 claims description 8
- 244000005700 microbiome Species 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 6
- 241000605222 Acidithiobacillus ferrooxidans Species 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 4
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 4
- 239000004571 lime Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000011081 inoculation Methods 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000009423 ventilation Methods 0.000 claims description 2
- 235000015097 nutrients Nutrition 0.000 abstract description 11
- 239000010865 sewage Substances 0.000 abstract description 9
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 19
- 238000007254 oxidation reaction Methods 0.000 description 17
- 230000003647 oxidation Effects 0.000 description 16
- 239000005864 Sulphur Substances 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 10
- 239000010801 sewage sludge Substances 0.000 description 10
- 229910052725 zinc Inorganic materials 0.000 description 10
- 238000001784 detoxification Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 235000021049 nutrient content Nutrition 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- 241000605272 Acidithiobacillus thiooxidans Species 0.000 description 6
- 229910052793 cadmium Inorganic materials 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 238000005065 mining Methods 0.000 description 6
- 230000020477 pH reduction Effects 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 210000003608 fece Anatomy 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 238000004737 colorimetric analysis Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002054 inoculum Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000010871 livestock manure Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 238000005121 nitriding Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 244000052616 bacterial pathogen Species 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009395 breeding Methods 0.000 description 2
- 230000001488 breeding effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000050 nutritive effect Effects 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 241001052560 Thallis Species 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 210000003495 flagella Anatomy 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 230000007483 microbial process Effects 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- VJZLQIPZNBPASX-OJJGEMKLSA-L prednisolone sodium phosphate Chemical compound [Na+].[Na+].O=C1C=C[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)COP([O-])([O-])=O)[C@@H]4[C@@H]3CCC2=C1 VJZLQIPZNBPASX-OJJGEMKLSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 238000011069 regeneration method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/20—Sludge processing
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- Treatment Of Sludge (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
Abstract
The method for removing heavy metal from sewage and sludge includes the following steps: using a bacterial strain whose name is LX5 and preservation number is CGHMCC NO.0727, adding ferrous sulfate 5-30 g/L and element sulfur 0.5-1 g/L, inoculating LX5 strain and culturing naturalized sludge, placing the naturalized sludge into reactor, stirring with raw material, aerating and settling, returning 10-20% of settled sludge into reactor and dehydrating residual settled sludge, regulating pH value of liquid phase portion to precipitate heavy metal and neutralizing solid phase portion for agricultural application. The removing rate of heavy metal from sludge is 90%-100% and the remaining rate of nutrients being in sludge is above 80%.
Description
The present invention relates to the method for thiobacillus ferrooxidant and removal sludge heavy-metal thereof, is a technology of utilizing thiobacillus ferrooxidant to remove heavy metal in the sewage sludge, belongs to field of environment engineering technology.
The most sewage works of China adopt activated sludge process to carry out sewage purification, can produce the sewage sludge that accounts for the about 0.3-0.7% of sewage flooding quantity when purifying waste water.Be example with China's municipal sludge only, at present year generation is up to 100,000,000 tons (wet mud meter), and with annual 10～15% speed increase.Owing to lack the disposal outlet of economical and effective and environmental safety, huge day by day and waste high concentration of these quantity is seriously perplexing the sound development of wastewater treatment in China cause for a long time.
Mud is arbitrarily thrown aside or the way of landfill, has not only greatly wasted plant nutrient such as great number of organic matters and nitrogen, phosphorus in the mud, and has become new environment hidden danger in soil and the water surrounding.
Mud contains nutritive element and organic matters such as abundant N, P, and N is 3～6%, and P is 1～2%, and organic matter about 40-70%, is good organic manure resource mostly, and its fertilizer efficiency is equivalent to the fine chicken manure, is better than farm manures such as pig cow dung.And the huge and high concentration of the generation of mud, consider that from disposal costs and changing waste into resources angle mud is a kind of organic solid castoff that agricultural resource utilization is worth that has.Yet the existing of heavy metal in the mud (in the most sewage sludges of China Cu, Zn, heavy metal content such as Cr, Ni can reach hundreds of to thousands of mg/kg, in the leather-making mud Cr in addition can reach 1-3 ten thousand mg/kg), limited the implementation of mud agricultural use to a great extent.Therefore, heavy metal (or claiming mud detoxification) is significant to the mud regeneration in the removal mud.
Mainly with the sulfide of insoluble, forms such as organism combined are present in the solid phase of mud to heavy metal in the mud.Therefore to remove the heavy metal in the mud, must manage heavy metal is dissolved out from solid phase.The removal of heavy metal (as electroplating sludge) is to adopt chemical extraction method in traditional mud, and this method is to utilize mineral acid or complexing agent such as H
2SO
4, HNO
3, HCl, EDTA etc. handle mud with dissolving and lixiviate heavy metal, though it can remove some heavy metal (as Zn, Cd, Ni etc.) at short notice significantly, but the chemical extraction method acid consumption is big, processing costs is high, operation is dangerous, be difficult to be committed to engineering reality, and to the removal effect of some heavy metal relatively poor (clearance as Cu is lower than 50%, and the clearance of Cr is lower than 40%).
In recent years, there is the investigator to attempt to utilize microbial process to dissolve and removes heavy metal in the mud.United States Patent (USP) 5,217,615 and 5,454,948 disclose the method that a kind of employing sulfur oxidizing bacterium (sulphur oxidizing bacteria) is removed sludge heavy-metal, and it is to utilize thiobacillus thiooxidans and grate sulfur thiobacillus to produce sulfuric acid with elementary sulfur as energy substance to dissolve heavy metal in the removal mud.Yet, have following defective in these two patents: (1) is because its oxidation ratio of adding elementary sulfur has only 6.2%～56.2%, this is not remained in the detoxification mud by bio-oxidation with regard to meaning 43.8～93.8% elementary sulfur, will cause " back acidification effect " in case be manured into soil, so-called " back acidification effect " is meant and has not elementary sulfur or other reduced sulfur of complete oxidation in the detoxification mud, after this mud is manured into soil, owing to sulfur oxidizing bacterium causes the rapid acidifying phenomenon of soil to the continuation oxidation of reduced sulfur, this " back acidification effect " limited the use value of detoxification mud as fertilizer sources.(2) the main poisonous heavy metal Cr in the mud can not effectively be removed, and its clearance only is 13～57%.
Thiobacillus ferrooxidant and thiobacillus thiooxidans belong to Thiobacillus, it also be middle temperature, aerobic, have a liking for acid, obligate chemoautotrophic bacteria, it than thiobacillus thiooxidans advantageously, it can pass through redox state sulphur, can pass through Oxidation of Fe again
2+Obtain energy and grow and propagation, and thiobacillus thiooxidans can only utilize reduced sulfur.
At present, thiobacillus ferrooxidant mainly is used to reclaim noble metals such as copper, gold, uranium in the biological hydrometallurgy field.Up to now, still there is not any patent report that relevant thiobacillus ferrooxidant is used for removing the mud heavy metal.Its major cause is, general thiobacillus ferrooxidant bacterial strain is to separate from the waste water of acid mining area, they have certain susceptibility to water soluble organic substance, organic pollutants such as special small molecular organic acid and anthracene, phenanthrene, PCBs have bigger murder by poisoning to it, and water soluble organic substance content can reach 500～1000mgC/kg (in mud solid content 3%) in the mud, and the thiobacillus ferrooxidant that therefore directly is used to come from acid mining area waste water carries out sludge heavy-metal and removes and often be difficult to successfully.
The object of the present invention is to provide the method for a kind of thiobacillus ferrooxidant and removal sludge heavy-metal thereof, the thiobacillus ferrooxidant bacterial strain can tolerate water soluble organic substance, and realize growth rapidly and breed therein, utilize this bacterial strain to remove heavy metal in the mud, its clearance height, the clearance of Zn, Cu, Cd, Ni reaches 95-100%, the clearance of Cr is more than 90%, plant nutrient loss is few in the mud, effectively avoids not the elementary sulfur of complete oxidation to residue in and causes " back acidification effect " in the detoxification mud.
Thiobacillus ferrooxidant bacterial strain provided by the invention, called after LX
5, classification number: Thiobacillus Thiobacillusferrooxidans, preserve at China Committee for Culture Collection of Microorganisms common micro-organisms center, and preservation date is on March 13rd, 2002, and preservation registration number is CGMCC NO.0727; This characteristic of bacteria is: form is a rod-short, 0.3～0.5 * 1.0～1.5 μ m, Gram-negative bacteria, optimum temperuture is 30～35 ℃, optimal pH 2～3, aerobic, have a liking for acid, obligate chemoautotrophic bacteria, it can tolerate 1000～5000mgC/kg water soluble organic substance, the propagation generation time is 6.5～10 hours therein.
Utilize above-mentioned thiobacillus ferrooxidant to remove the method for heavy metal in the mud, it is characterized in that:
1. in mud, add 5～30g/L ferrous sulfate and 0.5～1g/L elementary sulfur, inoculation 10～15% (v/v,
LX Hereinafter the same)
5Bacterial strain, ventilation and stirring 4-10 days, enlarged culturing obtains acclimation sludge;
2. in bio-reactor, add pending mud and 5～30g/L ferrous sulfate, 0.5～1g/L elementary sulfur,
The above-mentioned acclimation sludge of 10～20% (v/v) is ventilated and stir process 3-6 days, pumps and handles
Mud;
3. the mud of above-mentioned processing is through sedimentation, and the sedimentation mud of 10-20% is back in the bio-reactor
Replace acclimation sludge usefulness, add pending mud and 5～30g/L ferrous sulfate, 0.5～1g/L element
Sulphur, circular treatment;
4.80～90% residual settlement mud carries out processed, obtains removing the solid phase part of heavy metal and containing
The liquid phase part of heavy metal;
5. the liquid phase part that contains heavy metal is regulated pH by dropping into alkaline matter, make heavy metal precipitation wherein after,
Draining enters Sewage Plant and handles.
Above-mentioned thiobacillus ferrooxidant is removed in the method for heavy metal in the mud, remove behind the heavy metal the solid phase part through with in the alkaline matter and after directly agricultural, or directly be prepared into organic commercial fertilizer or matrix.Used alkaline matter refers to lime, sodium hydroxide or ammoniacal liquor.Wherein best is to use unslaked lime.
Thiobacillus ferrooxidant culture condition provided by the invention is:
1, substratum moiety (g/L)
(NH
4)
2SO
43.5; KCl0.116, K
2HPO
40.058, Ca (NO
3) 4H
2O0.0168, MgSO
47H
2O0.583, FeSO
47H
2O44.22,1 liter of distilled water.
2, transferring pH with dilute sulphuric acid is 2～3, places reciprocating type shaking table 180rpm shaking culture, and culture temperature is 30～35 ℃.
Know-why of the present invention is, with the nutritive substance of the contained inorganic salt of mud itself as thiobacillus ferrooxidant, add ferrous sulfate and sulphur powder simultaneously, thiobacillus ferrooxidant breeds in a large number, the metallic sulfide of insoluble in the direct oxidation mud (heavy metal often exists with the metallic sulfide form in the anaeration in normal temperature digested sludge) becomes the metal sulfate (directly mechanism) of solubility, or by Thiobacillus Ferrooxidans'Oxidation of Fe
2+And the Fe that produces
3+Come oxidized metal sulfide, wherein S
2-Be oxidized to element S, the latter and external source are added element S and further be oxidized to sulfuric acid under the effects of this bacterium, mud medium pH is reduced to below 2.0, and redox potential is increased to 750mV, the reduction of the pH stripping of metal in the accelerate sludge again conversely in this reaction.After ferric ion is reduced into ferrous ion, can be oxidized to ferric ion by oxidized ferrous thiobacillus, the working cycle of realization response (indirect mechanism) again.
The method of heavy metal in thiobacillus ferrooxidant provided by the invention and the removal mud thereof has the following advantages and positively effect:
1, this LX
5Bacterial strain is directly to be separated to from mud, compares with the thiobacillus ferrooxidant that derives from acid mining area waste water, and this bacterial strain has very strong organism tolerance, can utilize ferrous sulfate or sulphur powder to breed rapidly for energy substance in the mud that organism enriches.Experimental results show that, it can tolerate the above water soluble organic substance content of 1000mgC/kg, and realize growth rapidly and breed therein, be 6.5～10 hours generation time, and the thiobacillus ferrooxidant that derives from acid mining area waste water can not grow and breeding in content is the water soluble organic substance of 1000mgC/kg.Medical experiment proves that this bacterium is a non-pathogenic bacteria, and is harmless to human body and animal.
2, utilize the method for heavy metal in thiobacillus ferrooxidant provided by the invention and the removal mud thereof, the heavy metal removing rate height, the treatment time, the short wherein clearance of Zn, Cu, Cd, Ni can reach 95-100%, and the clearance of Cr is more than 90%.
3, available technology adopting thiobacillus thiooxidans and add elementary sulfur (being generally 3g/L) is removed heavy metal in the mud as energy matter method, its oxidation ratio of adding elementary sulfur has only 6.2%～56.2%, this just means that every liter of detoxification mud has a unoxidized elementary sulfur of 1.3～2.8g with residual, in a single day this detoxification mud be manured into soil and will cause " back acidification effect ", therefore greatly limited the use value of its as fertilizer sources.And the bacterial strain that the present invention adopts is a thiobacillus ferrooxidant, because thiobacillus ferrooxidant can pass through redox state sulphur (as elementary sulfur), can pass through Oxidation of Fe again
2+The acquisition energy is grown and (thiobacillus thiooxidans can only utilize reduced sulfur to propagation, and can not Oxidation of Fe
2+).Therefore, in the present invention, interpolation ferrous sulfate and oligo-elements sulphur have two benefits as the energy matter of thiobacillus ferrooxidant vital movement, the one, because the existence of the ferrous sulfate of one of energy matter, thiobacillus ferrooxidant reduces greatly to the dependency of elementary sulfur, and its add-on is reduced to 0.5～1g sulphur/L mud; The 2nd, the ferrous sulfate that adds can strengthen Thiobacillus Ferrooxidans'Oxidation elementary sulfur activity, therefore, in the present invention, the oxidation ratio of elementary sulfur can reach 100%, do not have the residual of elementary sulfur in the detoxification mud, this with regard to effectively avoid because of elementary sulfur not complete oxidation residue in the back acidification that detoxification mud causes.
4, compare with chemical extraction method, the present invention need not consumption acid (not needing pre-acidifying), reaction temperature and, operating environment close friend does not produce secondary pollution, running cost is cheap.Chemical extraction method is removed in the operating process of sludge heavy-metal, and (general add-on is the dense H of 0.5～0.89g owing to need add a large amount of mineral acids
2SO
4/ g dewatered sludge), mineral acid produces a large amount of bubbles and stink with containing organic abundant sludge reaction, makes severe operational environment.And the present invention utilizes microorganism self metabolism to produce acidifying and oxygenizement, reaction temperature and, no bubble and stink generation.
5, after this method is handled plant nutrient N, P in the mud and organic retention rate more than 80%, the retention rate 80-85% of N wherein, P is 75-80%, organic matter is 85-85%;
Fig. 1 removes the schema of sludge heavy-metal method for thiobacillus ferrooxidant.
Embodiment 1:
(1) sampling
Get the not dewatered sludge of jiangsu wuxi municipal sewage plant, this mud fundamental characteristics sees Table 1.
Table 1 is for the organic Zn Cu of examination mud fundamental characteristics pH solid content N P Cr Cd Ni
-------------??％??------------???????------------????mg/kg???------------7.86?????4.34?????2.96?????1.46????45.6????1868???????299?????311?????4.5??????????308
(2) separation of thiobacillus ferrooxidant and enlarged culturing:
Utilize the 9K substratum directly from mud, to be separated to thiobacillus ferrooxidant and 4 ℃ of preservations.Its substratum moiety (g/L) is: (NH
4)
2SO
45.0, KCl0.167, K
2HPO
40.083, Ca (NO
3)
24H
2O0.024; MgSO
47H
2O0.833, FeSO
47H
2O44.2,1 liter of distilled water, pH1.9.Draw 20ml mud in the sterilized above-mentioned substratum of 200ml, 180rpm shaking culture to redox potential (ORP) rises to more than the 500mV in 28 ℃ of reciprocating type shaking tables.Get the above-mentioned culture of 1ml subsequently and carry out doubling dilution to 10
-9, get 10
-4-10
-9Dilution diluent is coated on the flat board, cultivates the black bacterium colony to occur on the rear plate in 9-10 days.Picking black bacterium colony is made bacteria suspension and is done dilution by last method and separate, and so repeats after 2 times, and by coating, gram stain microscopy observes the consistence of thalli morphology, obtains the thiobacillus ferrooxidant of purifying.Adopt same liquid nutrient medium to carry out the enlarged culturing of this bacterium.
This thiobacillus ferrooxidant bacterial strain is named as LX
5Classification number: thiobacillus Thiobacillusferrooxidans, in specified depositary institution of Patent Office of the People's Republic of China---preserve at China Committee for Culture Collection of Microorganisms common micro-organisms center, and preservation date is on March 13rd, 2002, and preservation registration number is CGMCCNO.0727.This bacterium is characterized as: form is a rod-short: 0.3～0.5 * 1.0～1.5 μ m, and Gram-negative bacteria, single utmost point flagellum, optimum temperuture is 30～35 ℃, optimal pH 2～3 is aerobic, have a liking for acid, the inorganic chemoautotrophic bacteria of obligate.Medical experiment proves that this bacterium is a non-pathogenic bacteria, and is harmless to human body and animal.Compare with the thiobacillus ferrooxidant that derives from acid mining area waste water, this bacterial strain has very strong organism tolerance, can utilize ferrous sulfate or sulphur powder to breed rapidly for energy matter in the mud that organism enriches.Experimental results show that, it can tolerate the above water soluble organic substance content of 1000mgC/kg, and realize growth rapidly and breed therein, be 6.5～10 hours generation time, and the thiobacillus ferrooxidant that derives from acid mining area waste water can not grow and breeding in content is the water soluble organic substance of 1000mgC/kg.
(3) heavy metal biological is removed reaction in the mud
Add 30g/L ferrous sulfate and 0.5g/L elementary sulfur, the above-mentioned LX of inoculation 10% (v/v)
5Bacterial strain, the 180rpm shaking culture was handled 10 days in reciprocating type shaking table;
(4) interpretation of result:
Above-mentioned processing mud is 12, centrifugal 15min under 000 * g, 0.45 μ m membrane filtration, send with Nanjing Forestry University's forest reserves and environment institute and adopt ICP-AES (Optival, USA) measure Zn, Cu, Cr and S in the filtrate, adopt vacuum freezing and drying lyophilization (EDWARDS Pirani 501, USA) the solid phase part behind the dry filter simultaneously, and measuring full N wherein, full P and organic matter, wherein full N adopts semimicro Kelvin nitriding (K
2SO
4-CuSO
4-Se distillation method); Full P adopts HNO
3-HClO
4Disappear and boil, molybdenum blue colorimetric method is surveyed phosphorus; The outer heating method of potassium bichromate is measured organic.According to the difference of heavy metal and plant nutrient content in the sample before and after the test, the rate of loss of removal rate of heavy metal and plant nutrient in the calculating mud.As calculated, the clearance of heavy metal Zn, Cu, Cd, Ni reaches 100% in the sewage sludge, and the clearance of Cr is 90.1%, and the content of handling elementary sulfur in the mud of front and back is 0, the oxidation ratio 100% of institute's addition element sulphur; The full N of plant nutrient, full P and organic rate of loss are respectively 18.9%, 21.8% and 12.5%.
Dehydrated sludge in unslaked lime and after can as fertilizer sources use.Table 2 is handled the variation of front and back heavy metal and plant nutrient content for sewage sludge.
Table 2 is handled elementary sulfur, heavy metal and plant nutrient content in the sewage sludge of front and back
Embodiment 2:(1) sampling:
| Before the processing | ||||||||
| Elementary sulfur | ??N | ??P | Organic | ??Zn | ??Cu | ??Cr | ??Cd | ??Ni |
| ????????---------???％???------------ | ???----------???mg/kg???--------- | |||||||
| 0 | ?2.96 | ?1.46 | ??45.6 | ?1868 | ?299 | ?311 | ?4.5 | ?308 |
| After the processing | ||||||||
| Elementary sulfur | ??N | ??P | Organic | ??Zn | ??Cu | ??Cr | ?Cd | ?Ni |
| ??????????----------??％??----------- | ???----------???mg/kg??--------- | |||||||
| 0 | ??2.40 | ??1.14 | ???39.9 | ??0 | ??0 | ??30.8 | ?0 | ?0 |
Get the not dewatered sludge of jiangsu wuxi sewage work, this mud is identical with sewage sludge sample among the embodiment 1.
(2) separation of thiobacillus ferrooxidant, enlarged culturing:
With embodiment 1.
(3) startup of bio-reactor and operation
In bio-reactor, add the above-mentioned not mud of dehydration, add 20g/L ferrous sulfate and 1g/L elementary sulfur, add above-mentioned inoculum (10% simultaneously, v/v) stir and aerated culture to start the reaction of removal of microorganisms heavy metal, the pH that treats sewage sludge in the biological reactor reduces to (needing 3-6 days) at 2.0 o'clock by 7.86, by the mud in the peristaltic pump extraction bio-reactor, with its sedimentation of relief, the sedimentation mud of 15% (v/v) is back to bio-reactor again, remaining 85% solid-liquid separation;
(4) interpretation of result:
Above-mentioned processing mud carries out solid-liquid separation through solid-liquid separator, adopts the ICP method to measure Zn, Cu, Cr and S in the filtrate, adopts the dry filter residue of vacuum freezing and drying lyophilization, and measures full N wherein, full P and organic matter, and wherein full N adopts semimicro Kelvin nitriding (K
2SO
4-CuSO
4-Se distillation method); Full P adopts HNO
3-HClO
4Disappear and boil, molybdenum blue colorimetric method is surveyed phosphorus; The outer heating method of potassium bichromate is measured organic.According to the difference of heavy metal and plant nutrient content in the sample before and after the test, the rate of loss of removal rate of heavy metal and plant nutrient in the calculating mud.As calculated, the clearance of heavy metal Zn, Cu reaches 100% in the mud, and the clearance of Cd, Ni, Cr is respectively 95.5%, 98.5%, 92.9%, and the content of handling elementary sulfur in the mud of front and back is 0, the oxidation ratio 100% of institute's addition element sulphur; The full N of plant nutrient, full P and organic rate of loss are respectively 18.5%, 22.8% and 11.8%.
Dehydrated sludge in unslaked lime and after can as fertilizer sources use.Table 3 is the variation of sludge treatment front and back heavy metal and plant nutrient content.
Table 3 is handled elementary sulfur, heavy metal and plant nutrient content in the sewage sludge of front and back
Embodiment 3:(1) sampling: get the not dewatered sludge of Suzhou, Jiangsu sewage work, this mud fundamental characteristics sees Table 1.
| Before the processing | ||||||||
| Elementary sulfur | N | ?P | Organic | ?Zn | ?Cu | ?Cr | ?Cd | ?Ni |
| ??????---------???％???--------- | ????----------??mg/kg??--------- | |||||||
| 0 | 2.96 | ?1.46 | ??45.6 | ?1868 | ?299 | ?311 | ?4.5 | ?308 |
| After the processing | ||||||||
| Elementary sulfur | N | ?P | Organic | ??Zn | ?Cu | ?Cr | ?Cd | ?Ni |
| ???????---------??％??---------- | ????----------???mg/kg???--------- | |||||||
| 0 | 2.41 | ?1.13 | ??40.3 | ??0 | ??0 | ?30.8 | ?0.2 | ?4.6 |
The organic Zn Cu of table 4 mud fundamental characteristics pH solid content N P Cr Cd Ni
-------------??％??------------????????------------????mg/kg???------------8.05???5.15??????3.91??????2.46?????43.8????1144???????4814????281?????4.5??????????576
(2) preparation of the separation of thiobacillus ferrooxidant, enlarged culturing and inoculum:
With embodiment 1.
(3) startup of bio-reactor and operation
In bio-reactor, add the above-mentioned not mud of dehydration, add 20g/L ferrous sulfate and 0.5g/L elementary sulfur, add above-mentioned inoculum (10%, v/v) stir and aerated culture to start the reaction of removal of microorganisms heavy metal, the pH that treats sewage sludge in the biological reactor reduces to (needing 3-6 days) at 2.0 o'clock by 8.05, just can extract mud in the bio-reactor out by peristaltic pump, the mud of 20% (v/v) is back to bio-reactor again, and remaining 80% carries out solid-liquid separation through solid-liquid separator;
(4) interpretation of result:
Above-mentioned processing mud carries out solid-liquid separation through solid-liquid separator, adopt the ICP method to measure Zn, Cu, Cr and S in the filtrate immediately, adopt the dry filter residue of vacuum freezing and drying lyophilization, and measure full N wherein, full P and organic matter, wherein full N adopts semimicro Kelvin nitriding (K
2SO
4-CuSO
4-Se distillation method); Full P adopts HNO
3-HClO
4Disappear and boil, molybdenum blue colorimetric method is surveyed phosphorus; The outer heating method of potassium bichromate is measured organic.According to the difference of heavy metal and plant nutrient content in the sample before and after the test, the rate of loss of removal rate of heavy metal and plant nutrient in the calculating mud.As calculated, the clearance of heavy metal Zn, Cd reaches 100% in the mud, and the clearance of Cu, Ni, Cr is 98.2%, 98.6%, 92.2%, and the content of handling elementary sulfur in the mud of front and back is 0, the oxidation ratio 100% of institute's addition element sulphur; The full N of plant nutrient, full P and organic rate of loss are respectively 16.5%, 20.2% and 10.3%.
Dehydrated sludge in unslaked lime and after can as fertilizer sources use.Table 5 is the variation of sludge treatment front and back heavy metal and plant nutrient content.
Table 5 is handled elementary sulfur, heavy metal and plant nutrient content in the sewage sludge of front and back
| Before the processing | ||||||||
| Elementary sulfur | N | ?P | Organic | Zn | ?Cu | ?Cr | ?Cd | ?Ni |
| ????----------????％???---------- | ????----------????mg/kg???--------- | |||||||
| 0 | 2.96 | ?1.46 | 45.6 | 1144 | ?4814 | ?281 | ?4.5 | ?576 |
| After the processing | ||||||||
| Elementary sulfur | N | ?P | Organic | Zn | ?Cu | ?Cr | ?Cd | ?Ni |
| ????----------????％???---------- | ????----------???mg/kg???--------- | |||||||
| 0 | 2.41 | ?1.13 | 40.3 | 0 | ?72.2 | ?30.8 | ?0 | ?6.9 |
Using with sodium hydroxide or aqueous ammonia to replace unslaked lime in embodiment 1,2 or 3, is that those of ordinary skills can accomplish.
Claims (10)
1, thiobacillus ferrooxidant bacterial strain, called after LX
5, classification number: Thiobacillus Thiobacillusferrooxidans, preserve at China Committee for Culture Collection of Microorganisms common micro-organisms center, and preservation date is on March 13rd, 2002, and preservation registration number is CGMCC NO.0727; This characteristic of bacteria is: form is a rod-short, 0.3～0.5 * 1.0～1.5um, Gram-negative bacteria, optimum temperuture is 30～35 ℃, optimal pH 2～3, aerobic, have a liking for acid, obligate chemoautotrophic bacteria, it can tolerate the water soluble organic substance of 1000～5000mgC/kg, the propagation generation time is 6.5～10 hours therein.
2, utilize the described thiobacillus ferrooxidant of claim 1 to remove the method for heavy metal in the mud, it is characterized in that:
1) in mud, add 5～30g/L ferrous sulfate and 0.5～1g/L elementary sulfur, inoculation 10～15% (v/v,
LX5 bacterial strain Hereinafter the same), ventilation and stirring 4-10 days, enlarged culturing obtains acclimation sludge;
2) in bio-reactor, add pending mud and 5～30g/L ferrous sulfate, 0.5～1g/L elementary sulfur,
The above-mentioned acclimation sludge of 10～20% (v/v) ventilates and stir process 3-6 days, pumps to handle
Mud;
3) mud of above-mentioned processing is through sedimentation, and the sedimentation mud of 10-20% is back in the bio-reactor
Replace acclimation sludge usefulness, add pending mud and 5～30g/L ferrous sulfate, 0.5～1g/L elementary sulfur,
Circular treatment;
4) 80～90% residual settlement mud carries out processed, obtains removing the solid phase part of heavy metal and containing
The liquid phase part of heavy metal;
5) liquid phase part that contains heavy metal is regulated pH by dropping into alkaline matter, make heavy metal precipitation wherein after,
Draining.
3, thiobacillus ferrooxidant according to claim 2 is removed the method for heavy metal in the mud, it is characterized in that: wherein remove behind the heavy metal the solid phase part through with in the alkaline matter and after agricultural, or be prepared into organic commercial fertilizer or matrix.
4, according to the method for heavy metal in claim 2 or the 3 described thiobacillus ferrooxidant removal mud, it is characterized in that: used alkaline matter refers to lime, sodium hydroxide or ammoniacal liquor in its method.
5, according to the method for heavy metal in claim 2 or the 3 described thiobacillus ferrooxidant removal mud, it is characterized in that: used alkaline matter refers to lime or ammoniacal liquor in its method.
6, thiobacillus ferrooxidant according to claim 4 is removed the method for heavy metal in the mud, and it is characterized in that: used alkaline matter refers to lime or ammoniacal liquor in its method.
7, according to the method for heavy metal in claim 2 or the 3 described thiobacillus ferrooxidant removal mud, it is characterized in that: used alkaline matter refers to unslaked lime in its method.
8, thiobacillus ferrooxidant according to claim 4 is removed the method for heavy metal in the mud, and it is characterized in that: used alkaline matter refers to unslaked lime in its method.
9, thiobacillus ferrooxidant according to claim 5 is removed the method for heavy metal in the mud, and it is characterized in that: used alkaline matter refers to unslaked lime in its method.
10, thiobacillus ferrooxidant according to claim 6 is removed the method for heavy metal in the mud, and it is characterized in that: used alkaline matter refers to unslaked lime in its method.
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