CN1242934C - Microorganism metabolism type regulate and control method, in sulphate waste water treatment - Google Patents
Microorganism metabolism type regulate and control method, in sulphate waste water treatment Download PDFInfo
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000004065 wastewater treatment Methods 0.000 title abstract description 3
- 229910021653 sulphate ion Inorganic materials 0.000 title description 17
- 244000005700 microbiome Species 0.000 title description 10
- 230000004060 metabolic process Effects 0.000 title description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 48
- 230000002503 metabolic effect Effects 0.000 claims abstract description 25
- 239000002351 wastewater Substances 0.000 claims abstract description 19
- 239000010802 sludge Substances 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 230000007269 microbial metabolism Effects 0.000 claims description 7
- 244000005706 microflora Species 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- 235000015097 nutrients Nutrition 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
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- 238000003756 stirring Methods 0.000 claims description 2
- 241000894006 Bacteria Species 0.000 abstract description 18
- 238000000855 fermentation Methods 0.000 abstract description 18
- 230000004151 fermentation Effects 0.000 abstract description 18
- 230000000813 microbial effect Effects 0.000 abstract description 10
- 238000006477 desulfuration reaction Methods 0.000 abstract description 7
- 230000023556 desulfurization Effects 0.000 abstract description 7
- 230000001105 regulatory effect Effects 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000002053 acidogenic effect Effects 0.000 abstract description 4
- 239000002028 Biomass Substances 0.000 abstract description 3
- 238000013019 agitation Methods 0.000 abstract 1
- 239000010842 industrial wastewater Substances 0.000 abstract 1
- 230000037353 metabolic pathway Effects 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- 239000000758 substrate Substances 0.000 description 20
- 239000007795 chemical reaction product Substances 0.000 description 17
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 15
- 239000007791 liquid phase Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 14
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 13
- 238000010586 diagram Methods 0.000 description 9
- 239000004310 lactic acid Substances 0.000 description 7
- 235000014655 lactic acid Nutrition 0.000 description 7
- 235000019260 propionic acid Nutrition 0.000 description 7
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 241000606125 Bacteroides Species 0.000 description 4
- 241000205085 Desulfobacter Species 0.000 description 4
- 230000002860 competitive effect Effects 0.000 description 4
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 4
- 241000607534 Aeromonas Species 0.000 description 3
- 241000605829 Desulfococcus Species 0.000 description 3
- 241000605909 Fusobacterium Species 0.000 description 3
- 241000589516 Pseudomonas Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000011002 quantification Methods 0.000 description 3
- 241000193403 Clostridium Species 0.000 description 2
- 241000186541 Desulfotomaculum Species 0.000 description 2
- 241000605716 Desulfovibrio Species 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- -1 Ethanol Acetate Propionic acid Butyric acid Valeric acid Chemical compound 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- 241001467578 Microbacterium Species 0.000 description 2
- 241000194017 Streptococcus Species 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000011081 inoculation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 229940005605 valeric acid Drugs 0.000 description 2
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- 241000206591 Peptococcus Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 241000588901 Zymomonas Species 0.000 description 1
- VJMAITQRABEEKP-UHFFFAOYSA-N [6-(phenylmethoxymethyl)-1,4-dioxan-2-yl]methyl acetate Chemical compound O1C(COC(=O)C)COCC1COCC1=CC=CC=C1 VJMAITQRABEEKP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
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- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- VXHUBGOVNPJIEI-UHFFFAOYSA-N ethyl acetate;propanoic acid Chemical compound CCC(O)=O.CCOC(C)=O VXHUBGOVNPJIEI-UHFFFAOYSA-N 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
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- 230000005764 inhibitory process Effects 0.000 description 1
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Classifications
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- Y02W10/12—
Abstract
The present invention provides a method for regulating microbial metabolic types during the treatment of sulfate wastewater, which relates to the field of the biological treatment of high concentration industrial wastewater. The present invention has the following procedures: (1) a tank type acidogenic desulfurization reactor for continuously complete mixing and agitation is adopted, and light fillers are added into the reactor to increase the biomass; (2) active sludge is domesticated for 25 to 30 days; (3) the acidogenic desulfurization reactor is started quickly, and the start-up period is about 20 days; (4)the microbial restrictive ecological factors are quantitatively regulated; (5) the metabolic pathway of acidogenic bacteria is controlled to be alcohol-type fermentation; (6) the metabolic type of microbial community is controlled to be acetic acid type metabolic way; the purpose of the present invention can be achieved with another operation method, namely to control operation conditions of the biological desulfurization reaction system. The present invention solves the difficult problem of the lowness of the high concentration sulfate wastewater treatment capability at present; the microbial community is regulated stably in an optimal metabolic type, and the removal rate of sulfate in wastewater is more than 90%.
Description
Technical field: the present invention relates to high-concentration industrial-water biological treatment field.
Background technology: the high concentration sulfate wastewater of industries such as chemical industry, pharmacy, process hides, papermaking, fermentation and mining discharging is one of environomental pollution source that needs to be resolved hurrily.Utilize the diphasic anaerobic biological treatment to administer the widespread consensus that sulfate wastewater has obtained environmental engineering circle.This process system is made up of three unit, i.e. sulfate reduction unit, sulfide oxidation unit and product methane unit.Wherein, the sulfate reduction unit is the rate-limiting step of whole process system, it is the product acid phase of diphasic anaerobic technique system in essence, is to utilize sulphate reducing bacteria (Sulfate Reducing Bacteria, the vitriol that SRB) is rich in the reducing waste water in the organic acid fermentation stage.In this element, mainly exist two quasi-microorganisms-acid formers (Acidogenes, AB) and sulphate reducing bacteria.AB is converted into the organism in the waste water tunnings such as small molecular organic acid and alcohol by hydrolysis and acidification, thereby the electron donor of sulphate reducing is provided for SRB.The different fermented type of AB battalion can produce different tunnings, and SRB also exists than big-difference the ability of utilizing of different fermentations product.Therefore, the sulfate reduction unit is the operating performance instability often, and the vitriol clearance generally is lower than 80%.The bottleneck factor that addresses this problem is how by outside control measures, makes microflora best metabolic type occur, quickens the cometabolism relation between AB and SRB two populations.But, the further investigation and the report of microbial metabolism type in the at present both at home and abroad still unmatchful biological desulfurization process system.
Summary of the invention: in order to solve the low difficult problem of high concentration sulfate wastewater processing power, the invention provides a kind of Engineering Control countermeasure based on microorganism physiological ecology principle, realize the acetic acid type metabolic way of microflora, thereby increase substantially the clearance of vitriol in the waste water.Microbial metabolism type regulate and control method operation steps comprised that (1) adopts Continuous Flow to mix fully to stir slot type and produces sour desulphurization reactor during sulfate wastewater was handled, in establish gas one liquid one solid three-phase separator, and add light filler; (2) acclimated activated sludge; (3) start the biological desulphurization reactive system fast; (4) metabolic type of controlling microbial group is the acetic acid type metabolic way: work as COD/SO
4 2-＞5.0 o'clock, Ns＜10.0kg/m
3D, pH=5.0～6.0, ORP＜-300mV, ALK＞1000mg/L; As 5.0＞COD/SO
4 2-＞2.0 o'clock, Ns＜7.5kg/m
3D, pH=6.0～6.5 ,-400mV＜ORP＜-300mV, 1500mg/L＜ALK＜2000mg/L; As 2.0＞COD/SO
4 2-＞1.0 o'clock, Ns＜7.5kg/m
3D, pH=6.0～7.0 ,-400mV＜ORP＜-300mV, 1500mg/L＜ALK＜2000mg/L; Another working method is the operational conditions of control biological desulphurization reactive system: COD/SO
4 2-〉=2.0, Ns≤7.5kg/m
3D, pH=6.0～7.0, ORP=-320～450mV, ALK=1500～2000mg/L.The present invention is according to microorganism physiological ecology principle, regulating and controlling microbial group is stabilized in best metabolic type, thereby broken the constraint of the unpredictable and uncontrollable viewpoint of the metabolic type of microorganism in the wastewater treatment, made the vitriol clearance in the waste water reach 90%～100%.Compare with traditional technology, the present invention can improve more than 20% the processing power of sulfate wastewater.The reason that CONTROL PROCESS system microorganism forms the acetic acid type metabolic way is as follows: the AB metabolism produces ethanol, acetate, H
2With the volatile acid (VFA is as propionic acid, butyric acid and lactic acid) more than three carbon.Ethanol can be converted into acetate rapidly by SRB; H
2Can be utilized H
2Sulphate reducing bacteria (HSRB) make substrate; VFA can be utilized the sulphate reducing bacteria (FSRB) of the above volatile acid of three carbon, comprise sulphate reducing bacteria (p-SRB), the sulphate reducing bacteria (1-SRB) that utilizes lactic acid that utilizes propionic acid and utilize butyro-sulphate reducing bacteria (b-SRB) to do substrate producing a large amount of acetate that VFA also can be produced hydrogen acetogen (HPA) utilization and produce acetate and H
2Acetate is utilized the sulphate reducing bacteria (ASRB) of acetate and does substrate; H
2Can be utilized by HSRB again, therefore, build a biologic chain (see figure 8) by this substrate supply type relation between AB, SRB and the HPA.Could form complete vitriol anaerobic oxidation process when only being the liquid phase end products with acetate, its final product is CO
2And H
2S, thus realize the thorough removal of pollutent as far as possible.Acid formers battalion of CONTROL PROCESS system ethanol-type fermentation has two benefits to biological desulphurization: (1) ethanol-type fermentation is the fermented type that sulphate reducing bacteria needs.Because acid formers and sulphate reducing bacteria have the Ecological Mechanism of interdependence, sulphate reducing bacteria can promptly utilize the tunning of acid formers, reduces the inhibition of acidic ending product to microorganism active, also is beneficial to the steady running of reactor; (2) sulphate reducing bacteria is an acetate with the product ethanol conversion of acid formers ethanol-type fermentation, for follow-up product methane provides suitable substrate mutually, thereby quickens the process of process system biochemical reaction.Operational conditions by the sour desulphurization reaction of control product system can make the vitriol clearance in the waste water reach more than 90%.
Description of drawings: Fig. 1 produces sour desulphurization reactor and process route chart, Fig. 2 is ethanol distribution schematic diagram of volatile acid in the liquid phase end products when being the carbon source substrate, Fig. 3 is propionic acid distribution schematic diagram of volatile acid in the liquid phase end products when being the carbon source substrate, Fig. 4 is lactic acid distribution schematic diagram of volatile acid in the liquid phase end products when being the carbon source substrate, Fig. 5 is the distribution schematic diagram of volatile acid in the liquid phase end products when being the carbon source substrate with acetate, Fig. 6 is the distribution schematic diagram of volatile acid in the liquid phase end products when being the carbon source substrate with the butyric acid, Fig. 7 is different carbon sources vitriol clearance synoptic diagram when being substrate, Fig. 8 is that the biological chain type cometabolism of microorganism in the sulfate-reducing process concerns synoptic diagram, Fig. 9 is the output and the distribution schematic diagram of different tests stage volatile acid, and Figure 10 is the metabolic biological community structure pattern diagram of battalion's acetic acid type.
Embodiment:
1. determine the process form of reactor: the process form of reactor as shown in Figure 1, name to producing sour desulphurization reactor (this reactor is ZL 98240801.3 utility model patents), for adding light filler Continuous Flow stirred-tank reactor (CSTR), cubic capacity 22.0L, useful volume 9.7L, in establish gas-liquid-solid triphase separator and agitator.The reactor outer felt keeps 35 ± 1 ℃ of temperature around heating control apparatus.Add light fillers such as gac or Cortex walnut to increase biomass and to reduce sludge loss.Gac is strengthened muddy water in addition and is mixed, and increases the function of rate of mass transfer.Gac is a particulate state, particle diameter 0.3～0.5mm, proportion 1.41g/cm
3, bulk density 0.54g/cm
3, add gac 2.2L.
2. acclimated activated sludge: the inoculation of activated-sludge that produces sour desulphurization reactor is taken from the environment that is rich in vitriol, as bed mud, irrigation canals and ditches bottom precipitation or municipal sewage plant's second pond bed mud of enterprise's factory effluent discharge outlets such as pharmacy, papermaking, fermentation.The purpose of sludge acclimatization is to obtain target microorganism group, its structure forms that (specifically flora is referring to " water pollution control microbiology " based on acid formers population and sulphate reducing bacteria population, Ren Nanqi etc. write, Heilungkiang science tech publishing house, in December, 1993 first version), and, comprise that aerobic microbiological, part aerobic-anaerobic microbe and part anaerobion (as methanogen etc.) progressively eliminate with the microorganism of incompatibility working condition.
The activated sludge acclimatization method is as follows: will plant mud and mix with gac, the sulfate wastewater that adopts artificial preparation is as nutrient solution, and its COD concentration is 3000mg/L, SO
4 2-Concentration is 2000mg/L.The control medium pH value is greater than 5.0, and anaerobism is cultivated.Change nutrient solution in 5 days one time, reduce mud aerial exposure duration during operation as far as possible.Domestication is 25～30 days, the redox potential (ORP) of domestication muddy water mixed solution bottom when finishing is-200～-250mV.
3. the quick sour desulphurization reaction of the product system that starts: start the sour desulphurization reaction of product system and promptly start the sour desulphurization reactor of product, when starting reactor, the one-level controlled variable is active sludge inoculum size, former water COD/SO
4 2-Ratio, original water basicity; The secondary controlled variable is volatile acid (VFA) and SO in reactor pH value and redox potential (ORP), the liquid phase end products
4 2-Clearance.Active sludge inoculation biomass (MLVSS) is 10000～13000mg/L, adopts the artificial distribution, and as organic carbon source (COD), sodium sulfate is electron acceptor(EA) (SO with the molasses waste liquid
4 2-).Control COD/SO in the former water
4 2-Ratio is 5.0 (COD=3000mg/L, SO
4 2-=600mg/L).Add NaHCO
3Regulating influent alkalinity (ALK) is 500mg/L, and gas vulcanization hydrogen adopts the NaOH solution absorption.The 1st～10d flooding velocity 10.0L/d, hydraulic detention time (HRT) is 20h, improves flow behind the 11d to 20L/d, HRT is 10h.About 20d of the starting period of reactor, every index reaches following standard: the pH value is 5.5～6.0, ORP is for about-300mV, volatile acid (VFA) total amount is about 1500mg/L, SO in the liquid phase end products
4 2-Clearance reaches 80%, sulfide output reaches 2.0mmol/L.
4. the restricted ecological factor of quantification regulating and controlling microbial
Produce the microbial ecosystem that sour desulphurization reactor is a manual creation, according to the physiological ecology rule of acid formers and sulphate reducing bacteria, quantification is regulated and control restricted ecological factor-COD/SO
4 2-Ratio, vitriol rate of load condensate (Ns), pH value, redox potential (ORP) and basicity (ALK).When the vitriol clearance greater than 90% the time, the quantitative indices and the control measures of each factor are as shown in table 1 in the reactor.
Table 1 produces the quantification and the regulation and control of restricted ecological factor in the sour desulphurization reactor
The control measures of restricted ecological factor quantitative indices ecological factor
COD/SO
4 2-1. improve COD concentration or 2. reduce SO than 〉=2.0
4 2-Concentration
The vitriol rate of load condensate is HRT=6～8h and 2. MLVSS=15000～20000mg/L 1.
≤7.5
(Ns, kg/m
3D) and 3. H in the reactor
2S concentration is less than 225mg/L
1. Ns≤7.5kg/m
3D and 2. COD/SO
4 2-〉=2.0 Hes
PH value 6.0～7.0
3. ALK 〉=300mg/L in intaking
ORP is Ns and COD/SO 1.
4 2-Than the same; 2. pH=6.0～7.0 Hes
-320～-450
(mV) 3. control anaerobic state or 4. add reductive agent, iron powder
1. Ns and COD/SO
4 2-Than the same and 2. pH=6.0～7.0;
ALK
1500～2000 and 3. in the liquid phase end products VFA concentration less than 2000mg/L
(mg/L)
With the distribution proportion of acetate in VFA be 50%～80%
5. the pathways metabolism of acid formers is an ethanol-type fermentation in the sour desulphurization reactor of control product
The metabolic type of control acid formers is that ethanol-type fermentation is to be determined by the ability of utilizing of sulphate reducing bacteria (SRB) to different substrates in sulfate-reducing process.The distribution situation of volatile acid in liquid phase end products when Fig. 2～Fig. 6 is different carbon source substrate, Fig. 7 is the vitriol clearance when utilizing different carbon source substrate, wherein alphabetical implication is as follows: E-ethanol; A-acetate; The P-propionic acid; The B-butyric acid; The V-valeric acid; L-lactic acid; The total liquid phase end products of T-(volatile acid).As seen, the vitriol clearance was respectively 99.9% and 97.8% when ethanol and lactic acid were substrate, and the vitriol clearance only was 7.5%, 22.2%, 12.0% when acetate, propionic acid and butyric acid were substrate.Therefore, SRB utilizes the order of substrate to be: ethanol＞lactic acid＞＞propionic acid＞butyric acid＞acetate, this thermodynamics rule with sulfate reduction is consistent.According to microorganism physiological metabolism characteristic, when the meta-bolites of acidogenic fermentation bacterium was main with ethanol, its metabolic type was an ethanol-type fermentation.
5.1 the operational parameter control of acid formers battalion ethanol-type fermentation
The key parameter of regulation and control acid formers battalion ethanol-type fermentation is pH value, basicity (ALK), COD/SO
4 2-Ratio, HRT and volumetric loading rate.Table 2～table 5 is respectively above-mentioned parameter influence to SRB when different levels.
Table 2 pH value and basicity are to the influence of reactor operating performance
| The pH value | Basicity (mg/L) | SO 4 2-Clearance (%) | Sulfide generation (S 2-，mmol/L) | ORP (mV) | Operating performance and estimation of stability |
| 4.8～5.3 5.4～5.7 6.2～7.0 | 445～620 650～800 1400～1600 | 62.5 95.3 97.4 | 1.47 4.23 4.54 | -270～-275 -305～-315 -340～-355 | Weak effect, unstable effective, the edge stabilising effect is good, and is stable |
Annotate: HRT=10.6h, COD=3200-3600mg/L, SO
4 2-Concentration 640-680mg/L.
Table 3 COD/SO
4 2-Value is to the influence of reactor operating performance
| COD/SO 4 2- | SO 4 2-Clearance (%) | The S that produces 2- (mmol/L) | Volatile acid is formed weight percent (%) | PH value | Basicity (mg/L) | ||
| Ethanol | Acetate | Propionic acid+butyric acid+valeric acid | |||||
| 4.5∶1 3.6∶1 2.7∶1 1.9∶1 0.9∶1 | 97.4 97.1 88.3 65.0 38.8 | 4.54 6.35 7.15 8.19 8.10 | 10.8 4.7 0.0 0.0 0.0 | 60.1 70.6 70.6 71.5 73.6 | 29.1 24.7 29.4 28.5 26.4 | 6.2-7.0 | 1497 1608 1631 1883 1939 |
Annotate: HRT=10.6h, COD=3200-3600mg/L is by changing SO
4 2-Concentration adjustment COD/SO
4 2-Ratio.Regulate influent alkalinity.
Table 4 HRT is to the influence (mean value) of reactor operating performance
| HRT (h) | SO 4 2-Clearance (%) | The S that produces 2- (mmol/L) | PH value | Volatile acid is formed weight percent (%) | ||||
| Ethanol | Acetate | Propionic acid | Butyric acid | Valeric acid | ||||
| 10.6 8.1 6.2 5.2 | 88.3 85.7 80.7 70.6 | 7.15 6.70 6.09 5.11 | 6.34 6.51 6.47 6.28 | 0.00 0.00 0.00 9.15 | 70.25 68.18 66.95 57.39 | 11.39 9.76 9.61 8.99 | 16.19 19.79 20.94 21.52 | 2.18 2.27 2.51 2.96 |
Annotate: COD and SO
4 2-Concentration average out to 3600.0mg/L and 1200.0mg/L, COD/SO
4 2-=3: 1.
Table 5 volumetric loading rate is to the influence (mean value) of reactor operating performance
| Former water COD (mg/L) | Former water SO 4 2- (mg/L) | HRT (h) | COD (the kg/m that loads 3·d) | SO 4 2-Rate of load condensate (kg -/m 3·d) | SO 4 2-Clearance (%) | The S that produces 2- (mmol/L) |
| 3222.0 4815.8 7906.7 | 1213.1 1760.7 2831.2 | 6.2 7.0 8.7 | 12.09 16.44 21.72 | 4.55 6.01 7.58 | 80.7 83.6 82.2 | 6.09 8.88 13.17 |
The optimal operating parameter of reactor when thus, drawing acid formers battalion ethanol-type fermentation: the pH value is 6.2～6.9, and basicity is 1400～1600mg/L, COD/SO
4 2-=2.5～3.5, HRT is greater than 6.2h, and the COD rate of load condensate is lower than 22.0kg/m
3D, SO
4 2-Rate of load condensate is less than 7.6kg
-/ m
3The condition of d can guarantee acid formers battalion ethanol-type fermentation.
6. the acetic acid type metabolic way is sought by controlling microbial group
6.1 the key parameter of battalion of regulating and controlling microbial group acetic acid type metabolic way is COD/SO
4 2-Ratio, vitriol rate of load condensate, pH value, ORP and ALK.Table 6 is regulation and control levels of above-mentioned parameter.
The operation control condition of battalion of table 6 microflora acetic acid type metabolic way
| Experimental stage | Control condition | |||||
| COD/SO 4 2- | SO 4 2-Concentration (mg/L) | SO 4 2-Rate of load condensate Ns, Kg/m 3·d) | The pH value | ORP (mV) | Basicity (mg/L) | |
| High COD/SO 4 2-COD/SO in the ratio 4 2-Compare COD/SO 4 2-Ratio | ＞5.0 2.0～5.0 1.0～2.0 | ＜1000 1000～2500 2500→5000 | ＜10.0 ＜7.5 ＜7.5 | 5.0～6.0 6.0～6.5 6.0～7.0 | ＜-300 -300～-400 -300～-400 | ＞1000 1500～2000 1500～2000 |
6.2 the criterion of battalion of microflora acetic acid type metabolic way
Table 7 has compared under the identical operational conditions, when adding vitriol in the waste water and not adding vitriol, produces the difference of sour desulphurization reactor Continuous Flow test microbial metabolism type.By applicant's division, the fermented type that produces sour phase reactor when not adding vitriol is an ethanol-type.Producing has clearly a phenomenon in the sour desulphurization reactor, although promptly the operational conditions of each experimental stage is different, acetate is main component in the liquid phase end products, and its distribution proportion accounts for 50.6～72.2%.
The comparison of acidic ending products distribution when table 7 produces that sour desulphurization reactor adds and do not add vitriol
| Produce sour desulphurization reactor | Distribution/the mmolL of voltaile fatty acid in the liquid phase end products (VFA) -1 | Distribution proportion/the % of acetate | |||||
| Acetate | Propionic acid | Butyric acid | Lactic acid | Ethanol | |||
| Add vitriol (acetic acid type metabolism) | COD/SO 4 2-＝5.0 COD/SO 4 2-＝3.0 COD/SO 4 2-＝4.2 COD/SO 4 2-＝2.0 | 17.6±0.61 22.0±3.38 22.6±3.78 22.3±1.41 | 6.7±0.12 23±0.16 1.9±.04 4.4±0.03 | 7.1±0.08 7.4±0.07 4.9±0.02 8.7±0，03 | 2.8±0.11 1.4±0.01 1.8±0.01 4.2±0.05 | 0.5±0.02 0.7±0.01 0.2±0.04 2.1±0.04 | 50.6±1.86 64.7±3.15 72.2±2.33 58.5±1.41 |
| Do not add vitriol (ethanol-type fermentation) | 12.6±2.25 | 2.3±0.85 | 2.5±0.67 | 13±0.79 | 13.4±2.74 | 39.42±3.43 | |
Fig. 9 also reflects the output of different tests stage volatile acid and the distribution proportion of acetate intuitively.Wherein, the COD/SO in stage 1
4 2-Than being 2.0, the COD/SO in stage 2
4 2-Than being 3.0, the COD/SO in stage 3
4 2-Than being 6.0, the COD/SO in stage 4
4 2-Than being 4.0.It is " acetic acid type " metabolic way that the applicant defines the acidization that the distribution proportion of this acetate in the liquid phase end products have comparative advantage.
According to Fig. 8, it is leading whether the distribution proportion of acetate in the liquid phase end products can account for, and depends on two aspects: whether the competitive capacity of (1) P-SRB, 1-SRB and b-SRB surpasses ASRB; (2) ASRB is to the ability of utilizing of acetate.
6.2.1ASRB the ability of utilizing to acetate
Fig. 2～Fig. 7 proves that SRB utilizes the ability of different carbon sources to be respectively ethanol＞lactic acid＞propionic acid＞butyric acid＞acetate.Be that SRB utilizes the The sulfate reduction rate of acetate minimum.This is to utilize the standard free energy of acetate to be determined by SRB on the one hand, prior reason is that concentration of substrate (COD) is not a limiting factor in the sour desulphurization reactor of product, in the resourceful habitat of substrate, for the purpose of utilizing substrate fast and preserving energy, must be that p-SRB, 1-SRB and b-SRB etc. form dominant population gradually in competition process, utilize ethanol, propionic acid, lactic acid, butyric acid etc. by non-complete oxidation type katabolism mode, end product is an acetate.Therefore, as long as key parameter control is proper, acetate must be the product of this biological chain type cometabolism relation.And the acetic acid type metabolic way is that acetate is endways in the product due to a large amount of accumulation in essence.
6.2.2ASRB competitive capacity
Judge whether a population occupies the index of advantage mainly according to its quantity and activity.Table 8 is SRB population count result stationary phase in different tests stage.As seen, the quantitative relation of dominant population is: 1-SRB＞p-SRB＞b-SRB＞ASRB.This with end products in the composition of VFA just corresponding.The competitive capacity that is the ASRB population is well below p-SRB, 1-SRB and b-SRB.
Table 8 different tests stage SRB population count
| COD/SO 4 2- | Different SRB population counts (individual/ml) | |||||
| l-SRB | p-SRB | HSRB | b-SRB | ASRB | HPA | |
| 3.0 5.0 2.0 | 4.1×10 15 8.9×10 15 7.7×10 13 | 2.8×10 15 2.1×10 15 3.5×10 13 | 3.3×10 14 1.7×10 14 4.3×10 12 | 2.7×10 13 6.5×10 12 9.5×10 11 | 7.4×10 10 1.4×10 10 3.7×10 11 | 1.3×10 12 4.1×10 12 2.6×10 11 |
The ASRB population to acetate to utilize ability to be lower than p-SRB, l-SRB and b-SRB etc. be the SRB population of carbon source with the volatile acid, its competitive capacity is again well below other SRB population.This has constituted the necessary and sufficient condition of judging the acetic acid type metabolic way.
6.3 the biological community structure of battalion's acetic acid type metabolic way
Table 9 is different COD/SO
4 2-Under condition, produce sour desulphurization reactor group's ecological characteristic and the dominant population qualification result of stationary phase.In view of the above, set up the biological community structure mode chart of battalion's acetic acid type metabolic way, as shown in figure 10.
The different COD/SO of table 9
4 2-Than microflora's ecological characteristic and dominant population thereof under the condition
| Coenotype | The ecological characteristic of group | ||||
| Dominant population | The pH value | ORP (mV) | ALK (mg·L -1) | The ratio that is evenly distributed of acetate | |
| High carbon-sulfur ratio stable type group of carbon-sulfur ratio stable type group in the low carbon-sulfur ratio stable type group of low carbon-sulfur ratio metastable type group | AB: Microbacterium/Peptococcus/Bacteroides fermentation unit cell belongs to SRB: Desulfovibrio/Desulfobacter/desulfurization silk Pseudomonas AB: Bacteroides/Microbacterium/Aeromonas/Fusobacterium/zymomonas SRB: Desulfobacter/Desulfococcus/desulfurization silk Pseudomonas AB: streptococcus/Bacteroides/Aeromonas/Fusobacterium/Clostridium SRB: Desulfotomaculum/Desulfovibrio/Desulfobacter/Desulfococcus/desulfurization silk Pseudomonas AB: Bacteroides/Aerobacter/cilium Bacillus/Fusobacterium, Aeromonas/Clostridium/streptococcus SRB: Desulfococcus/Desulfotomaculum/Desulfobacter | 5.1±0.8 5.7±2.4 6.2±1.2 6.9±1.7 | -280±30 -320±35 -380±25 -430±40 | 1200±57 2000±85 1500±122 1700±145 | 50.6±1.8 58.5±1.4 64.7±3.1 72.2±2.3 |
Claims (3)
1. microbial metabolism type regulate and control method during a sulfate wastewater is handled, its operation steps comprises successively: (1) is adopted Continuous Flow to mix fully to stir slot type and is produced sour desulphurization reactor, in establish gas-liquid-solid three-phase separator, and add light filler; (2) acclimated activated sludge; (3) start the biological desulphurization reactive system fast; The metabolic type that it is characterized in that microflora in (4) control biological desulphurization reactive system is the acetic acid type metabolic way: work as COD/SO
4 2-＞5.0 o'clock, vitriol rate of load condensate＜10.0kg/m
3D, pH=5.0～6.0, redox potential＜-300mV, basicity＞1000mg/L; As 5.0＞COD/SO
4 2-＞2.0 o'clock, vitriol rate of load condensate＜7.5kg/m
3D, pH=6.0～6.5 ,-400mV＜redox potential＜-300mV, 1500mg/L＜basicity＜2000mg/L; As 2.0＞COD/SO
4 2-＞1.0 o'clock, vitriol rate of load condensate＜7.5kg/m
3D, pH=6.0～7.0 ,-400mV＜redox potential＜-300mV, 1500mg/L＜basicity＜2000mg/L.
2. microbial metabolism type regulate and control method during sulfate wastewater according to claim 1 is handled is characterized in that the activated sludge acclimatization method is as follows: will plant mud and mix with gac, and adopt sulfate wastewater as nutrient solution, its COD concentration is 3000mg/L, SO
4 2-Concentration is 2000mg/L; The control medium pH value is greater than 5.0, and anaerobism is cultivated; Change nutrient solution in 5 days one time, reduce mud aerial exposure duration during operation as far as possible; Domestication is 25～30 days, the redox potential of domestication muddy water mixed solution bottom when finishing is-200～-250mV.
3. microbial metabolism type regulate and control method during sulfate wastewater according to claim 1 is handled is characterized in that the start-up course of biological desulphurization reactive system is: control COD/SO in the former water
4 2-Ratio is 5.0; Add NaHCO
3The adjusting influent alkalinity is 500mg/L; Flooding velocity was 10.0 liters/day in the 1st～10 day, and hydraulic detention time is 20 hours, improved flow to 20 liter/day after the 11st day, and hydraulic detention time is 10 hours; The starting period of reactor is 20 days.
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