CN104710017A - Method for treating acidic polymetallic sulfate industrial wastewater by use of sulfate-reducing bacteria - Google Patents
Method for treating acidic polymetallic sulfate industrial wastewater by use of sulfate-reducing bacteria Download PDFInfo
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Abstract
The invention relates to a method for treating acidic polymetallic sulfate industrial wastewater by use of sulfate-reducing bacteria (SRB). The method adopts domestic sewage as a diluent to adjust the acidity of industrial wastewater, and fermented soybean meal or corn germ meal is added into domestic sewage to serve as a composite carbon source of anaerobic microbial SRB to treat the acidic polymetallic sulfate industrial wastewater. Domestic sewage is wide in source and rich in nitrogen, sulfur and phosphorus and thus provides abundant nutrition for SRB, the fermented soybean meal and corn germ meal are easy to be absorbed and utilized, and the consumption of both carbon sources and nitrogen sources is reduced by the formed composite carbon source, so that the problem of high cost of the carbon source is solved. As domestic sewage is used for diluting acidic wastewater containing polymetallic sulfate, not only are the problems of harsh SRB application conditions and high treatment cost solved, but also convenience is provided for reclaiming polymetal in sulfate wastewater. The method not only solves the problem of industrial wastewater pollution to guarantee normal running of enterprises, but also lowers the cost to improve the performance of the enterprises.
Description
Technical field:
The present invention relates to a kind for the treatment of process of acidic multimetallic vitriol trade effluent, especially be the thinner regulating trade effluent acidity with sanitary sewage, and add the dregs of beans of fermentation or corn germ cake is anaerobion sulphate reducing bacteria (Sulfate-reducing bacteria at sanitary sewage, SRB) compounded carbons, the acid method containing many metal sulfates waste water of process.
Background technology:
Acidic multimetallic sulfate wastewater source is more extensive, mainly comprise the industrial water drainages such as mining wastewater, non-ferrous metal and solution of gold smelting plant trade effluent, Non-ferrous Metals Processing Factory's acid washing water, Electroplate Factory's plating piece washing water, Steel Plant's pickling draining and electrolysis, agricultural chemicals, medicine, tobacco, paint, pigment, many metal-salts chemical industry, these waste water annual emissions account for 12% of trade effluent according to statistics.Can multiple contaminates be caused after this type of waste water entered environment, as corrosion pipeline equipment, hinder self purification of water body, make the hardening soil, the H produced
2s has serious toxic action to organism, and atmosphere pollution, many metal ions by biological decomposition, constantly cannot accumulate and are difficult to remove, causing long-term hazards to environmental and human health impacts in the environment.
Existing method of wastewater treatment mainly contains two kinds: (1) physico-chemical processes (as neutralisation, reverse osmosis, ion-exchange, electrodialysis etc.).Neutralisation adopts alkaline matter to neutralize, and creates the calcium sulfate being slightly soluble in water in a large number, causes secondary pollution; In addition due to polymetallic cosedimentation, the solid waste of generation needs to carry out piling up thus generation expense at occurring in nature, by also can polluted underground water after rain drop erosion.The process operation complexity that desalt such as reverse osmosis, ion-exchange, electrodialysis, expensive.(2) artificial swamp method.Wetland method floor space is large, and the impact by environment is very large; And process is not thorough, and the hydrogen sulfide of effusion has pollution to environment; When acidity is higher, the improvement of wetland method has its limitation, and expense is also higher.
In recent years, the microbial technique process acidic multimetallic sulfate wastewater of sulphate reducing bacteria (Sulfate-reducing bacteria, SRB) is utilized to achieve greater advance.During with srb assay process peracidity sulfate wastewater, the supercarbonate of generation can make the pH value of processed waste water raise, and the hydrogen sulfide reaction that the many metal ions in waste water can also and produce generates the very low metallic sulfide precipitation of solubleness and removes.The processing costs of SRB facture is low, process that many metal species are many, suitability strong, non-secondary pollution.
H
2S+M
2+→MS↓+2H
+
Wherein M is the metallic cations such as Cd, Fe, Ni, Cu, Cr, Zn.
First the key issue of sulphate reducing bacteria microbiological treatment technology is carbon source.According to the katabolism mechanism of SRB, SRB except with vitriol as except final electron acceptor(EA), also need additional carbon and provide energy for it, as shown in Figure 1.
Carbon source mainly provides the carbon skeleton of cell to the effect of microorganism growth metabolism, provides the energy needed for cell activities, as the energy and the electron donor of SRB growth, is the limiting factor affecting SRB growth.Nitrogenous source is the same with carbon source, is the essential substance of synthesized micro-organism cellularstructure composition.Therefore, select any material to do Carbon and nitrogen sources and become the key issue that can this technology industrially apply.Carbon source is divided into organic carbon source and the large class of inorganic carbon source two.Thought that SRB only utilized limited matrix as organic carbon source and electron donor in the past, in recent years, owing to selecting the substratum of different carbon source, the organic carbon source that SRB utilizes and electron donor kind constantly expand, and find so far to support that its matrix grown is more than kind more than 100.
Renze T., et al.Biological sulphate reduction using gas-lift reactor fed withhydrogen and carbon dioxide as energy and carbon source.Biotech.Bioeng., 1994,44 (5): 586-594, with H
2, CO, CO
2for inorganic carbon source and the energy of SRB, treatment S O
4 2-concentration high (3.7g/L) and effective (water outlet is 0.1g/L only), but its source is limited, and toxicity is very big.
Yin Xiuzhen etc. " sulphate reducing bacteria administers the experimental study of Acidic Waste Water from Coal Mines " Institutes Of Technology Of Taiyuan's master thesis, 2007, when taking molasses as carbon source, inlet flow-patterm 3.0, but this method HRT time is longer, rinses excessive mud by improving backflow flow velocity and adopt N
2(6L/h) stripping H
2s, processing cost is high.
" corn cob is that carbon source the realizes acidic mine waste water biological treatment " industrial safety such as Wan Youling, Li Longhai and environmental protection, 2004,30 (5): 11-15, when taking corn cob as carbon source, can treatment S O
4 2-concentration is well below 3.0g/L.
" sanitary sewage the is carbon source process vitriol mine wastewater feasibility test " water resources such as Xiao Liping and Hydraulic Projects journal, 2008,19 (6): 49-52, using sanitary sewage as carbon source, as [COD]/[SO
4 2-] when being 2.5, the clearance of sulfate radical is up to 83.2%, Fe
2+the removal of 96% is all reached, Mn under different ratio
2+it is then the removal effect that lower C/S is issued to 87%.
Second key issue of sulphate reducing bacteria microbiological treatment technology is pH.PH is the principal element affecting SRB metabolic activity, the too low or too high activity that all can affect SRB of pH, affects its treatment effect to acid waste water simultaneously.Xu Yaling, Wu Jiandong " pH value is on the impact of sulphate reducing bacteria granule sludge performance " process water and waste water, 2010,41 (1): 32-35, SRB is generally adapted at growth in neutral pH range, the SRB of different investigator's report grows optimal ph difference, and general pH value sulfate reduction when 6.0-8.0 is feasible; Time between 6.48-7.43, sulfate reduction effect is best; Maximum sulfate reduction rate can be obtained when pH value is 6.6.Highly acidity is an acid distinguishing feature containing many metal sulfates waste water, and pH generally only has 1.5-4.5.In existing process method for waste water, pH is partial to neutrality more, which limits its application.From pH value angle, carry out neutralizing the acid problem that can solve waste water with alkaline matter simply, but produce various salt thus, cause secondary pollution.Because the increase of inorganic salt can improve the osmotic pressure of water, have detrimentally affect to limnobios, plant-growth, in salinization area, the salt in the surface water, underground water will endanger soil quality further, thus can not reach emission standard.
The effect of basicity in Waste Water Treatment participates in setting up effective acid-base buffer system, reduces the rangeability of system pH.In anaerobic system, pH value is that the buffer system set up by weak acid and weak base all kinds of in system determines, weak acid and weak base comprises: RCOO
-, NH
3, CO2, H
2s,
h
2o etc.
Su Delin etc. " the basicity change of ABR reactor and study on regulation " environmental science, 2006,27 (10): 2024-2027, in system for anaerobic treatment, fermentable often produces a large amount of H
2cO
3with voltaile fatty acid (VFA), need to have suitable basicity in system to neutralize, to prevent pH value from declining, maintain the activity of anaerobion.
Wang Aijie etc. " in sulfate-reducing process the balance of basicity and adjustment " Harbin Institute of Technology's journal, 2003,35 (6): 651-654, the basicity in research discovery system for anaerobic treatment mainly sulfate reduction causes system basicity to increase, and pH value raises.Meanwhile, cushion the VFA that acid-producing bacteria produces during basicity postscript, resist due to CO
2generation and dissolve impact on pH value, maintain pH value needed for reaction system.In certain limit, pH value increases along with the raising of basicity, but also depends on the factors such as the ratio of VFA in the water quality of waste water, organic loading rate, end meta-bolites.Meanwhile, influent alkalinity for reaction system basicity balance and adjustment and to maintain microbic activity be also necessary.
Sanitary sewage has certain basicity, if by initial pH on wastewater=2.01, containing acidic mine waste water sanitary sewage (pH=7.41) dilution of 2500mg/L sodium sulfate, only need dilute the pH=7.01 that 8 times just can make system, and dilute with water needs dilution 10 under the same conditions
5doubly.
Not only containing large amount of organic in sanitary sewage, as Mierocrystalline cellulose, starch, carbohydrate and fat protein etc., and muriate containing inorganic salts, vitriol, phosphoric acid salt, supercarbonate and sodium, potassium, calcium, magnesium etc.Total feature is that nitrogenous, sulphur and phosphorus are high, nutritious, can do the Carbon and nitrogen sources of microbial bacteria race, but due to a large amount of carbon nitrogen source of high concentration sulphate consumption in application in the past, therefore simple sanitary sewage can not meet the needs of high concentration sulphate reduction.
Summary of the invention:
Object of the present invention is just for above-mentioned existing key technical problem, in line with the epoch theory of the treatment of wastes with processes of wastes against one another, environmental protection, take sanitary sewage as the thinner of acidic multimetallic sulfate wastewater, make it to reach the appropriate pH environment keeping microorganism active, and make the method for the compounded carbons process acidic multimetallic vitriol trade effluent of SRB with natural organic matter.
The object of the invention is to be achieved through the following technical solutions:
The method of sulphate reducing bacteria method process acidic multimetallic vitriol trade effluent, take sanitary sewage as the thinner regulating trade effluent acidity, and add the dregs of beans of fermentation or corn germ cake as anaerobion sulphate reducing bacteria (Sulfate-reducing bacteria at sanitary sewage, the method of compounded carbons process acidic multimetallic sulfate wastewater SRB), comprises the following steps:
A, that soybean meal or corn germ cake are placed in vessel is airtight, and spontaneous fermentation 3 ~ 5 days is for subsequent use;
B, the dregs of beans fully fermented or corn germ cake are added sanitary sewage by solid-to-liquid ratio 1:20 ~ 1:40 wear into below 180 orders, make the compounded carbons being suitable for SRB growth;
C, from SRB exclusive substratum for subsequent use, draw SRB bacterium liquid, acidic multimetallic sulfate wastewater mixes with SRB bacterium liquid by 10+1 ~ 10+5 by volume;
D, to mix containing the acidic multimetallic sulfate wastewater of SRB by carbon-sulfur ratio 1:1 ~ 1:3 with compounded carbons solution, mensuration sulfate concentration, metal ion content and pH, and pass into anaerobism moving-burden bed reactor with the flow velocity of 0.2L/h ~ 0.5L/h;
E, the waste water of above-mentioned process is carried out water cycle, pass into anaerobism moving-burden bed reactor with the flow velocity of 0.2L/h ~ 0.5L/h;
F, SO
4 2-with the S generated after SRB effect
2-be combined with many kinds of metal ions and form metallic sulfide and precipitate, SO in acidic multimetallic sulfate wastewater
4 2-concentration is down to below 500mg/L, and water outlet is neutral, reaches discharge of wastewater national grade ii standard.
Beneficial effect: sanitary sewage wide material sources, and be rich in nitrogen, sulphur and phosphorus, for SRB provides sufficient nutrient, fermented bean dregs and corn germ cake are easily absorbed and used, the compounded carbons formed decreases the consumption of Carbon and nitrogen sources, solves the economy problems of carbon source.With sanitary sewage, acidity is diluted containing many metal sulfates waste water, participate in natural organic matter simultaneously and make SRB compounded carbons, not only solve the problem that SRB application conditions is harsh and processing cost is high, also for the many metals in reclaim(ed) sulfuric acid salt waste water provide convenience.The method is applied to bargh, not only can solve the pollution problem of trade effluent, ensures the normal operation of enterprise, and has saved cost, improve the performance of enterprises.The method of wastewater treatment of a great potential.
Accompanying drawing explanation
The catabolic process of accompanying drawing 1SRB
Accompanying drawing 2 sanitary sewage water quality parameter
Accompanying drawing 3 anaerobism moving-burden bed reactor
1 water inlet container 2 peristaltic pump 3 thermostatically heating rod 4 anaerobic reactor 5 water bath device 6 thermometer 7 submersible pump 8 voltage stabilizing bottle 9 zinc ammonia complexing solution 10 wet test meter 11 discharging devices
Embodiment:
Below in conjunction with drawings and Examples, the present invention is described in further detail:
The method of sulphate reducing bacteria method process acidic multimetallic vitriol trade effluent, take sanitary sewage as the thinner regulating trade effluent acidity, and add the dregs of beans of fermentation or corn germ cake as anaerobion sulphate reducing bacteria (Sulfate-reducing bacteria at sanitary sewage, the method of compounded carbons process acidic multimetallic sulfate wastewater SRB), comprises the following steps:
A, that soybean meal or corn germ cake are placed in vessel is airtight, and spontaneous fermentation 3 ~ 5 days is for subsequent use;
B, the dregs of beans fully fermented or corn germ cake are added sanitary sewage by solid-to-liquid ratio 1:20 ~ 1:40 wear into below 180 orders, make the compounded carbons being suitable for SRB growth;
C, from SRB exclusive substratum for subsequent use, draw SRB bacterium liquid, acidic multimetallic sulfate wastewater mixes with SRB bacterium liquid by 10+1 ~ 10+5 by volume;
D, to mix containing the acidic multimetallic sulfate wastewater of SRB by carbon-sulfur ratio 1:1 ~ 1:3 with compounded carbons solution, mensuration sulfate concentration, metal ion content and pH, and pass into anaerobism moving-burden bed reactor with the flow velocity of 0.2L/h ~ 0.5L/h;
E, the waste water of above-mentioned process is carried out water cycle, pass into anaerobism moving-burden bed reactor with the flow velocity of 0.2L/h ~ 0.5L/h;
F, SO
4 2-with the S generated after SRB effect
2-be combined with many kinds of metal ions and form Polymetallic sulphide and precipitate, SO in acidic multimetallic sulfate wastewater
4 2-concentration is down to below 500mg/L, and water outlet is neutral, reaches discharge of wastewater national grade ii standard.
Testing device used is anaerobism moving-burden bed reactor, and useful volume is 7.5L, in right cylinder, material is synthetic glass, and reactor is built-in with submersible pump, plays stirring action, make strength of solution in reactor homogeneous, and fully contact with carbon source, sulfate reduction is carried out smoothly.Water inlet adopts upflowing, and hydraulic detention time is controlled by the flooding velocity of peristaltic pump.
Testing apparatus is in water bath with thermostatic control, and temperature keeps (35 ± 1) DEG C, stirs with intermittent mode, and every 30min stirs once, and each stirring continues 15-20min.When test is carried out, water inlet solution is entered by peristaltic pump, and flooding velocity is controlled by peristaltic pump, the solution entered is at the lowermost end of anaerobism moving-burden bed reactor, reacted by the stirring action and SRB that slip into pump, the waste water after SRB metabolism is discharged by water outlet, the H that metabolism produces
2the gases such as S are by venting port, and absorbed by zinc ammonia complexing solution by voltage stabilizing bottle, residual gas is by emitting after wet test meter.
Embodiment 1
A, that soybean meal is placed in vessel is airtight, and spontaneous fermentation 3 days is for subsequent use;
B, the dregs of beans fully fermented is added sanitary sewage by solid-to-liquid ratio 1:20 wear into below 180 orders, make the compounded carbons being suitable for SRB growth;
C, get mine, Jilin Ji'an pH=1.56 containing 500mgL
-1fe
2+acidic sulfate-containing wastewater 1L, its sulfate concentration [SO
4 2-] 3gL
-1, add SRB bacterium liquid in the ratio of 10+1;
D, by the above-mentioned acidity containing SRB containing Fe
2+sulfate wastewater and compounded carbons solution press carbon-sulfur ratio [SO
4 2-]/[COD] for after 1:2 mixes, record sulfate concentration 198.73mgL
-1, Fe
2+concentration 3.83mgL
-1with pH 5.80, pass into the anaerobism MBBR of effective volume 7.5L with the flow velocity of 0.2L per hour;
E, go out water cycle, the waste water of above-mentioned process is passed into the anaerobism moving-burden bed reactor of effective volume 7.5L with the flow velocity of 0.2L per hour;
F, SO
4 2-the S generated after reacting with anaerobion
2-with Fe
2+in conjunction with formation FeS precipitation, acid containing Fe
2+sO in sulfate wastewater
4 2-clearance 87.32%, SO
4 2-concentration is down to 25.20mgL
-1, Fe
2+clearance 85.90%, Fe
2+concentration is down to 0.54mgL
-1, water outlet pH is 6.92, reaches discharge of wastewater national grade ii standard.
Embodiment 2
A, that corn germ cake is placed in vessel is airtight, and spontaneous fermentation 4 days is for subsequent use;
B, the corn germ cake fully fermented is added sanitary sewage by solid-to-liquid ratio 1:30 wear into below 180 orders, make the compounded carbons being suitable for SRB growth;
C, get mine, Liaoning pH=2.07 containing 1000mgL
-1cu
2+acidic sulfate-containing wastewater 1L, its vitriol (SO
4 2-) concentration 8gL
-1, add SRB bacterium liquid in the ratio of 10+3;
D, by the above-mentioned acidity containing SRB containing Cu
2+sulfate wastewater and compounded carbons solution press carbon-sulfur ratio [SO
4 2-]/[COD] for after 1:3 mixes, record sulfate concentration 259.36mgL
-1, Cu
2+concentration 1.37mgL
-1with pH 6.07, pass into the anaerobism moving-burden bed reactor of effective volume 7.5L with the flow velocity of 0.3L per hour;
E, go out water cycle, the waste water of above-mentioned process is passed into the anaerobism moving-burden bed reactor of effective volume 7.5L with the flow velocity of 0.3L per hour;
F, SO
4 2-the S generated after reacting with anaerobion
2-with Cu
2+in conjunction with formation CuS precipitation, acid containing Cu
2+sO in sulfate wastewater
4 2-clearance reaches 81.20%, SO
4 2-concentration is down to 48.76mgL
-1, Cu
2+clearance >99%, water outlet pH is 7.04, reaches discharge of wastewater national grade ii standard.
Embodiment 3
A, that soybean meal is placed in vessel is airtight, and spontaneous fermentation 5 days is for subsequent use;
B, the dregs of beans fully fermented is added sanitary sewage by solid-to-liquid ratio 1:40 wear into below 180 orders, make the compounded carbons being suitable for SRB growth;
C, get Tonghua, Jilin Province mine pH=2.0 containing 3000mg/L Zn
2+acidic sulfate-containing wastewater 1L, its vitriol (SO
4 2-) concentration 15gL
-1, add SRB bacterium liquid in the ratio of 10+5;
D, by the above-mentioned acidity containing SRB containing Zn
2+sulfate wastewater and compounded carbons solution press carbon-sulfur ratio [SO
4 2-]/[COD] for after 1:2.5 mixes, record sulfate concentration 5227.24mgL
-1, Zn
2+concentration 22.24mgL
-1with pH 6.25, pass into the anaerobism moving-burden bed reactor of effective volume 7.5L with the flow velocity of 0.4L per hour;
E, go out water cycle, the waste water of above-mentioned process is passed into the anaerobism moving-burden bed reactor of effective volume 7.5L with the flow velocity of 0.4L per hour;
F, SO
4 2-the S generated after reacting with anaerobion
2-with Zn
2+in conjunction with formation ZnS precipitation, acid containing Zn
2+sO in sulfate wastewater
4 2-clearance reaches 91.67%, SO
4 2-concentration is down to 435.43mgL
-1, Zn
2+clearance 84.44%, Zn
2+concentration is down to 3.46mgL
-1, water outlet pH is 7.27, reaches discharge of wastewater national grade ii standard.
Claims (1)
1. the method for a sulphate reducing bacteria method process acidic multimetallic vitriol trade effluent, it is characterized in that, take sanitary sewage as the thinner regulating trade effluent acidity, and add the dregs of beans of fermentation or corn germ cake as anaerobion sulphate reducing bacteria (Sulfate-reducing bacteria at sanitary sewage, the method of compounded carbons process acidic multimetallic sulfate wastewater SRB), comprises the following steps:
A, that soybean meal or corn germ cake are placed in vessel is airtight, and spontaneous fermentation 3 ~ 5 days is for subsequent use;
B, the dregs of beans fully fermented or corn germ cake are added sanitary sewage by solid-to-liquid ratio 1:20 ~ 1:40 wear into below 180 orders, make the compounded carbons being suitable for SRB growth;
C, from SRB exclusive substratum for subsequent use, draw SRB bacterium liquid, acidic multimetallic sulfate wastewater mixes with SRB bacterium liquid by 10+1 ~ 10+5 by volume;
D, to mix containing the acidic multimetallic sulfate wastewater of SRB by carbon-sulfur ratio 1:1 ~ 1:3 with compounded carbons solution, mensuration sulfate concentration, metal ion content and pH, and pass into anaerobism moving-burden bed reactor with the flow velocity of 0.2L/h ~ 0.5L/h;
E, the waste water of above-mentioned process is carried out water cycle, pass into anaerobism moving-burden bed reactor with the flow velocity of 0.2L/h ~ 0.5L/h;
F, SO
4 2-with the S generated after SRB effect
2-be combined with many kinds of metal ions and form metallic sulfide and precipitate, SO in acidic multimetallic sulfate wastewater
4 2-concentration is down to below 500mg/L, and water outlet is neutral, reaches discharge of wastewater national grade ii standard.
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Cited By (7)
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|---|---|---|---|---|
| CN106495390A (en) * | 2015-09-08 | 2017-03-15 | 铜仁市万山区盛和矿业有限责任公司 | A kind of processing method of acid waste water |
| CN108192807A (en) * | 2018-01-10 | 2018-06-22 | 轻工业环境保护研究所 | A kind of energy resource system by means of sulfur cycle |
| CN109231450A (en) * | 2018-10-23 | 2019-01-18 | 南京大学环境规划设计研究院股份公司 | A kind of cohesion nutrient source SRB sludge immobilization particle and preparation method thereof for heavy metal containing wastewater treatment |
| CN110563249A (en) * | 2019-08-16 | 2019-12-13 | 安徽省地质矿产勘查局321地质队 | Biological treatment system and method for acidic mining wastewater |
| CN113526790A (en) * | 2021-07-21 | 2021-10-22 | 上海市政工程设计研究总院（集团）有限公司 | Anaerobic remediation system and treatment method for mine wastewater |
| CN113860517A (en) * | 2021-10-21 | 2021-12-31 | 南昌航空大学 | Method for treating chemical nickel plating cleaning wastewater by using sulfate reducing bacteria |
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| CN106495390A (en) * | 2015-09-08 | 2017-03-15 | 铜仁市万山区盛和矿业有限责任公司 | A kind of processing method of acid waste water |
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| CN110563249A (en) * | 2019-08-16 | 2019-12-13 | 安徽省地质矿产勘查局321地质队 | Biological treatment system and method for acidic mining wastewater |
| CN113526790A (en) * | 2021-07-21 | 2021-10-22 | 上海市政工程设计研究总院（集团）有限公司 | Anaerobic remediation system and treatment method for mine wastewater |
| CN113860517A (en) * | 2021-10-21 | 2021-12-31 | 南昌航空大学 | Method for treating chemical nickel plating cleaning wastewater by using sulfate reducing bacteria |
| CN117585853A (en) * | 2023-12-15 | 2024-02-23 | 广东江铜桃林生态环境有限公司 | Biological low-carbon vulcanization treatment system and treatment method for heavy metal mine acidic wastewater |
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Application publication date: 20150617 |