CN102276060A - Method for treating acidic heavy-metal-containing sulfate wastewater by sulfate reducing bacteria - Google Patents
Method for treating acidic heavy-metal-containing sulfate wastewater by sulfate reducing bacteria Download PDFInfo
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- CN102276060A CN102276060A CN2011102200723A CN201110220072A CN102276060A CN 102276060 A CN102276060 A CN 102276060A CN 2011102200723 A CN2011102200723 A CN 2011102200723A CN 201110220072 A CN201110220072 A CN 201110220072A CN 102276060 A CN102276060 A CN 102276060A
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Abstract
The invention relates to a method for treating acidic heavy-metal-containing sulfate wastewater by sulfate reducing bacteria (SRB). The method comprises the following steps of: putting soybeans into a utensil, fermenting, and preparing a carbon source which is suitable for SRB growth by using the fermented soybeans; mixing the acidic heavy metal sulfate wastewater and the carbon source, and introducing the mixture into an anaerobic moving bed biological film reactor; and combining S<2-> generated by SO4<2-> under the action of the SRB and heavy metal ions to form a heavy metal sulfide precipitate. The concentration of the SO4<2-> in the acidic heavy-metal-containing sulfate wastewater is reduced to below 250 mg/L, when the pH value of inflow is equal to 1.5 to 53, the pH value of effluent is kept 6.12 to 7.41, and the discharge standard of national secondary sewage is met; and acidic inflow and neutral effluent are realized, a large amount of alkali for neutralizing wastewater is saved, and SRB method in which other carbon sources are adopted cannot achieve the effect. The removal rate of the fully-fermented soybeans serving as the carbon source on the SO4<2-> is higher than that of organic matter such as glucose and the like, and the cost is far lower than that of synthetic organic solvents. Therefore, the problems of severe SRB application condition and high treatment cost are solved, and the favorable condition is provided for recovering heavy metal in the sulfate wastewater.
Description
Technical field:
The present invention relates to a kind of treatment process of sulfate wastewater, especially the anaerobion method that is carbon source with full fermentation soya bean is handled the method for hydrosulphate waste water.
Background technology:
The hydrosulphate wastewater source that contains heavy metal is extensive, mainly comprise industrial water drainages such as mining wastewater, non-ferrous metal, the dedusting draining of gold smelting factory, acidleach calcining (roasting of sulfide ores after product) draining, 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, heavy metallic salt chemical industry, China's annual emissions accounts for 12% of trade effluent according to statistics.
This type of waste water can cause multiple pollution after entering environment: sour water makes the hardening soil, and growth harms the crops; Be dissolved in the H in the water
2S has serious toxic action to organism, and escaping in the air also can atmosphere pollution; Heavy metal ion can't be by biological decomposition in environment, constantly accumulates and is difficult to remove, and environment and HUMAN HEALTH are caused long-term hazards.
Traditional improvement method mainly contains two kinds: the one, and Wingdale or lime neutralisation adopt the method that adds lime or Wingdale in waste water, the neutralizing acid wastewater.But this method produces a large amount of calcium sulfate and heavy metal precipitation is piled up in environment, and the secondary pollution that causes is difficult to remove.The 2nd, the wetland method.The advantage of wetland method is a less investment, and working cost is low, but floor space is big, is subjected to such environmental effects serious; And processing is not thorough, and when acidity was higher, the improvement of wetland method had its limitation, and a lot of people query to its long-term effectiveness.
Other processing cost as methods such as ion exchange method, electrodialysis and reverse osmosiss is all higher.In recent years, the microbial technique that utilizes sulphate reducing bacteria (SRB) is handled the hydrosulphate waste water that contains heavy metal carried out big quantity research, and obtained bigger progress.The srb assay processing costs is low, suitability is strong, and its principle is as final electron acceptor(EA), with SO with vitriol
4 2-Be reduced to S
-2Form precipitation with heavy metal and remove, avoid secondary pollution.
Sulphate reducing bacteria needs external carbon, nitrogenous source.Wherein carbon source is the limiting factor that influences the SRB growth as the energy and the electron donor of SRB growth, and nitrogenous source is the essential substance of synthesized micro-organism cellularstructure composition.Carbon source is divided into organic carbon source and inorganic carbon source two big classes, therefore, selects what material is done carbon, can nitrogenous source becomes this technology in industrial key in application problem.
H
2, CO, CO
2Be inorganic carbon source, treatment S O
4 2-Concentration height (3.7g/L) and effective (water outlet is 0.1g/L only), but its source is limited, and toxicity is very big.CO content caused negative impact up to 20% o'clock to SRB in the gas phase, but SRB still can grow.The required organic carbon source of SRB should be the short carbon chain organism.Thought in the past that SRB only utilized limited matrix as organic carbon source and electron donor, in recent years, owing to select the substratum of different carbon sources for use, organic carbon source and electron donor kind that SRB utilizes constantly enlarge, find so far to support that the matrix of its growth has surpassed kind more than 100, as being carbon source with molasses, domestic refuse acid fermentation product, voltaile fatty acid (VFA), corn cob etc., when glucose is carbon source, but treatment S O
4 2-Concentration is up to 3.0g/L.
In addition, because of SRB only survives under neutrallty condition, and the sulfate wastewater that contains heavy metal mostly is acid, and difficult for this class wastewater treatment, therefore, pH is the principal element that influences the SRB metabolic activity.PH crosses the low or too high activity that can influence SRB, influences it simultaneously to SO
4 2Reduction effect.The SRB growth optimal ph of different investigator's reports is sample not, the general pH value was at 6.0～8.0 o'clock, sulfate reduction is feasible, 6.48 in the time of between～7.43, the sulfate reduction effect is best, can obtain maximum sulfate reduction rate when the pH value is 6.6, has research to think that SRB is more suitable for growth under 7.0～7.8 the slight alkalinity condition, be 5.0～9.0 to the tolerance range of pH value.Recently have research report SRB can also grow under the strong acidic condition of pH4.0, its patient maximum pH is 9.5.High acidity is a distinguishing feature that contains heavy metal hydrosulphate waste water, and pH generally has only 2.5～4.5.People's neutralisation commonly used or sulfuration method were handled sulfate wastewater in the past, needed to drop into a large amount of neutralizing agent or vulcanizing agent, and cost is higher.When handling the peracidity sulfate wastewater with srb assay, [H
+] influence the activity and the microbic activity of enzyme on the cell walls with the enzyme interacting of cytolemma.Suitable carbon, the nitrogenous source that therefore, if can select to improve the capacity antacid of SRB, can reduce processing cost again then are the vital difficult problems of srb assay industrialization.At present, can do carbon source in the kind of having studied more than 100 and support all to exist or the application conditions harshness in the matrix of SRB growth, or the high problem of processing cost.
Summary of the invention:
Purpose of the present invention just is at above-mentioned the deficiencies in the prior art, provides a kind of sulphate reducing bacteria (SRB) to handle the acid method that contains heavy metal sulfate waste water.
The objective of the invention is to be achieved through the following technical solutions:
Sulphate reducing bacteria is handled the acid method that contains heavy metal sulfate waste water, comprises following order and step:
A, immersion soya bean are to expanding;
B, soaked soya bean is steamed or boil;
C, the soya bean that will steam or boil place vessel, controlled temperature at 50 ℃ with bottom fermentation 3-5 days, to growing haircuts;
D, the soya bean that will fully ferment add water mill in 1: 25 ratio of solid-liquid and become the following soya-bean milk of 200 orders, make the carbon source that is suitable for the sulfate reduction bacteria growing;
E, acidity is contained heavy metal sulfate waste water mix, feed the anaerobism MBBR with the flow velocity of 0.2L-0.5L per hour with carbon source;
F, SO
4 2-S with the generation of SRB effect back
2-Form the heavy metal sulfide precipitation with heavy metal ion, acidity contains SO in the heavy metal sulfate waste water
4 2-Concentration is reduced to below the 250mg/L, reaches discharging standards.
The described acidity of step e contains heavy metal sulfate waste water and the carbon source ratio of mixture is SO
4 2-/ COD=1/3.
Described acidity contains the pH=1.5-5.3 of heavy metal sulfate waste water.
Beneficial effect: do the carbon source that SRB grows with soybean, the different carbonaceous organic materials of the various structures in the soybean can be used as carbon source, and each amino acid can be used as nitrogenous source and utilized by microorganism, increases the SRB activity simultaneously, reaches acid water inlet, neutral water outlet; Increase the per-cent of COD and total nitrogen behind the fermented soybean greatly, reduced the consumption of carbon, nitrogenous source, better solved the economy problems of carbon source.Various compositions in the soybean can provide stable energy and electron donor for SRB, soybean is by fermentation, macromole in the soybean resolves into small molecules and some insoluble compounds is resolved into the solubility low molecular compound, for bacterium utilizes, through testing COD and the nitrogenous percentage that full fermented soybean can improve it; For SRB provides competent natural organic carbon, nitrogenous source.With full fermented soybean is carbon, nitrogenous source, and the hydrosulphate waste water that contains heavy metal is carried out the acidity test, and pH was at 1.5 o'clock in water inlet, and water outlet pH can rise to 6.12, and Δ pH is 4.7, and system is strong to the surge capability of acid; When water inlet pH was between 1.5-6.0, water outlet pH was stabilized in 6.12～7.41, meets national B-grade sewage emission standard pH=6.0～9.0; Realized acid water inlet, neutral water outlet has been saved and has been used in a large number and the alkali of waste water, and this also is to adopt the srb assay institute of other carbon source not reach.With full fermented soybean is carbon, nitrogenous source, intakes under different pH, with water inlet pH raises, the sulfate radical clearance obviously raises, when pH is 2.0, and SO
4 2-Clearance increases to 80.89%, and pH is 3.0 o'clock in water inlet, and the clearance of sulfate radical is 91.21, and the pH7.0 effect is best, reaches 92.31%, and pH is during by 3-8 in water inlet, and the sulfate radical clearance can remain on more than 90%, is much higher than the prior art index.Full fermented soybean is to SO
4 2-Clearance is higher than glucose, and price is far below glucose, and is lower than the best Sodium.alpha.-hydroxypropionate of sulfate radical clearance effect.Making carbon source with full fermented soybean and not only solved the harsh and high problem of processing cost of SRB application conditions, also is non-ferrous metal in the reclaim(ed) sulfuric acid salt waste water condition of providing convenience.
Embodiment:
Be described in further detail below in conjunction with embodiment:
Sulphate reducing bacteria (SRB) is handled the acid method that contains heavy metal sulfate waste water, comprises following order and step:
A, immersion soya bean are to all expanding;
B, soaked soya bean is steamed or boil;
C, the soya bean that will steam or boil place vessel, controlled temperature at 50 ℃ with bottom fermentation 3-5 days, to growing haircuts;
D, the soya bean that will fully ferment add water mill in 1: 25 ratio of solid-liquid and become the following soya-bean milk of 200 orders, make the carbon source that is suitable for sulphate reducing bacteria (SRB) growth;
E, the acid heavy metal sulfate wastewater of pH=1.5-6.3 is mixed with carbon source, acid heavy metal sulfate wastewater and carbon source ratio of mixture are SO
4 2-/ COD=1/3 feeds the anaerobism MBBR with the flow velocity of 0.2L-0.5L per hour;
F, SO
4 2-S with the generation of SRB effect back
2-Combine formation heavy metal sulfide precipitation with heavy metal ion, acidity contains SO in the heavy metal sulfate waste water
4 2-Concentration is reduced to below the 250mg/L, reaches discharging standards.
Embodiment 1
A, get the 10g soya bean, soak to all expanding;
B, soaked soya bean is steamed or boil;
C, the soya bean that will steam or boil place vessel, controlled temperature at 50 ℃ with bottom fermentation 3 days, to growing haircuts;
D, the soya bean that will fully ferment add water mill in 1: 25 ratio of solid-liquid and become the following soya-bean milk of 200 orders, make the carbon source 300L that is suitable for sulphate reducing bacteria (SRB) growth;
E, get the Fe that contains of certain mine pH=1.5
+ 2(185mg/L), Fe
+ 3(450mg/L) hydrosulphate waste water 1L, its sulfate radical (SO
4 2-) concentration 3.0g/L, press SO
4 2-The mixed of/COD=1/3 feeds the anaerobism MBBR of effective volume 7.5L with the flow velocity of 0.3L per hour;
F, SO
4 2-At the S that generates with SRB effect back
2-Combine formation iron content sulfide precipitation with iron ion, SO in the acid sulfate wastewater of iron content
4 2-Clearance reaches 92.3%, SO
4 2-Concentration is reduced to 231mg/L, reaches discharging standards.
Embodiment 2
A, get the 10g soya bean, soak to all expanding;
B, soaked soya bean is steamed or boil;
C, the soya bean that will steam or boil place vessel, controlled temperature at 50 ℃ with bottom fermentation 4 days, to growing haircuts;
D, the soya bean that will fully ferment add water mill in 1: 25 ratio of solid-liquid and become the following soya-bean milk of 200 orders, make the carbon source 300L that is suitable for the sulfate reduction bacteria growing;
E, get the Cu that contains of certain mine pH=3.0
+ 2Hydrosulphate waste water 1L (550mg/L), its vitriol (SO
4 2-) concentration 3.0g/L, press SO
4 2-The mixed of/COD=1/3 feeds the anaerobism MBBR of effective volume 7.5L with the flow velocity of 0.4L per hour;
F, SO
4 2-At the S that generates with SRB effect back
2-Combine formation copper bearing sulphide precipitation with cupric ion, SO in the acid sulfate wastewater of cupric
4 2-Clearance reaches 92.7%, SO
4 2-Concentration is reduced to 220mg/L, reaches discharging standards.
Embodiment 3
A, get the 10g soya bean, soak to all expanding;
B, soaked soya bean is steamed or boil;
C, the soya bean that will steam or cook place vessel, controlled temperature at 50 ℃ with bottom fermentation 5 days, to growing haircuts;
D, the soya bean that will fully ferment add water mill in 1: 25 ratio of solid-liquid and become the following soya-bean milk of 200 orders, make the carbon source 300L that is suitable for the sulfate reduction bacteria growing;
E, get certain mine pH=3.5 and contain Zn
+ 2Hydrosulphate waste water 1L (400mg/L), its vitriol (SO
4 2-) concentration 3.4g./L, press SO
4 2-The mixed of/COD=1/3 feeds the anaerobism MBBR of effective volume 7.5L with the flow velocity of 0.5L per hour;
F, SO
4 2-The S that after reacting, generates with anaerobion
2-Combine formation with zine ion and contain the zinc sulfide precipitation, contain SO in the zincic acid sulfate wastewater
4 2-Clearance reaches 92.9%, SO
4 2-Concentration is reduced to 242mg/L, reaches discharging standards.
Claims (3)
1. a sulphate reducing bacteria is handled the acid method that contains heavy metal sulfate waste water, it is characterized in that, comprises following order and step:
A, immersion soya bean are to expanding;
B, soaked soya bean is steamed or boil;
C, the soya bean that will steam or boil place vessel, controlled temperature 50 ℃ with bottom fermentation 3-5 days, grow haircuts to z;
D, the soya bean that will fully ferment add water mill in 1: 25 ratio of solid-liquid and become the following soya-bean milk of 200 orders, make the carbon source that is suitable for the sulfate reduction bacteria growing;
E, acidity is contained heavy metal sulfate waste water mix, feed the anaerobism MBBR with the flow velocity of 0.2L-0.5L per hour with carbon source;
F, SO
4 2-The S that after the SRB effect, generates
2-Combine formation heavy metal sulfide precipitation with heavy metal ion, acidity contains SO in the heavy metal sulfate waste water
4 2-Concentration is reduced to below the 250mg/L, reaches discharging standards.
2. handle the acid method that contains heavy metal sulfate waste water according to the described sulphate reducing bacteria of claim 1, it is characterized in that the described acidity of step e contains heavy metal sulfate waste water and the carbon source ratio of mixture is SO
4 2-/ COD=1/3.
3. handle the acid method that contains heavy metal sulfate waste water according to the described sulphate reducing bacteria of claim 1, it is characterized in that described acidity contains the pH=1.5-5.3 of heavy metal sulfate waste water.
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| CN103086578A (en) * | 2013-03-05 | 2013-05-08 | 中国科学院新疆生态与地理研究所 | Method for treating quintavalent-antimony-containing wastewater with sulfate mixed bacteria |
| CN103362550A (en) * | 2013-05-10 | 2013-10-23 | 合肥学院 | Method for performing in situ treatment on acid mine water by using crop seed husks |
| CN104710017A (en) * | 2015-02-08 | 2015-06-17 | 吉林大学 | Method for treating acidic polymetallic sulfate industrial wastewater by use of sulfate-reducing bacteria |
| CN104773925A (en) * | 2015-04-23 | 2015-07-15 | 合肥工业大学 | Method for simultaneously treating refuse leachate and acidy mine drainage |
| CN104944575A (en) * | 2015-05-29 | 2015-09-30 | 江汉大学 | Biological treatment method of acidic sulfate wastewater containing Fe<3+> and Cu<2+> |
| CN105950170A (en) * | 2016-05-30 | 2016-09-21 | 青岛理工大学 | Novel contaminated site Cu in-situ detoxification method based on biogas residues |
| CN106219824A (en) * | 2016-09-09 | 2016-12-14 | 成都九十度工业产品设计有限公司 | A kind of process technique containing heavy metal metallurgy waste water |
| 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 |
| CN106565012A (en) * | 2016-10-09 | 2017-04-19 | 辽宁工程技术大学 | Method for processing coal mine acid wastewater through sulfate reducing bacteria and spontaneous combustion coal gangue in synergetic manner |
| CN105800796B (en) * | 2016-05-10 | 2019-04-09 | 昆明理工大学 | A kind of flotation waste water biological treatment |
| CN112777874A (en) * | 2021-01-20 | 2021-05-11 | 喻婕 | Method for treating acidic wastewater containing heavy metals |
| CN112795604A (en) * | 2020-12-25 | 2021-05-14 | 南京农业大学 | Method for preparing sulfated polysaccharide from acidic mine wastewater |
| CN114149087A (en) * | 2021-12-01 | 2022-03-08 | 中南大学 | Method for treating arsenic-containing waste liquid by using agricultural wastes and microorganisms |
| CN114538714A (en) * | 2022-03-08 | 2022-05-27 | 青海洁神环境科技股份有限公司 | Sewage treatment method adopting MBBR (moving bed biofilm reactor) in cooperation with BBR (BBR) |
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- 2011-08-03 CN CN2011102200723A patent/CN102276060A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 《以大豆为碳源厌氧微生物法处理酸性含铁硫酸盐废水》 20100722 郭颖超 《以大豆为碳源厌氧微生物法处理酸性含铁硫酸盐废水》 网络出版 2,18,23,27-30,,34,44,摘要 1-3 , * |
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| CN103086578A (en) * | 2013-03-05 | 2013-05-08 | 中国科学院新疆生态与地理研究所 | Method for treating quintavalent-antimony-containing wastewater with sulfate mixed bacteria |
| CN103362550A (en) * | 2013-05-10 | 2013-10-23 | 合肥学院 | Method for performing in situ treatment on acid mine water by using crop seed husks |
| CN103362550B (en) * | 2013-05-10 | 2015-06-24 | 合肥学院 | Method for performing in situ treatment on acid mine water by using crop seed husks |
| CN104710017A (en) * | 2015-02-08 | 2015-06-17 | 吉林大学 | Method for treating acidic polymetallic sulfate industrial wastewater by use of sulfate-reducing bacteria |
| CN104773925A (en) * | 2015-04-23 | 2015-07-15 | 合肥工业大学 | Method for simultaneously treating refuse leachate and acidy mine drainage |
| CN104944575A (en) * | 2015-05-29 | 2015-09-30 | 江汉大学 | Biological treatment method of acidic sulfate wastewater containing Fe<3+> and Cu<2+> |
| 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 |
| CN106495390B (en) * | 2015-09-08 | 2019-10-15 | 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 |
| CN105800796B (en) * | 2016-05-10 | 2019-04-09 | 昆明理工大学 | A kind of flotation waste water biological treatment |
| CN105950170A (en) * | 2016-05-30 | 2016-09-21 | 青岛理工大学 | Novel contaminated site Cu in-situ detoxification method based on biogas residues |
| CN106219824B (en) * | 2016-09-09 | 2019-05-17 | 南通市金宏电化设备有限公司 | A kind for the treatment of process of the waste water containing heavy metal metallurgy |
| CN106219824A (en) * | 2016-09-09 | 2016-12-14 | 成都九十度工业产品设计有限公司 | A kind of process technique containing heavy metal metallurgy waste water |
| CN106565012B (en) * | 2016-10-09 | 2019-04-02 | 辽宁工程技术大学 | The method that sulfate reducing bacteria cooperates with self-igniting coal gangue processing Acidic Waste Water from Coal Mines |
| CN106565012A (en) * | 2016-10-09 | 2017-04-19 | 辽宁工程技术大学 | Method for processing coal mine acid wastewater through sulfate reducing bacteria and spontaneous combustion coal gangue in synergetic manner |
| CN112795604A (en) * | 2020-12-25 | 2021-05-14 | 南京农业大学 | Method for preparing sulfated polysaccharide from acidic mine wastewater |
| CN112795604B (en) * | 2020-12-25 | 2024-04-19 | 南京农业大学 | Method for preparing sulfated polysaccharide by using acid mine wastewater |
| CN112777874A (en) * | 2021-01-20 | 2021-05-11 | 喻婕 | Method for treating acidic wastewater containing heavy metals |
| CN114149087A (en) * | 2021-12-01 | 2022-03-08 | 中南大学 | Method for treating arsenic-containing waste liquid by using agricultural wastes and microorganisms |
| CN114538714A (en) * | 2022-03-08 | 2022-05-27 | 青海洁神环境科技股份有限公司 | Sewage treatment method adopting MBBR (moving bed biofilm reactor) in cooperation with BBR (BBR) |
| CN115432890A (en) * | 2022-09-21 | 2022-12-06 | 无锡市道格环保科技有限公司 | Treatment device and method for reducing pollutant discharge in chromium-containing metal ion wastewater |
| CN115432890B (en) * | 2022-09-21 | 2024-01-23 | 无锡市道格环保科技有限公司 | Treatment device and method for reducing pollutant emission in chromium-containing metal ion wastewater |
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