WO2021120364A1 - 一种生物处理酸性矿山废水同时回收铁离子的方法及系统 - Google Patents
一种生物处理酸性矿山废水同时回收铁离子的方法及系统 Download PDFInfo
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- C02F3/345—Biological treatment of water, waste water, or sewage characterised by the microorganisms used for biological oxidation or reduction of sulfur compounds
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- C02F2101/00—Nature of the contaminant
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- Y02W10/00—Technologies for wastewater treatment
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Definitions
- the invention belongs to the field of wastewater treatment, and relates to a method and system for biologically treating acid mine wastewater and simultaneously recovering iron ions.
- Acid mine wastewater is currently a challenging environmental problem facing the global mining industry. It is a type of low-pH, high-iron-ion drainage produced by biological and chemical reactions during mining or waste slag accumulation. Extremely acidic (pH: 2.0-3.5), rich sulfate (SO 4 2- : 2000-6000mg/L), high iron content (Fe 2+ or Fe 3+ : 500-4500mg/L), toxic metals (As, The existence of Cd, Cu, Pb, Ni, etc.) is a typical feature of AMD. AMD's direct emissions seriously threaten the safety of the water and soil environment and the ecosystem around the mining area, causing huge losses to people's production and life.
- the neutralization precipitation method is a relatively mature method for treating AMD wastewater. It mainly uses alkaline reagents such as lime or limestone to neutralize acidity, and uses acid-base neutralization reaction to precipitate AMD metal ions and sulfate radicals to purify sewage and improve The purpose of wastewater pH.
- Precipitating metal ions and sulfates in AMD in the form of minerals can achieve the dual purpose of simultaneous recovery of useful ions and repair of AMD.
- AMD treatment technology based on sulfate reduction has been extensively studied in recent years.
- Sulfate-reducing bacteria can use hydrogen or organic matter as electron donors to reduce sulfate to sulfide ions, increase the pH of the solution, and generate biogenic sulfur at the same time.
- Ions can form corresponding sulfide precipitates with metal ions (Fe, Zn, Cu, etc.) in AMD to achieve the purpose of recovering valuable ions in AMD.
- Chinese invention patent 200910038782.7 discloses a method of using Citrobacter to reduce sulfate in AMD and precipitating metals, so that all metal ions are converted into sulfide form, which is conducive to recycling;
- Chinese invention patent 200810054487.6 discloses that sulfate-reducing bacteria are the main body
- the biological treatment of acid mine wastewater technology achieves the dual effects of recovering elemental sulfur and treating wastewater.
- the S 2- precipitated metal ions after the reduction of SO 4 2- can make the AMD treatment process achieve the purpose of resource utilization and harmlessness.
- the stability of biological treatment systems based on sulfate reduction is not easy to control.
- Sulfate-reducing bacteria are mostly heterotrophic and obligate anaerobic microorganisms, which are extremely sensitive to the oxygen content, pH value, carbon source types and metal ions in the system. sensitive. It is reported in the literature that a large amount of iron ions in AMD can inhibit the activity of sulfate-reducing bacteria and reduce the sulfate-reducing capacity by 39-100%. Although some enhancement methods can improve the tolerance of bioreactors, such as the use of mixed bacteria for bioenhancement, they cannot completely solve the disadvantages of the need for carbon source addition, absolute anaerobic conditions, and neutral pH requirements (pH 5-7). In addition, Chinese invention patent 201610153310.6 discloses an acid mine wastewater treatment system based on biological mineralization.
- the acid mine wastewater is passed through a biological oxidation mineralization unit to form iron secondary minerals to remove part of the iron ions and sulfuric acid in the acid mine wastewater. Roots to reduce the burden of subsequent ash neutralization treatment.
- This method uses acidophilic Thiobacillus ferrooxidans, which can realize the mineralization process under in-situ conditions, but the disadvantages are that the efficiency of biological mineralization treatment is low, and the microorganisms are directly applied to wastewater treatment, and there is a tendency for microorganisms to be easily lost.
- the problem is that it is difficult to fully apply to the actual mine wastewater treatment process. Therefore, the development of a new type of processing technology to realize the resource utilization and harmlessness of AMD is still a problem that needs to be solved urgently in the environmental field.
- the purpose of the present invention is to solve the above-mentioned shortcomings of the prior art and provide a system for biologically treating acid mine wastewater while recovering iron ions.
- Another object of the present invention is to provide a method for biologically treating acid mine wastewater while recovering iron ions.
- a system for biologically treating acid mine wastewater and simultaneously recovering iron ions comprises: the system comprises: a biological mineralization unit, a biological reduction tank unit, and an alkali regulating tank unit; the biological mineralization unit includes two Part: the multi-stage water drop aeration tank at the front end and the advection catch tank at the back end.
- the biological reduction unit includes a distribution tank and a biological reduction tank.
- the alkali adjustment unit includes an alkali adjustment tank and a distribution tank.
- the outlet of the regulating unit is connected with the top of the biomineralization unit through a circulating pump and a pipeline to form a circulating acid mine wastewater treatment system.
- the biomineralization unit (1) is preferably provided with an internal circulation: the end of the advection water collection tank (5) is circulated to the top of the first-stage water drop aeration tank (4) through a circulating pump and a pipeline.
- the bottom and the top of the biological reduction tank (7) are connected through a circulating pump and a pipeline.
- the end of the distribution tank (9) and the alkali regulating tank (8) are provided with an internal circulation, which is connected with a pipeline through a circulation pump.
- the multi-stage water drop aeration tank and the flat flow collection tank of the biomineralization reaction unit are filled with acidophilic iron oxidizing bacteria biofilm; the biological reduction tank is filled with acidophilic iron reduction Bacteria biofilm.
- the biomineralization reaction tank is characterized by wide and shallow, and the biological reduction tank is characterized by narrow and deep.
- the number of water falling aeration stages of the water falling aeration tank is greater than 3; an S-shaped return plate is arranged in the advection water collecting tank of the biomineralization unit.
- a method for biologically treating acid mine wastewater and simultaneously recovering iron ions comprising:
- the method for biologically treating acid mine wastewater while recovering iron ions preferably includes:
- the acid mine wastewater is introduced into the system of the present invention for cyclic treatment to recover jarosite minerals or Shi’s minerals.
- the specific process is as follows: the wastewater is directly introduced into the biomineralization unit, oxygenated by the falling water aeration tank, and in the acidophilic aeration tank. Biomineralization occurs under the action of iron oxidizing bacteria, and the subsequent flow through the advection sump for further mineralization. The end of the advection sump and the top of the falling water aeration are constructed through a peristaltic pump to build a multi-cycle biomineralization process to promote mineralization.
- Sedimentation rate waste water consumes part of oxygen through the advection sump, flows through the gentle flow of the distribution pool, and then enters the biological reduction tank.
- the unmineralized iron ions are reduced to ferrous ions through biological reduction Recycling treatment in the tank improves the reduction efficiency;
- the wastewater enters the alkali adjustment tank after reduction, and the pH of the solution is increased to meet the needs of the acidophilic iron oxidizing bacteria in the next cycle treatment process.
- the pH of the solution is fully adjusted through the cycle process in the alkali adjustment unit;
- the distribution tank enters the next batch processing system. After multiple cycles of treatment, jarosite minerals or Shi's minerals are recovered from the bottom of the biomineralization unit and the acidophilic iron oxidizing bacteria biological filler.
- the acidophilic iron oxidizing bacteria are cultured aerobic and colonized on the composite biological filler to prepare the acidophilic iron oxidizing bacteria biofilm: the liquid culture medium of the acidophilic iron oxidizing bacteria is used for inoculation Culture, the formula is (NH 4 ) 2 SO 4 : 3.5g/L, MgSO 4 ⁇ 7H 2 O: 0.58g/L, KCl: 0.055g/L, KH 2 PO 4 ⁇ 3H 2 O: 0.029g/L, Ca(NO 3 ) 2 ⁇ 4H 2 O: 0.0168g/L and FeSO 4 ⁇ 7H 2 O: 22.4g/L: pH: 2.5, the first use of pure strains is 20% (volume ratio) inoculation amount, and subsequent direct use The last batch of bacteria-containing effluent is inoculated, and the inoculation volume is gradually reduced (20-5%), after 3-5 batches of culture and colonization, each culture is 3-5 days.
- the acidophilus iron-reducing bacteria are cultured statically and colonized on the composite biological filler to prepare the acidophilus iron-reducing bacteria biofilm.
- the medium of iron-reducing bacteria the formula is: (NH 4 ) 2 SO 4 :0.15g/L, MgSO 4 ⁇ 7H 2 O: 0.5g/L, KCl: 0.05g/L, KH 2 PO 4 ⁇ 3H 2 O :0.05g/L, Ca(NO 3 ) 2 ⁇ 4H 2 O: 0.0144g/L, yeast extract: 0.2g/L, C 6 H 12 O 6 :1g/L and Fe 2 (SO 4 ) 3 ⁇ 3H 2 O: 8.92 g/L, pH: 2.8.
- the amount of each inoculation is 20% (volume ratio), the pure strain is used for the first time, and the subsequent batch of bacteria-containing effluent is used for inoculation. A total of 3-5 batches of culture and colonization are carried out, and each culture is 7-12 days.
- the acidophilic iron oxidizing bacteria is Acidithiobacillus ferrooxidans LX5, which is deposited in the General Microbiology Center of the Chinese Microbial Culture Collection Management Committee, and the deposit number is CGMCC No.0727; the acidophilic iron reducing bacteria It is Acidiphilium cryptum JZ-6, deposited in the General Microbiology Center of China Microbial Culture Collection Management Committee, and the deposit number is CGMCC No.11036.
- an acidophilic iron oxidizing bacteria culture medium with a concentration of 1/10-1/2 is additionally added to the acid mine wastewater for the purpose of providing nutrients necessary for the growth of bacteria.
- the number of falling water aeration stages is greater than three.
- an S-shaped return plate is arranged in the collecting tank of the biomineralization unit.
- the waste water is circulated from the end of the advection sump of the biomineralization unit to the top of the water drop aeration tank, and the reflux rate is 0.4-0.8L/min.
- wastewater is circulated from the bottom of the biological reduction tank to the top of the tank, and the reflux rate is 0.8-1.2 L/min.
- the effluent from the distribution tank of the alkali adjustment unit is recycled to the adjustment tank, and the reflux rate is 0.05-0.2L/min.
- the circulating flow rate from the end of the alkali adjustment unit to the top of the water drop aeration tank of the biomineralization unit is set to 6-10 mL/min, and the time for a single biomineralization-biological reduction-alkali adjustment process is 3 -7 days.
- the alkali regulating tank is filled with 45-50 g/L of granular calcium carbonate with a particle size of 1-3 ⁇ m.
- the pH of the biomineralization unit in the treatment process is maintained at 1.8-3.0, and the pH of the effluent from the alkali regulating tank is at 2.0-3.0.
- the strains screened in the present invention are adapted to the solution environment of acid mine wastewater, and can be directly treated in situ conditions, and their activity is not inhibited by metal ions and other substances in the wastewater;
- Acidophilic iron oxidizing bacteria are Aerobic bacteria and iron-reducing bacteria are facultative aerobic bacteria, they are easy to cultivate, aerobic growth is rapid, and the treatment process is not restricted by strict anaerobic;
- the removal rate of iron and sulfate radical in a single cycle can be calculated by theory Therefore, the operation cycle can be accurately adjusted according to actual needs;
- Cyclic treatment can greatly reduce the content of metal ions and sulfate radicals in acid mine wastewater, and can significantly reduce the burden of subsequent lime neutralization treatment, so that the final treated effluent meets Class II National Emission Standard (GB 8978-1996);
- the recovered iron secondary mineral is an environmental material that can be used as an adsorption material and heterogeneous Fenton catalyst for water treatment and soil remediation.
- Figure 1 is a schematic diagram of the experimental device of the present invention.
- 1 Biological mineralization unit
- 2 Biological reduction tank unit
- 3 Alkali adjustment tank unit
- 4 Falling water aeration tank
- 5 Advection water collection tank
- 6 Distribution tank
- 7 Biological reduction tank
- 8 Alkali adjustment Pool
- 9 Distribution pool.
- JZ-6 classified as Acidiphilium sp., deposited in the General Microbiology Center of China Microbial Culture Collection Management Committee, deposited at the Institute of Microbiology, Chinese Academy of Sciences, No. 3, Beichen West Road, Chaoyang District, Beijing. The preservation date is On July 2, 2015, the deposit number was CGMCC No.11036.
- a method and device for biologically treating mine wastewater and recovering iron ions at the same time, the specific steps include:
- the formula of acidophilic iron oxidizing bacteria LX5 liquid medium is: (NH 4 ) 2 SO 4 : 3.5g/L, MgSO 4 ⁇ 7H 2 O: 0.58g/L, KCl: 0.055g/L, KH 2 PO 4 ⁇ 3H 2 O: 0.029 g/L, Ca(NO 3 ) 2 ⁇ 4H 2 O: 0.0168 g/L, and FeSO 4 ⁇ 7H 2 O: 22.4 g/L: pH: 2.5.
- the liquid culture medium of eosinophilic iron oxidizing bacteria LX5 was used for filming treatment.
- the eosinophilic iron oxidizing bacteria LX5 was cultured in a pure sterile medium at 180 rpm to a density of 10 8 cells/mL, and then inoculated at 20%. Compare the inoculation of the elastic film composite filler in the biomineralization unit.
- the inoculation amount of the first batch is 20% and the time is 5 days.
- the effluent of the second batch and above is directly inoculated, and the inoculation amount is 10%.
- the time is 5 days
- the third batch of inoculation amount is 5%, and the time is 3 days.
- the iron oxidizing bacteria colonize the biofilm of the elastic film composite filler to form brown-red iron oxidizing organisms. membrane.
- the medium of acidophilus iron-reducing bacteria JZ-6 the formula is: (NH 4 ) 2 SO 4 :0.15g/L, MgSO 4 ⁇ 7H 2 O: 0.5g/L, KCl: 0.05g/L, KH 2 PO 4 ⁇ 3H 2 O: 0.05g/L, Ca(NO 3 ) 2 ⁇ 4H 2 O: 0.0144g/L, yeast extract: 0.2g/L, C 6 H 12 O 6 : 1g/L and Fe 2 ( SO 4 ) 3 ⁇ 3H 2 O: 8.92g/L, pH: 2.8; after the iron oxidizing bacteria are cultured in a pure sterile medium to a density of 10 8 cells/mL, the inoculation ratio is 20% Inoculate the biological filler in the biological reduction unit.
- the eosinophilic iron oxidizing bacteria biofilm is placed in a wide and shallow water drop aeration tank and a advection water collection tank, the water drop aeration tank is set at the front end, and the advection water collection tank is set at the back end of the multi-stage water drop aeration tank ,
- the end of the pool and the top of the water drop aeration are constructed through a peristaltic pump to construct a cyclic biomineralization process; the acidophilic iron-reducing bacteria biofilm is placed in a narrow and deep biological reduction pool, and the peristaltic pump builds a cycle from the bottom to the top of the pool.
- Biological reduction treatment process ;
- the biomineralization unit is composed of five water drop aeration tanks (volume 3L) and one collection tank (volume 15L). Each drop tank is filled with 6 combined fillers, and the collection tank is filled with 30 fillers for a total of 60 A combination of fillers.
- the total height of the water drop is 125cm, an S-shaped return plate is set in the sump, the return rate in the end of the sump and the top of the water drop aeration is set to 0.6L/min, the pH of the biomineralization unit is maintained at 1.8-3.0; the volume of the biological reduction unit It is 30L, and 66 composite packings are suspended and filled on average, and the flow rate of circulation from bottom to top is set to 1L/min;
- the back end of the reduction tank is connected with an alkali adjustment tank, the alkali adjustment unit is equipped with an internal circulation, and the end of the alkali adjustment unit's distribution pool is connected with the top of the water drop aeration tank to form a circulating treatment system;
- the effective volume of the alkali conditioning tank is 3L, and it is filled with 150g calcium carbonate with a particle size of 1-3 ⁇ m.
- the effluent is refluxed at a flow rate of 116mL/min, and the effluent is connected to the top of the water drop aeration tank at a flow rate of 8.5mL/min. It constitutes a treatment system with a single cycle treatment time of 5 days, and the pH of the effluent from the alkali regulating tank is maintained at 2.0-3.0;
- the actual acid mine wastewater composition of the abandoned copper mine in Tongling, Jiangxi is shown in Table 1. After adding a half-concentration iron oxidizing bacteria culture medium to the actual mine wastewater, it is introduced into the treatment system for recycling treatment.
- the single biomineralization-bioreduction-alkali adjustment treatment cycle is 5 days, and 50g calcium carbonate in the alkali adjustment tank is replaced every 5 days, and 1g/L glucose is supplemented in the bioreduction tank.
- the effluent is neutralized by lime, which can significantly reduce the amount of lime and the neutralization waste generated.
- the amount of lime required is reduced from 5.4g/L to 2.6g/L, and the neutralization is produced
- the amount of waste residue is reduced from 23.8g/L to 7.4g/L.
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Claims (19)
- 一种生物处理酸性矿山废水同时回收铁离子的系统,其特征在于所述的系统包含:生物矿化单元(1)、生物还原池单元(2)和碱调节池单元(3);所述的生物矿化单元(1)包括两部分:前端的多级跌水曝气池(4)和后端的平流集水池(5),所述的生物还原单元(2)包括配水池(6)和生物还原池(7),所述的碱调节单元(3)包括碱调节池(8)和配水池(9),所述的碱调节单元(3)出水处与生物矿化单元(1)顶端通过循环泵和管道连通,构成循环的酸性矿山废水处理系统。
- 根据权利要求1所述的系统,其特征在于所述的生物矿化单元(1)设置内循环:平流集水池(5)末端通过循环泵和管道循环至第一级跌水曝气池(4)顶端;所述的生物还原池(7)底部与顶部通过循环泵和管道连通;所述的配水池(9)末端与碱调节池(8)设置内循环,通过循环泵和管道连接。
- 根据权利要求1所述的系统,其特征在于所述的跌水曝气池和平流集水池均填充嗜酸性铁氧化菌生物膜;所述的生物还原池填充嗜酸性铁还原菌生物膜。
- 根据权利要求3所述的系统,其特征在于所述生物矿化反应池的特征为宽而浅,所述的生物还原池的特征为窄而深。
- 根据权利要求1所述的系统,其特征在于跌水曝气池的跌水曝气级数大于3级;所述的生物矿化单元平流集水池内设置S形回流板。
- 一种生物处理酸性矿山废水同时回收铁离子的方法,其特征在于包含:将酸性矿山废水中额外加入一定量的铁氧化菌培养基,引入系统,进行循环生物矿化-生物还原-生物矿化处理,最终在生物矿化单元回收黄钾铁矾矿物或施氏矿物。
- 根据权利要求6所述的方法,其特征在于包含:将酸性矿山废水引入权利要求1-5中任一项所述的系统进行循环处理,回收黄钾铁矾矿物或施氏矿物,具体过程为:废水直接引入生物矿化单元,经跌水曝气池充氧,在嗜酸性铁氧化菌的作用下发生生物矿化作用,后续流经平流集水池进行进一步的矿化,平流集水池末端与跌水曝气顶端通过蠕动泵构筑多次循环生物矿化处理过程,促进矿化沉淀率;废水经由平流集水池消耗部分氧气,流经配水池平缓水流后,进入生物还原池,在嗜酸性铁还原菌的作用下将未矿化的铁离子还原为亚铁离子,通过生物还原池内循环处理提高还原效率;废水经还原后进入碱调节池,提升溶液pH以适应下一循环处理过程嗜酸性铁氧化菌的溶液需求,经 过碱调节单元内循环过程充分调整溶液pH;废水最后由配水池进入下一批次处理系统,经过多次循环处理后,从生物矿化单元底部及嗜酸性铁氧化菌生物填料上回收黄钾铁矾矿物或施氏矿物。
- 根据权利要求7所述的方法,其特征在于将嗜酸性铁氧化菌好氧培养,将其定殖在复合生物填料上制备得到嗜酸性铁氧化菌生物膜;将嗜酸性铁还原菌静置培养,将其定殖在复合生物填料上制备得到嗜酸性铁还原菌生物膜。
- 根据权利要求5所述的方法,其特征在于所述的嗜酸性铁氧化菌为氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans)LX5,保藏于中国微生物菌种保藏管理委员会普通微生物中心,保藏编号为CGMCC No.0727;所述的嗜酸性铁还原菌为嗜酸菌(Acidiphilium sp.)JZ-6,保藏于中国微生物菌种保藏管理委员会普通微生物中心,保藏编号为CGMCC No.11036。
- 根据权利要求7所述的方法,其特征在于所述酸性矿山废水中额外加入1/10-1/2浓度的嗜酸性铁氧化菌培养基。
- 根据权利要求7所述的方法,其特征在于跌水曝气池的跌水曝气级数大于3级。
- 根据权利要求7所述的方法,其特征在于所述的生物矿化单元平流集水池内设置S形回流板。
- 根据权利要求7所述的方法,其特征在于废水从生物矿化单元平流集水池末端循环至跌水曝气池顶端,回流速度为0.4-0.8L/min。
- 根据权利要求7所述的方法,其特征在于废水从生物还原池底部循环到池顶部,回流速度为0.8-1.2L/min。
- 根据权利要求7所述的方法,其特征在于碱调节单元的配水池出水再循环至调节池内,回流速度为0.05-0.2L/min。
- 根据权利要求7所述的方法,其特征在于碱调节单元末端到生物矿化单元跌水曝气池顶端的循环流速设置为6-10mL/min,单次生物矿化-生物还原-碱调节处理过程时间为3-7天。
- 根据权利要求7所述的方法,其特征在于所述的碱调节池内填充45-50g/L的颗粒状碳酸钙,粒径为1-3μm。
- 根据权利要求7所述的方法,其特征在于所述处理过程生物矿化单元pH维 持在1.8-3.0,碱调节池出水pH在2.0-3.0。
- 根据权利要求7所述的方法,其特征在于所述在单次生物矿化-生物还原-碱调节处理过程,添加1g/L葡萄糖至生物还原池,更换1/3碱调池中的碳酸钙。
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