CN1654363A - Biological leaching method for supplying bottom material by suspending sulfur stuffing mode - Google Patents
Biological leaching method for supplying bottom material by suspending sulfur stuffing mode Download PDFInfo
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- CN1654363A CN1654363A CNA2005100489837A CN200510048983A CN1654363A CN 1654363 A CN1654363 A CN 1654363A CN A2005100489837 A CNA2005100489837 A CN A2005100489837A CN 200510048983 A CN200510048983 A CN 200510048983A CN 1654363 A CN1654363 A CN 1654363A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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Abstract
The present invention discloses biological leaching method with sulfur oxidizing bacterium to eliminate heavy metal from sludge by means of suspended sulfur stuffing to provide substrate. The biological leaching technology is to utilize sulfur oxidizing bacterium in leaching out heavy metal from sludge to make sludge become harmless. Inside sludge, sulfur oxidizing bacterium can propagate fast to leach out heavy metal in high efficiency and speed. Suspending sulfur stuffing to provide sulfur oxidizing bacterium inside sludge with substrate can utilize sulfur in high efficiency and facilitate the recovery of residual sulfur, and has greatly lowered cost, fast pH lowering in sludge and great amount leaching out of heavy metal from sludge.
Description
Technical field
The present invention relates to a kind of biological leaching method with suspending sulfur form of bio-carrier supplying bottom.
Background technology
The excess sludge production of municipal sewage plant is huge, and how rationally handling with the disposal excess sludge becomes a very severe problem.According to China's national situation, the most economically viable recycling sludge approach is the soil utilization, yet a large amount of heavy metals is accumulated in the mud and has limited the soil utilization of mud in the municipal sewage treatment process.The raw sludge character of municipal sewage plant is very complicated, and Xu Ying has carried out summing up description to its main proterties
[1]Bioleaching is the innoxious research focus of sludge heavy-metal in recent years, and it utilizes indigenous microorganism acid production in the mud heavy metal stripping in the mud to be reached the purpose of mud detoxification.It is simple to operate, Financial cost is lower, and the removal efficiency of heavy metals height, need not special control in the operational process, and system is equal energy leaching metal in 10-37 ℃ of scope, and any kind mud can both have good development prospect with this method leaching metal.And bioleaching main body microorganism is a thiobacterium, and the substrate that different types of thiobacterium utilized is not quite similar.It wherein is the thiobacterium of substrate with the elemental sulfur, the increment conditional request is lower, bioleaching efficient height, and the required easy storage and transport of substrate Sulfur capacity, and can combine with existing aerobic sludge digestion method, existing operation facility be can make full use of, running cost and capital cost reduced, so receive publicity day by day.
Bioleaching reactor has various ways, is generally cylindrically, and generally speaking by different two classes of dividing of oxygenation mode, a class is that reactor carries out the continuously stirring oxygenation, and the aspect ratio value of this class reactor is little
[2]And another kind of aspect ratio value is bigger, is generally the bottom and is provided with the aeration head of connection air compressor machine to carry out oxygenation
[3]
The required substrate of thiobacterium is an elemental sulfur, promptly common alleged sulphur, and these raw material sources are extensive, and cost is lower.Yet if bioleaching process kind sulphur usage quantity is too high, the engineering that certainly will influence this technology is used, and therefore how the more economical sulphur that utilizes efficiently becomes an important limiting factor.Traditional elemental sulfur addition method is to join in the reactor with powder-form, though bioleaching is effective, but causes the waste of unnecessary sulphur and remains the disadvantageous effect of sulphur to the mud subsequent processes.Elemental sulfur is made into solid form and places reactor with hang, is a kind of new approaches for thiobacterium supplying bottom in the mud, more economical and efficient utilize elemental sulfur, thereby further improve the economic feasibility of bioleaching technology.
Reference:
[1] Xu Ying. mud is disposed and environmental influence as farming is fertile. Environmental Pollution and Control, 1993,15 (8): 23-27
[2]Filali-Meknassi?Y,Tyagi?R?D,Narasiah?K?S.Simultaneous?sewage?sludgedigestion?and?metal?leaching:effect?of?aeration.Process?Biochemistry,2000,36:263-273
[3]Benmoussa?H,Tyagi?R?D,Campbell?P?G?C.Simultaneous?sewage?sludgedigestion?and?metal?leaching?using?an?internal?loop?reactor.Water?Research,1997,31(10):2638-2654
Summary of the invention
The present invention seeks to provides a kind of biological leaching method with suspending sulfur form of bio-carrier supplying bottom in order to overcome the deficiency of powdery sulphur dosing method.This method not only can effectively be fallen doctor negative consumption, and avoids behind the bioleaching too much residue sulphur to be mingled in handling in the mud and the mud subsequent processes is had a negative impact.
It is the sulphur filler to be hung be fixed in the bioleaching reactor, inject municipal sewage plant's raw sludge of the 1/2-3/5 of bioleaching reactor useful volume then, bioleaching reactor bottom aeration aerating, inoculate into thiobacterium liquid by the 2-5% volume ratio of raw sludge, sulfur oxidizing bacterium in the mud utilizes suspending sulfur to be substrate, can carry out heavy metal biological leaching in the mud.
The making method of sulphur filler is: elemental sulfur in high temperature 120-150 ℃ fusing, is cast in it in mould then, is provided with the rope of longitudinal axis in mould, cooling gets final product.
The preparation method of thiobacterium liquid is: get the 150-200mL raw sludge in the 500mL Erlenmeyer flask, adding sulphur grain weight amount/sludge volume equals the sulphur powder of 5-10g/L, at 100-200r/min, and 25-28 ℃ of following shaking culture, reduce to below 2.0 until sludge pH, obtain first round mixed bacteria liquid; Get the first round mixed bacteria liquid of cultured 5-10% volume ratio, be added in the 150-200mL raw sludge, add the sulphur powder that sulphur grain weight amount/sludge volume equals 5-10g/L, shaking culture, pH drops to below 2.0, obtains second and takes turns mixed bacteria liquid; Get second of cultured 5-10% volume ratio and take turns mixed bacteria liquid, be added in the 150-200mL raw sludge, add the sulphur powder that sulphur grain weight amount/sludge volume equals 5-10g/L, shaking culture, pH drops to below 2.0, obtains thiobacterium liquid.
The invention has the beneficial effects as follows, the sulphur filler places reactor with suspension type, can utilize sulphur preferably, tradition substrate form (being that the sulphur powder adds) is because of gravity settling and the not enough reactor bottom that is deposited on of stirring intensity, thereby influence the dissolving of heavy metal in the mud, and cause the serious waste of elemental sulfur.And can save the consumption of elemental sulfur greatly and can not cause the problem of sulphur deposition according to this method.
Embodiment
The present invention proposes, and elemental sulfur places bioleaching reactor with suspension type, can realize that sulfur oxidizing bacterium reduces sludge pH and heavy metal stripping in the mud is reached innoxious purpose thereby produce sulfuric acid its utilization in the mud.But and efficient recovery elemental sulfur.
The present invention adopts aforesaid method Treating Municipal Sewage residue raw sludge working method as follows:
1) making of the cultivation of thiobacterium inoculation liquid and sulphur filler:
Get the 150-200mL raw sludge in the 500mL Erlenmeyer flask, add the sulphur powder that sulphur grain weight amount/sludge volume equals 5-10g/L, at 100-200r/min, 25-28 ℃ of following shaking culture reduced to below 2.0 until sludge pH, obtains first round mixed bacteria liquid; Get the first round mixed bacteria liquid of cultured 5-10% volume ratio, be added in the 150-200mL raw sludge, add the sulphur powder that sulphur grain weight amount/sludge volume equals 5-10g/L, shaking culture, pH drops to below 2.0, obtains second and takes turns mixed bacteria liquid; Get second of cultured 5-10% volume ratio and take turns mixed bacteria liquid, be added in the 150-200mL raw sludge, add the sulphur powder that sulphur grain weight amount/sludge volume equals 5-10g/L, shaking culture, pH drops to below 2.0, obtains thiobacterium liquid.150 ℃ of fusings down, make it be fixed into the sulphur filler elemental sulfur.
2) bioleaching reactor of suspending sulfur filler running:
The bioleaching reactor that is adopted is cylindrical, and height is 47cm, and bottom radius is 4.5cm, and cubic capacity is 3L, along the bioleaching reactor height 4 thief holes is set in turn, and spacing is 10cm.According to raw sludge volume ratio in sulphur filler and the bioleaching reactor is to carry out at 1: 20.The sulphur filler is hung in the bioleaching reactor, the raw sludge of packing into, and by inoculation liquid and raw sludge volume ratio 2-5% with in the thiobacterium inoculation liquid adding bioleaching reactor.The bioleaching reactor bottom is provided with aeration head, connects air compressor machine and carries out aeration aerating.The aeration rate that bioleaching reactor adopts is per minute volume of air and raw sludge volume ratio 0.05-0.15.Sludge pH, redox potential (ORP), SO are measured by the centrifugal solid-liquid separation of carrying out in mud sampling back
4 2-And dissolved heavy metal content in the supernatant liquor.
Embodiment 1
This test is the sludge heavy-metal bioleaching of bench scale.Adopt the residue raw sludge initial properties as follows: pH value 6.86, SS 9.2g/L, SO
4 2-456.7mg/L, Cu 243.8mg/kg dewatered sludge, Zn 2935.5mg/kg dewatered sludge.
(1) bioleaching reactor configuration and sulphur filler are installed: at 150 ℃ of baking oven internal heating 45min, pour the sulphur powder into mould (the plastics axis vertically passes) after the fusion fast, treat its cooled and solidified after, the sulphur filler.Get 5 sulphur fillers then and connect the bunchiness shape, the top of reactor is fixed on the top, hangs in the reactor.The 2.5L raw sludge is loaded in the reactor, and 2% inoculum size adds the mix sulphur bacterium liquid of cultivating by volume simultaneously.Bioleaching reactor is made by synthetic glass, carries out oxygenation in the bottom by micro porous aeration head, and air flow quantity is per minute volume of air and raw sludge volume ratio 0.15.
(2) the suspending sulfur packed column reactor is to the heavy metal biological leaching situation: operating temperature is a normal temperature, and mobility scale reaches heavy metal result of extraction preferably at 11-19 ℃ through operation in 19 days.The sludge pH value was respectively 4,2.5,19 days pH values and finally reduces to 2.3 by 6.86 initial reductions gradually in the 11st day and 15 days in the reactor; SO in the mud
4 2-Concentration then rises to final 6598.5mg/L from initial hundreds of mg/L, and this can reflect better that sulfur oxidizing bacterium in the mud is to hanging on the situation of utilizing of sulphur filler in the reactor.Cu and Zn dissolution efficiency from mud in the mud, promptly the clearance of Cu and Zn can reach 72.6% and 81.3% respectively.For investigating the firm situation that the sulphur filler is washed away by aeration in mud, promptly whether can in operational process, occur coming off and cause the deposition of sulphur at reactor bottom, behind the end of run, the sulphur filler that hangs is taken out, slowly emit mud in the reactor from the reactor thief hole, the sulphur deposition phenomenon does not appear in the result bottom, illustrates that this sulphur filler has better anti-scouring capability.
By this lab scale evidence, this suspension can better guarantee the removal effect of heavy metal in the mud and can effectively utilize sulphur for the sulphur mode, reduces the sulphur consumption, is a kind of feasible way of bioleaching reactor substrate supply.
Embodiment 2
This test utilizes volume to carry out for the bioleaching reactor of 3L.Adopt the residue raw sludge initial properties as follows: pH value 7.52, SS 20.2g/L, SO
4 2-348.1mg/L, ORP:-45mV, Cu290.4mg/kg dewatered sludge, Zn 3687.4mg/kg dewatered sludge.
(1) bioleaching reactor configuration and sulphur filler are installed: at 150 ℃ of baking oven internal heating 45min, pour the sulphur powder into mould (the plastics axis vertically passes) after the fusion fast, treat its cooled and solidified after, the sulphur filler.Get 5 sulphur fillers then and connect the bunchiness shape, the top of reactor is fixed on the top, hangs in the reactor.The 2.5L raw sludge is loaded in the reactor, and 5% inoculum size adds the mix sulphur bacterium liquid of cultivating by volume simultaneously.Bioleaching reactor is made by synthetic glass, carries out oxygenation in the bottom by micro porous aeration head, and air flow quantity is per minute volume of air and raw sludge volume ratio 0.05.
(2) the suspending sulfur packed column reactor is to the heavy metal biological leaching situation: the operating temperature mobility scale reaches heavy metal result of extraction preferably at 16-23 ℃ through operation in 16 days.The sludge pH value is by 7.52 initial reductions gradually in the reactor, and bioleaching finishes the pH value of back mud and reduces to 2.17; The ORP of mud from beginning-45mV is linear to rise, and is 511mV in the time of 16 days; SO in the mud supernatant liquor
4 2-Concentration rises to final 7430.3mg/L from initial 348.1mg/L; Cu and Zn dissolution efficiency from mud in the mud, promptly the clearance of Cu and Zn can reach 76.2% and 75.1% respectively.
Claims (3)
1. biological leaching method with suspending sulfur form of bio-carrier supplying bottom, it is characterized in that, is 1 with the sulphur filler according to sulphur volume/raw sludge volume: 20-1: 30 ratios hang and are fixed in the bioleaching reactor, inject municipal sewage plant's raw sludge of the 1/2-3/5 of bioleaching reactor useful volume then, bioleaching reactor bottom aeration aerating carries out with the aeration rate of per minute volume of air and raw sludge volume ratio 0.05-0.15.Inoculate into thiobacterium liquid by the 2-5% volume ratio of raw sludge, the sulfur oxidizing bacterium in the mud utilizes suspending sulfur to be substrate, can carry out heavy metal biological leaching in the mud.
2. a kind of biological leaching method according to claim 1 with suspending sulfur form of bio-carrier supplying bottom, it is characterized in that, described sulphur filler making method is: with elemental sulfur in high temperature 120-150 ℃ fusing, then it is cast in the mould, be provided with the rope of longitudinal axis in mould, cooling gets final product.
3. a kind of biological leaching method according to claim 1 with suspending sulfur form of bio-carrier supplying bottom, it is characterized in that, the preparation method of described thiobacterium liquid is: get the 150-200mL raw sludge in the 500mL Erlenmeyer flask, adding sulphur grain weight amount/sludge volume equals the sulphur powder of 5-10g/L, at 100-200r/min, 25-28 ℃ of following shaking culture reduced to below 2.0 until sludge pH, obtains first round mixed bacteria liquid; Get the first round mixed bacteria liquid of cultured 5-10% volume ratio, be added in the 150-200mL raw sludge, add the sulphur powder that sulphur grain weight amount/sludge volume equals 5-10g/L, shaking culture, pH drops to below 2.0, obtains second and takes turns mixed bacteria liquid; Get second of cultured 5-10% volume ratio and take turns mixed bacteria liquid, be added in the 150-200mL raw sludge, add the sulphur powder that sulphur grain weight amount/sludge volume equals 5-10g/L, shaking culture, pH drops to below 2.0, obtains thiobacterium liquid.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI495521B (en) * | 2012-11-06 | 2015-08-11 | Univ Nat Kaohsiung 1St Univ Sc | Bioremediation system and method for treating metal-contaminated soils or sediments |
CN106277684A (en) * | 2016-09-09 | 2017-01-04 | 九江学院 | Immobilization sulfur-oxidizing bacteria biological rotating disk reaction unit and application |
CN108486097A (en) * | 2018-05-17 | 2018-09-04 | 浙江大学 | The dual immobilization biological matter charcoal particle of sulphur-bacterium and preparation and bioleaching method |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1016633A1 (en) * | 1998-12-29 | 2000-07-05 | Pâques Bio Systems B.V. | Process for the treatment of waste water containing heavy metals |
CA2279525A1 (en) * | 1999-08-03 | 2001-02-03 | Institut National De La Recherche Scientifique | Hybrid biological and chemical process for decontaminating municipal sewage sludge |
CN1206376C (en) * | 1999-09-07 | 2005-06-15 | 比利顿知识产权有限公司 | Bioleaching of sulphide minerals |
JP2002011429A (en) * | 2000-06-28 | 2002-01-15 | Taiheiyo Cement Corp | Treatment process of heavy metal in waste |
PE20020630A1 (en) * | 2000-10-06 | 2002-07-11 | Billiton Sa Ltd | LEACHING IN PILES OF SULFURED MINERALS |
JP2003275707A (en) * | 2002-03-20 | 2003-09-30 | Hokkaido Technology Licence Office Co Ltd | Method for extracting and stabilizing heavy metal in waste |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI495521B (en) * | 2012-11-06 | 2015-08-11 | Univ Nat Kaohsiung 1St Univ Sc | Bioremediation system and method for treating metal-contaminated soils or sediments |
CN106277684A (en) * | 2016-09-09 | 2017-01-04 | 九江学院 | Immobilization sulfur-oxidizing bacteria biological rotating disk reaction unit and application |
CN108486097A (en) * | 2018-05-17 | 2018-09-04 | 浙江大学 | The dual immobilization biological matter charcoal particle of sulphur-bacterium and preparation and bioleaching method |
CN108486097B (en) * | 2018-05-17 | 2020-03-17 | 浙江大学 | Sulfur-bacterium dual immobilized biomass charcoal particles and preparation and bioleaching methods thereof |
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