CN103086580A - Method for quickly removing heavy metals in municipal sludge - Google Patents
Method for quickly removing heavy metals in municipal sludge Download PDFInfo
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- CN103086580A CN103086580A CN2012104758438A CN201210475843A CN103086580A CN 103086580 A CN103086580 A CN 103086580A CN 2012104758438 A CN2012104758438 A CN 2012104758438A CN 201210475843 A CN201210475843 A CN 201210475843A CN 103086580 A CN103086580 A CN 103086580A
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Abstract
The invention discloses a method for quickly removing heavy metals in municipal sludge. The method comprises the following steps of: (1) based on raw sludge as a material, adding 10-25g/L S as a primer and performing enrichment culture of thiobacillus thiooxidans; then, adding the thiobacillus thiooxidans obtained as a strain into another culture liquid which uses raw sludge as a material and 10-20g/L S as the primer for secondary enrichment culture of thiobacillus thiooxidans; performing enrichment culture for at least three times, so that the bacterial liquid becomes a high concentration thiobacillus thiooxidans inoculated bacterial liquid; and (2) adjusting concentration of sludge to be treated to 1-5%, inoculating by the bacterial inoculating liquid which is cultured by at least three times, wherein the inoculating amount is at least 5% of sludge to be treated in volume, adding 10-20g/L S as the primer, adjusting pH value to 4 at 25-32 DEG C, and leaching and culturing for 2 days. According to the method, when the content of overproof heavy metals in sludge is in a range of 2 times of farm-oriented standard, all overproof heavy metals can be removed within 2 days.
Description
Technical field
The present invention relates to field of Environment Protection, relate to particularly a kind of method of quick removal municipal sludge heavy metal.
Background technology
Along with the quickening of urbanization process and the raising of wastewater treatment rate, the output of municipal sludge grows with each passing day.Only Xiamen City's sludge yield of 2007 just reaches 9.5*10
4M
3(water ratio 76%).Most cities mud all contains abundant organic matter and the nutrients such as N, P, K, and the farmland reuse is main path and the optimal selection that recycling sludge utilizes, but its heavy metal content problem becomes the biggest obstacle that it is applied to soil.
Low, the practical a kind of economical and effective of bioleaching running cost in existing several removal municipal sludge heavy metal technology (chemical process, electrochemical process, phytoremediation, supercritical fluid extraction), has potential heavy metal removal method.The method is except having the effect of removing Heavy Metals in Sludge, and has the effect of synchronously killing pathogenic bacteria in mud.
Its principle is to add suitable microbial substrates in raw sludge, utilize the direct effect of the acidophilia thiobacilluss such as thiobacillus ferrooxidant and thiobacillus thiooxidans or the indirect action of its meta-bolites, by oxidation, reduction, complexing, absorption, dissolution process, insoluble heavy metal in mud is separated lixiviate out, then remove a large amount of heavy metals by solid-liquid separation technique.Therefore, inquiring into suitable leaching condition is to improve the key of heavy metal leaching effect.
Wong and Henry carry out the test of sequence batch (bioleaching with thiobacillus ferrooxidant to Canadian anaerobically digested sludge.Result shows, pH is that the removal efficient of 4 o'clock heavy metals is best, and the pH value〉4 or＜1.5 o'clock, bioleaching can be suppressed.The optimum temperature of bioleaching is 25～35 ℃, and when surpassing 40 ℃, the clearance of heavy metal sharply descends.B1aiS etc. are in the sequencing batch reactor experiment, two kinds of thiobacilluss have been studied to the removal effect of the U.S. 23 kinds of Heavy Metals in Sludges, after the leaching of 10 days, thiobacillus thiooxidans and thiobacillus ferrooxidant are close to the clearance of heavy metal, the clearance of Zn can reach respectively 85% and 82%, the clearance of Cd be respectively 82% and 74%, two kind of bacterium all can be advantageously applied to the removal of heavy metal.Wangdans etc. (2009) are respectively with FeSO
47H
2O, simple substance S powder are that substrate is studied, and result shows the bioleaching through 14d, take simple substance S powder during as substrate, substrate be 6g/L mud sample Cu, that Zn leaches rate is the highest, is respectively 18.8 and 34.8; With FeSO
47H
2When O is substrate, substrate be 25g/L mud sample Cu, that Zn leaches rate is the highest, is respectively 29.1 and 36.8.This kind sequence batch (bioleaching needs the long period (6～12 days) just can reach high clearance.So people begin continuous flow reactor has been carried out more research.
Utilize thiobacillus thiooxidans to remove Heavy Metals in Sludge as (2005) such as Huang Ming, result shows, be 5g/L and be accompanied by under 15% acclimation sludge reflux conditions at the matrix dosing ratio, the sludge acclimatization cycle can be shortened to 5 days, Cu, the clearance of Zn and Cd has reached respectively 7O.8%, 8O.4% and 78.9%; Simultaneously, in mud, remaining heavy metal content can satisfy the national standard of agricultural sludge.The same year, Huang Ming etc. (2005) studies show that take elemental sulfur as substrate: at the matrix dosing ratio as 5g/L and be accompanied by under 15% acclimation sludge reflux conditions, the sludge acclimatization cycle can be shortened to Cd, the clearance of Cu, Zn and Cd has reached respectively 70.8%, 80.4% and 78.9%.Then, Huang Ming etc. (2006) are take ferrous sulfate as substrate, utilize the SBR technique of simplifying to carry out bioleaching, show: be at the substrate dosing ratio that 10g/L, sludge seeding amount are 30%, room temperature is continuous aeration operation 2d under the condition of 25 ℃, clearance to Cu and Zn reaches 78.3% and 77.7%, near 99%, the residual heavy metal content after leaching is processed in mud meets the national standard of agricultural sludge to the clearance of Cd.2009 with ferrous sulfate as substrate, the further impact of research sludge concentration on the leaching effect of heavy metal, result shows: the sludge concentration of bioleaching should be controlled at 25.6g/L, and after leaching 3d, in the municipal sludge of Guilin, residual heavy metal content meets the national standard of agricultural sludge.The leaching effect that studies show that simple substance sulphur granule heavy metal when 165 μ m in 2010 is best.But this cover continuous flow reactor method equipment complexity copy do loaded down with trivial details.
Because exceed standard heavy metal kind, content, initial pH value gap of different areas different sewage factory is very far away, the removal of giving sludge heavy-metal particularly industrialization brings very large difficulty.
Summary of the invention
The object of the present invention is to provide a kind of method of quick removal municipal sludge heavy metal, to solve the above problem of background technology.
Technical scheme provided by the invention is as follows:
A kind of method of quick removal municipal sludge heavy metal comprises the steps:
(1) take raw sludge as material, add the S(sulphur of 10-20g/L) be substrate, enrichment culture thiobacillus thiooxidant (Thiobacillus thiooxidans), complete to base consumption; Afterwards take the thiobacillus thiooxidant of gained as bacterial classification, add to another take raw sludge as material, the S of 10-20g/L is the nutrient solution of substrate, carries out secondary enrichment culture thiobacillus thiooxidant; Enrichment culture is carried out three times at least, makes this bacterium liquid become the thiobacillus thiooxidant inoculation liquid of high density.
(2) concentration of pending mud is adjusted to 1-5%, and the S that adds 10-20g/L is substrate, and the pH value is adjusted to 4, uses the inoculation liquid inoculation of carrying disease germs of cultivating through at least three times, and inoculum size is at least 5% of pending sludge volume, and temperature 25-32 ℃, leaching was cultivated 2 days.
Raw sludge of the present invention can derive from sewage work etc.
In preferred embodiment of the present invention, step (1) enrichment culture number of times is 3 times.In theory, the more concentration of incubation times are higher; In actual production, only need every day with leaching after sludge liquid to be concentrated stay enough amounts and make bacterial classification and get final product, easy and simple to handle.
In preferred embodiment of the present invention, the pH value is surveyed in being judged as that each enrichment culture finishes, if the pH value is lower than 2 be judged as substrate and substantially consume fully.Also can adopt bacterium to count to reaching finite concentration is standard, but quick not as surveying the pH value, simple, directly perceived.
In preferred embodiment of the present invention, it is 150-250r/min that rotating speed is cultivated in the leaching of step (2).
In preferred embodiment of the present invention, the inoculum size of step (2) is 5-15%
In optimum embodiment of the present invention, in step (1) take the S of 10g/L as substrate; In step (2) take the S of 10g/L as substrate; With the bacterium inoculation of three cultivations, concentration is 15%, and the pH value of pending mud is adjusted to 4,32 ℃ of temperature, and rotating speed is 200r/min.
When the content of the heavy metal that exceeds standard in mud in 2.0 times of scopes of agricultural standards, in step (1) take the S of 10g/L as substrate; In step (2) take the S of 10g/L as substrate; With the bacterium inoculation of three cultivations, inoculum size is 15%, and the concentration of pending mud is adjusted to 1.0-3.0%, and the pH value is adjusted to 4,32 ℃ of temperature; Leaching was cultivated 2 days.
Principle of the present invention is as follows: the acidophilia thiobacillus of original minute quantity in raw sludge, by the optimization to bacterial classification kind, spawn culture number of times, leaching condition, sludge concentration etc., screen suitable microorganism (thiobacillus thiooxidant) and fast enriching and be cultured to enough concentration (at every turn cultivate or leaching with pH＜2 till).Utilize the indirect action of direct effect or its meta-bolites of thiobacillus thiooxidant, by processes such as oxidation, reduction, complexing, absorption, dissolvings, the insoluble heavy metal in mud is separated lixiviate out, then remove a large amount of heavy metals by solid-liquid separation technique.Heavy metal in filtrate reclaims by modes such as alkaline purifications afterwards.
Seen from the above description, the invention provides a kind of method of quick removal municipal sludge heavy metal, utilize method of the present invention, can be with the heavy metal in mud, especially heavy metal Zn, Cu, Cr, Ni clearance in short 2 days reaches respectively 59.01%, 64.11%, 58.32%, 64.90%.Namely work as the content of exceed standard in mud heavy metal Zn, Cu, Cr, Ni in 2.0 times of scopes of agricultural standards, all can remove all heavy metals that exceed standard in 2 days, sludge manure reaches agricultural standards after concentrated accent pH, directly as agricultural fertilizer.And the present invention need not additionally to add bacterial classification, has reduced cost.The substrate that uses is single substrate S, is convenient to calculate consumption, and reduces workload and cost.Method of the present invention can be for due to different areas different sewage factory, the exceed standard mud of heavy metal kind, content, initial pH value of difference, in actual production, after first production mud, after only needing every day with leaching, sludge liquid to be concentrated stays enough amounts and makes bacterial classification and get final product, easy and simple to handle, be convenient to industrialization.
Description of drawings
Fig. 1 is different substrate kinds and the concentration impact on Zn, the Cu amount of leaching in the embodiment of the present invention;
Fig. 2 is the impact of bacterium incubation times on Zn, the Cu amount of leaching in the embodiment of the present invention;
Fig. 3 a is temperature and the pH impact on the Zn amount of leaching in the embodiment of the present invention;
Fig. 3 b is temperature and the pH impact on the Cu amount of leaching in the embodiment of the present invention;
Fig. 4 is that in the embodiment of the present invention, sludge concentration leaches the impact of rate on Zn, Cu.
Embodiment
Embodiment
One, the selection of method research:
A) substrate kind and concentration choice experiment: take the raw sludge of Sha Men Shi STAFF Ya Sewage Plant as material, thiobacillus thiooxidant (Thiobacillus thiooxidans) substrate elemental sulfur (5,10,20g/L), Sulfothiorine (10,20,40g/L) and thiobacillus ferrooxidant (Thiobacillus ferooxidan) substrate FeSO are set
4.7H
2O(10,20,40g/L) totally 9 processing, carry out the heavy metal leaching and cultivate (25 ℃ of normal temperature, rotating speed 200r/min), measure common heavy metal Zn in filtrate, Cu concentration after 6 days.
B) spawn culture number of times and consumption choice experiment: the more concentration of thiobacillus thiooxidant incubation times are higher, and experiment is adopted and cultivated bacterium and once cultivate bacterium two bacterial classifications for three times, and concentration is 0,2%, 5%, 10%, 15% 5 grade, totally ten processing; Take the S of 10g/L as substrate, 25 ℃ of normal temperature, rotating speed 200r/min carry out the heavy metal leaching to be cultivated, and measures filtrate Zn, Cu concentration on the 4th day.
C) leaching condition optimizing experiment: take the S of 10g/L as substrate, 5% 3 time is cultivated bacterium is bacterial classification, CK25 (25 ℃ of normal temperature), T1 (25 ℃ of normal temperature are set, initial pH is adjusted to 4), 25 ℃ of T2(normal temperature), 32 ℃ of CK32(high temperature), T3 (32 ℃ of high temperature, initial pH is adjusted to 4), 32 ℃ of T4(high temperature) 6 processing, rotating speed 200r/min carries out the heavy metal leaching and cultivates, and measures filtrate Zn, Cu concentration on the 4th day.
D) sludge concentration choice experiment: take the S of 10g/L as substrate, cultivate bacterium for 5% 3 time as 32 ℃ of bacterial classification, high temperature, initial pH is adjusted to 4 and is condition, sludge concentration 0,0.5,1.0,2.0,3.0,5.0,8.0%7 concentration are set, rotating speed 200r/min carries out the heavy metal leaching and cultivates, and measures filtrate Zn, Cu concentration on the 4th day.
Two, sludge manure production and heavy metal content are identified:
A) mud production: (Zn, Cu, Cr, Ni exceed standard with Xiamen area mud, Pb, Cd, As, the Hg mud in the agricultural standards scope) be material, the result of study of selecting with above-mentioned four prescription methods namely take the S of 10g/L as substrate, cultivate bacterium for 15% 3 time as 32 ℃ of bacterial classification, high temperature, initial pH is adjusted to 4 and is condition, rotating speed 200r/min carries out the heavy metal leaching and cultivates, and measures the concentration of filtrate Zn, Cu, Pb, Cd, Cr, Ni, As, Hg 8 heavy metal species on the 3rd day.
B) mensuration of 8 heavy metal species: the concentration of 8 heavy metal species in mud before and after the mensuration leaching.Zn, Cu, Pb, Cd, Cr, Ni adopt chloroazotic acid digestion, and VARIAN AA240FS atomic absorption spectrophotometer is measured.As, Hg adopt GB NY/T1978-2010 method to measure.Calculate the clearance of four kinds of heavy metals that exceed standard (Zn, Cu, Cr, Ni).
Result:
One, the selection result of method:
1, substrate kind and concentration are selected:
Result shows: three kinds of substrates with elemental sulfur to leach effect best, wherein, it is the highest that the amount of leaching of Zn is that the S of concentration 10g/L processes, and concentration 20g/L occupies second (be about 10g/L 98.70%), and the amount of leaching of Cu is opposite with Zn (concentration 10g/L be treated to 20g/L 98.05%) just in time.The more economical material benefit of 10g/L when heavy metal content is low.
2, spawn culture number of times and consumption are selected:
Result shows: three times each concentration of bacterium is processed the amount of leaching of Zn, Cu all apparently higher than a bacterium.What the Zn amount of leaching was the highest is that three bacteria concentrations 10% are processed, and 15% processing is taken second place; What the Cu amount of leaching was the highest is that three bacteria concentrations 15% are processed, and 10% processing is taken second place; Three bacteria concentrations 5% are processed the Zn amount of leaching and are 92.09% of the highest amount of leaching, and Cu is 81.30%.Enough with three bacteria concentration 5% lignin-sludges for the mud that heavy metal concentration is lower.
3, leaching condition optimizing:
Result shows: 1. 32 ℃ of lower Zn, the amount of leaching of Cu two metals and the rates that leach are all greater than 25 ℃.2. at two kinds of temperature, Zn each peak that leaches of processing all appears at the 3rd day; What Cu amount of leaching under 32 ℃ was maximum also appears at the 3rd day, but under 25 ℃ the amount of leaching maximum appear at the 4th day, illustrate that high temperature accelerates Cu and leaches.3. transfer pH to the amount of leaching of 32 ℃ of lower Zn, Cu and leach the rate impact not quite, leaching rate but lower pH acceleration Zn, Cu at 25 ℃, improving the amount of leaching.
4, sludge concentration is selected:
Result shows: Zn leaches rate when concentration 2% the highest, and concentration 1% is taken second place; Cu leaches rate when concentration 3% the highest, and concentration 2% is taken second place.Zn, Cu leach rate in concentration greater than 5% the time and descend rapidly.
Two, heavy metal content qualification result up to standard in sludge manure:
Result shows: only with 2 day time, adopt in the Xiamen sludge manure that the leaching proper method of above research produces that the clearance of 4 kinds of heavy metal Zns that exceed standard, Cu, Cr, Ni is respectively 59.01%, 64.11%, 58.32%, 64.90%(table 1), namely work as the content of exceed standard in mud heavy metal Zn, Cu, Cr, Ni and all can remove all heavy metals that exceed standard in 2.0 times of scopes of agricultural standards, sludge manure reaches agricultural standards after concentrated accent pH, directly as agricultural fertilizer.
Table 1: heavy metal content research up to standard in sludge manure
Claims (8)
1. a method of removing fast the municipal sludge heavy metal, comprise the steps:
(1) take raw sludge as material, the S that adds 10-20g/L is substrate, and the enrichment culture thiobacillus thiooxidant is complete to base consumption; Afterwards take the thiobacillus thiooxidant of gained as bacterial classification, add to another take raw sludge as material, the S of 10-20g/L is the nutrient solution of substrate, carries out secondary enrichment culture thiobacillus thiooxidant; Enrichment culture is carried out three times at least, makes this bacterium liquid become the thiobacillus thiooxidant inoculation liquid of high density;
(2) concentration of pending mud is adjusted to 1-5%, uses the inoculation liquid inoculation of carrying disease germs of cultivating through at least three times, and inoculum size is at least 5% of pending sludge volume, and the S that adds 10-20g/L is substrate, and the pH value is adjusted to 4, and temperature 25-32 ℃, leaching was cultivated 2 days.
2. the method for a kind of quick removal municipal sludge heavy metal as claimed in claim 1, it is characterized in that: also comprise step (3), the mud after processing stays enough amounts and makes bacterial classification, directly adds next time pending mud to carry out next time production.
3. the method for a kind of quick removal municipal sludge heavy metal as claimed in claim 1, it is characterized in that: described raw sludge derives from sewage work.
4. the method for a kind of quick removal municipal sludge heavy metal as claimed in claim 1, it is characterized in that: step (1) enrichment culture number of times is 3 times.
5. the method for a kind of quick removal municipal sludge heavy metal as claimed in claim 1 or 2 is characterized in that: the pH value is surveyed in being judged as that each enrichment culture finishes, if the pH value is lower than 2 be judged as substrate and substantially consume fully.
6. the method for a kind of quick removal municipal sludge heavy metal as claimed in claim 1 is characterized in that: it is 150-250r/min that rotating speed is cultivated in the leaching of step (2).
7. the method for a kind of quick removal municipal sludge heavy metal as claimed in claim 1, it is characterized in that: the inoculum size of step (2) is 5-15%.
8. the method for a kind of quick removal municipal sludge heavy metal as claimed in claim 1 is characterized in that:
When the content of the heavy metal that exceeds standard in mud in 2.0 times of scopes of agricultural standards, in step (1) take the S of 10g/L as substrate; In step (2), pending sludge concentration is adjusted to 1.0-3.0%, take the S of 10g/L as substrate; With the bacterium inoculation of three cultivations, inoculum size is that 15%, pH value is adjusted to 4,32 ℃ of temperature; Leaching was cultivated 2 days.
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Cited By (9)
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| CN104058565A (en) * | 2014-06-28 | 2014-09-24 | 南京理工大学 | Method for treating pickled sludge by using ferrous oxide thiobacillus |
| CN104478184A (en) * | 2014-11-28 | 2015-04-01 | 新疆天物科技发展有限公司 | Clean utilization method for municipal sludge |
| CN105731749A (en) * | 2016-03-16 | 2016-07-06 | 福州大学 | Method of removing heavy metal Cd in sludge through bioleaching |
| CN105731750A (en) * | 2016-03-16 | 2016-07-06 | 福州大学 | Method for removing heavy metal in sludge by means of bioleaching by aid of mixed substrates |
| CN105776788A (en) * | 2016-04-19 | 2016-07-20 | 福州大学 | Method for removing heavy metal Cu in sludge of urban sewage treatment plant in bioleaching mode |
| CN107244999A (en) * | 2017-05-24 | 2017-10-13 | 攀枝花市绿态美生物科技有限公司 | It is a kind of to remove microbial bacterial agent of removing heavy metals and its preparation method and application |
| CN108191183A (en) * | 2018-01-23 | 2018-06-22 | 广东工业大学 | The minimizing technology of heavy metals in city sewage sludge |
| CN110040926A (en) * | 2019-04-28 | 2019-07-23 | 四川大学 | The two stage biological leaching continuous processing of heavy metal chromium in efficient removal leather-making mud |
| CN114850195A (en) * | 2022-07-06 | 2022-08-05 | 矿冶科技集团有限公司 | Stabilizing agent for lead, arsenic and cadmium and method for treating multi-metal calcium-based slag mud by using stabilizing agent |
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| CN104058565A (en) * | 2014-06-28 | 2014-09-24 | 南京理工大学 | Method for treating pickled sludge by using ferrous oxide thiobacillus |
| CN104478184A (en) * | 2014-11-28 | 2015-04-01 | 新疆天物科技发展有限公司 | Clean utilization method for municipal sludge |
| CN105731750B (en) * | 2016-03-16 | 2018-10-30 | 福州大学 | A kind of method of mixed-matrix bioleaching removal sludge heavy-metal |
| CN105731749A (en) * | 2016-03-16 | 2016-07-06 | 福州大学 | Method of removing heavy metal Cd in sludge through bioleaching |
| CN105731750A (en) * | 2016-03-16 | 2016-07-06 | 福州大学 | Method for removing heavy metal in sludge by means of bioleaching by aid of mixed substrates |
| CN105731749B (en) * | 2016-03-16 | 2018-10-30 | 福州大学 | A kind of method of bioleaching removal Heavy Metals in Sludge Cd |
| CN105776788B (en) * | 2016-04-19 | 2019-03-08 | 福州大学 | A kind of method that bioleaching removes heavy metal Cu in sludge from wastewater treatment plant |
| CN105776788A (en) * | 2016-04-19 | 2016-07-20 | 福州大学 | Method for removing heavy metal Cu in sludge of urban sewage treatment plant in bioleaching mode |
| CN107244999A (en) * | 2017-05-24 | 2017-10-13 | 攀枝花市绿态美生物科技有限公司 | It is a kind of to remove microbial bacterial agent of removing heavy metals and its preparation method and application |
| CN108191183A (en) * | 2018-01-23 | 2018-06-22 | 广东工业大学 | The minimizing technology of heavy metals in city sewage sludge |
| CN110040926A (en) * | 2019-04-28 | 2019-07-23 | 四川大学 | The two stage biological leaching continuous processing of heavy metal chromium in efficient removal leather-making mud |
| CN114850195A (en) * | 2022-07-06 | 2022-08-05 | 矿冶科技集团有限公司 | Stabilizing agent for lead, arsenic and cadmium and method for treating multi-metal calcium-based slag mud by using stabilizing agent |
| CN114850195B (en) * | 2022-07-06 | 2022-09-23 | 矿冶科技集团有限公司 | Stabilizing agent for lead, arsenic and cadmium and method for treating multi-metal calcium-based sludge by using stabilizing agent |
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Effective date of registration: 20210708 Address after: No. 169, Huanmei North Road, Guankou Town, Jimei District, Xiamen City, Fujian Province 361000 Patentee after: XIAMEN TASMAN BIO-TECH Co.,Ltd. Address before: 361012 No. 780, Jiahe Road, Xiamen, Fujian Patentee before: SUBTROPICAL CROPS INSTITUTE OF FUJIAN PROVINCE |