CN105776788B - A kind of method that bioleaching removes heavy metal Cu in sludge from wastewater treatment plant - Google Patents
A kind of method that bioleaching removes heavy metal Cu in sludge from wastewater treatment plant Download PDFInfo
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- CN105776788B CN105776788B CN201610242943.4A CN201610242943A CN105776788B CN 105776788 B CN105776788 B CN 105776788B CN 201610242943 A CN201610242943 A CN 201610242943A CN 105776788 B CN105776788 B CN 105776788B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/02—Biological treatment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/06—Sludge reduction, e.g. by lysis
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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
- Y02W10/20—Sludge processing
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Abstract
The invention discloses the methods of heavy metal Cu in a kind of bioleaching removal sludge from wastewater treatment plant, solve the problems, such as that it is agricultural that the sludge after processing can be used as fertilizer containing more heavy metal Cu in sludge from wastewater treatment plant.The specific steps of which are as follows: Thiobacillus original in sludge progress enrichment culture is obtained acclimation sludge, and with this inoculum the most, it is added in primary sludge, and add Na2S2O3And FeSO4Substrate, Na2S2O3Dosage is controlled in 3~5g/L, FeSO4Dosage is controlled in 4~6g/L, and air is blasted into sludge with 1.0~1.5/min, and stir with certain revolving speed, and temperature is controlled at 20~30 DEG C, carries out bioleaching to sludge.By 3~4d bioleaching time, so that the removal rate of heavy metal Cu reaches 90% or more.The present invention has rational design, practical.
Description
Technical field
The present invention relates to a kind of method of heavy metal Cu in removal sludge from wastewater treatment plant, especially a kind of biology leaching
Filter off the method except heavy metal Cu in sludge from wastewater treatment plant.
Background technique
Sludge is the inevitable outcome during municipal sewage plant's processing sewage.With the hair of domestic sewage disposal cause
Exhibition, sewage plant total process water yield are continuously increased, and degree for the treatment of is continuously improved, and the sludge quantity of generation also increasingly increases.Obviously, so
If a large amount of sludge is dealt with improperly, the normal operation of sewage treatment plant not only will affect, but also because containing a large amount of in sludge
Harmful substance, such as heavy metal, bacterium, various parasitic ovums, a large amount of pathogenic microorganism, it is easy to cause secondary pollution.
In addition, the nutrients such as organic matter and nitrogen rich in, phosphorus, potassium in sludge, if untreated any discharge, not only pollutes
Environment, while being also the serious waste to resource.To prevent secondary pollution caused by sludge and guaranteeing the normal of sewage treatment plant
Operation and treatment effect, realize that the minimizing of sludge, innoxious, stable and recycling are that current environmental area is urgently to be solved and ask
Topic.Rationally handle, dispose and make full use of the effective way of sludge to have important practical significance so research is found.
It is that recycling sludge utilizes that heavy metal in sludge is many kinds of, which mainly to have Cu, Pb, Zn, Ni, Cr, Hg and Cd etc.,
Main obstacle.To handle generated sludge based on sanitary sewage, content of beary metal is usually lower, and to handle trade effluent
Based on generated sludge, content of beary metal is often higher.It migrated since heavy metal has the characteristics that hardly possible, be easily enriched with and endanger big
Have become the main factor of limitation sludge agricultural use.Whether municipal sludge or industrial sludge, since it contains mostly
The heavy metal element being more toxic, will be to sewage treatment plant or even using the regional periphery life of sewage sludge if dealt with improperly
State environment, which is constituted, to be seriously endangered.Therefore, reduction or the exceeded heavy metal element removed in sludge become effectively disposition and utilize dirty
The key of mud.Currently, to solve harm that heavy metals in city sewage sludge element may cause ecological environment and to sludge agriculture
The research that restriction is carried out is more, but majority is carried out from stable and reduction heavy metal element toxicity angle, from reduction
The total quantifier elimination of Heavy Metals in Sludge is relatively fewer.
Bioleaching is directly acted on using natural some microorganisms or the indirectly-acting of its metabolite, such as aoxidizes,
The effects of reduction, acidification, leaches the certain slightly solubilities of sludge or insoluble composition (such as heavy metal, sulphur) separation.Again by sludge
It is dehydrated, realizes the purpose of removal Heavy Metals in Sludge.Bioleaching has the advantage that compared with chemical leaching, can save
About acid consumption is not required to acid adding and carries out pre-acidified to sludge, can digest and combine with aerobic sludge, and existing operation is made full use of to set
It applies, reduces operating cost and capital cost；Rapidly, leaching is high-efficient, and the time is short for starting, is suitable for processing any type sludge；Operation
Simply, operational process is not necessarily to Special controlling, can leaching heavy metal within the scope of 10 DEG C~37 DEG C；Sludge after bioleaching,
Dewatering greatly improves, and when dehydration does not need addition flocculating agent, effectively saves sludge dewatering cost；Bioleaching can be effective
It goes removing heavy metals that can kill pathogen again, and declines VSS.
The main bacteria that bioleaching uses is Thiobacillus ferrooxidans (Thiobacillus ferrooxidans, T.f)
With the acidophilic thiobacillus such as Thiobacillus thioxidans (Thiobacillus thiooxidans, T.t), in its metabolic processes
In, the effects of generating oxidation, reduction, be acidified, dissolve.The weight in using bioleaching technology removal sludge from wastewater treatment plant
Metal in the prior art, has portion of techniques to be inoculated with thallus using purebred T.f and T.t as leaching, and such method is complicated for operation,
Processing cost is high, is not easy large-scale use；Also the part prior art does not need additional inoculated bacteria, using intrinsic in sludge
Bacterium carries out enrichment culture and obtains acclimation sludge, and then acclimation sludge is seeded in primary sludge and carries out bioleaching, but is required
The energy substance concentration of addition is high, and acclimation sludge inoculum concentration is big, and the removal effect of heavy metal is general.
Summary of the invention
In order to solve deficiency in the prior art, the purpose of the present invention is to provide one kind with Na2S2O3And FeSO4For energy
The side of heavy metal Cu in the low bioleaching removal sludge from wastewater treatment plant of the addition concentration of source substance and energy substance
Method.
To achieve the above object, the invention adopts the following technical scheme:
A kind of method that bioleaching removes heavy metal Cu in sludge from wastewater treatment plant comprising following steps:
(1) first time enrichment culture: taking the primary sludge of sewage treatment plant, and the Na of 3~5g/L is added into primary sludge2S2O3
With the FeSO of 4~6g/L4For substrate, intrinsic Thiobacillus thioxidans and Thiobacillus ferrooxidans in enrichment culture primary sludge are rich
Collection culture to sludge pH is down to 2.5 hereinafter, acclimation sludge after obtaining first time enrichment culture；
(2) second of enrichment culture: the acclimation sludge after taking first time enrichment culture 4~6% is inoculated into life by volume
In sludge, the Na of 3~5g/L is added2S2O3With the FeSO of 4~6g/L4For substrate, enrichment culture at identical conditions, until
PH value is down to 2.5 hereinafter, obtaining the acclimation sludge after second of enrichment culture；
Second of enrichment culture is repeated at least once more, gained acclimation sludge mixed liquor is inoculum；
(3) bioleaching: using step (2) resulting inoculum, 4~6% be inoculated into primary sludge by volume, addition 3
The Na of~5g/L2S2O3With the FeSO of 4~6g/L4For substrate, initial pH value is adjusted to 5~7, and leaching is trained at a temperature of 20~30 DEG C
The effects of 3~4 days feeding, Thiobacillus thioxidans and Thiobacillus ferrooxidans pass through oxidation, restore, acidification, by the weight in primary sludge
Ni metal separation is leached to water phase；
(4) sludge settling: the sludge settling after step (3) to be carried out to bioleaching obtains the sludge of low metal Cu content
With the sewage of high metal Cu content.
Na is added into resulting sewage after step (4) sludge settling2S carries out precipitated metal, is separated by solid-liquid separation, respectively obtains
Supernatant and solid heavy metals precipitating.
The aeration intensity of the leaching culture of step (3) is controlled at 1.0~1.5L/ (minL).
The speed of agitator of the leaching culture of step (3) is 150~250r/min.
After leaching culture 3~4 days, sludge pH is down to 2.0 or less.
The invention adopts the above technical scheme, have it is following the utility model has the advantages that
1) Thiobacillus thioxidans of itself and Thiobacillus ferrooxidans bioleaching in sludge are enriched with；After required enrichment culture
The inoculum concentration of acclimation sludge is low, and inoculation volume ratio is 4~6%, and the inoculation volume ratio that patent CN103274575A needs is 10
~15%；
2) with Na2S2O3And FeSO4Energy substance is provided for Thiobacillus as substrate, due to having collaboration between the two
Effect, compared to individually with substrate sulphur powder or individually with substrate FeSO4As energy substance, can be provided to T.t and T.f better
Growing environment；
3) Na added needed for2S2O3And FeSO4Dosage it is low, respectively only need 3~5g/L a Na2S2O3With 4~6g/L
FeSO4, and using S as substrate in patent CN103274575A, the amount for needing to add S is 10~20g/L；
4) good to the removal effect of heavy metal Cu, the maximum material removal rate of metal in sludge Cu is 92.3% after leaching, leaching
Sludge afterwards can be used for land use.
Amount of substrate needed for the present invention is low, and the cost for removing Heavy Metals in Sludge Cu is low, good to the removal effect of heavy metal Cu,
Design is rationally, practical.
Specific embodiment
A kind of method that bioleaching removes heavy metal Cu in sludge from wastewater treatment plant comprising following steps:
(1) first time enrichment culture: taking the primary sludge of sewage treatment plant, and the Na of 3~5g/L is added into primary sludge2S2O3
With the FeSO of 4~6g/L4For substrate, intrinsic Thiobacillus thioxidans and Thiobacillus ferrooxidans in enrichment culture primary sludge are rich
Collection culture to sludge pH is down to 2.5 hereinafter, acclimation sludge after obtaining first time enrichment culture；
(2) second of enrichment culture: the acclimation sludge after taking first time enrichment culture 4~6% is inoculated into life by volume
In sludge, the Na of 3~5g/L is added2S2O3With the FeSO of 4~6g/L4For substrate, enrichment culture at identical conditions, until
PH value is down to 2.5 hereinafter, obtaining the acclimation sludge after second of enrichment culture；
Second of enrichment culture is repeated at least once more, gained acclimation sludge mixed liquor is inoculum；
(3) bioleaching: using step (2) resulting inoculum, 4~6% be inoculated into primary sludge by volume, addition 3
The Na of~5g/L2S2O3With the FeSO of 4~6g/L4For substrate, initial pH value is adjusted to 5~7, and leaching is trained at a temperature of 20~30 DEG C
The effects of 3~4 days feeding, Thiobacillus thioxidans and Thiobacillus ferrooxidans pass through peroxidating, restore, acidification, will be in primary sludge
Heavy metal Cu separation is leached to water phase；
(4) sludge settling: the sludge settling after step (3) to be carried out to bioleaching obtains the sludge of low metal Cu content
With the sewage of high metal Cu content.
Na is added into resulting sewage after step (4) sludge settling2S carries out precipitated metal, is separated by solid-liquid separation, respectively obtains
Supernatant and solid heavy metals precipitating.
The primary sludge is the excess sludge that cyclic activated sludge system handles that city domestic sewage generates.
The aeration intensity of the leaching culture of step (3) is controlled at 1.0~1.5L/ (minL).
The speed of agitator of the leaching culture of step (3) is 150~250r/min.
After leaching culture 3~4 days, sludge pH is down to 2.0 or less.
Embodiment 1
A kind of method that bioleaching removes heavy metal Cu in sludge from wastewater treatment plant comprising following steps:
(1) first time enrichment culture: taking the primary sludge of sewage treatment plant, and the Na of 3g/L is added into primary sludge2S2O3With
The FeSO of 6g/L4For substrate, intrinsic Thiobacillus thioxidans and Thiobacillus ferrooxidans, enrichment culture in enrichment culture primary sludge
2.5 are down to hereinafter, acclimation sludge after obtaining first time enrichment culture to sludge pH；
(2) second of enrichment culture: the acclimation sludge after taking first time enrichment culture 5% is inoculated into raw dirt by volume
In mud, the Na of 3g/L is added2S2O3With the FeSO of 6g/L4For substrate, enrichment culture at identical conditions, until pH value is down to
2.5 hereinafter, obtain the acclimation sludge after second of enrichment culture；
Second of enrichment culture is repeated at least once more, gained acclimation sludge mixed liquor is inoculum；
(3) bioleaching: using step (2) resulting inoculum, 5% be inoculated into primary sludge by volume, adds 3g/L
Na2S2O3With the FeSO of 6g/L4For substrate, initial pH value is adjusted to 6, leaching culture 3 days at a temperature of 20 DEG C, sulfur oxide sulphur bar
Heavy metal Cu separation in primary sludge is leached to water by the effects of bacterium and Thiobacillus ferrooxidans are restored by oxidation, acidification
Phase；
(4) sludge settling: the sludge settling after step (3) to be carried out to bioleaching obtains the sludge of low metal Cu content
With the sewage of high metal Cu content.
Na is added into resulting sewage after step (4) sludge settling2S carries out precipitated metal, is separated by solid-liquid separation, respectively obtains
Supernatant and solid heavy metals precipitating.
The primary sludge is the excess sludge that cyclic activated sludge system handles that city domestic sewage generates.
The aeration intensity of the leaching culture of step (3) is controlled at 1.0L/ (minL).
The speed of agitator of the leaching culture of step (3) is 150r/min.
After leaching culture 3 days, sludge pH is down to 2.0 or less.
Embodiment 2
A kind of method that bioleaching removes heavy metal Cu in sludge from wastewater treatment plant comprising following steps:
(1) first time enrichment culture: taking the primary sludge of sewage treatment plant, and the Na of 4g/L is added into primary sludge2S2O3With
The FeSO of 4g/L4For substrate, intrinsic Thiobacillus thioxidans and Thiobacillus ferrooxidans, enrichment culture in enrichment culture primary sludge
2.5 are down to hereinafter, acclimation sludge after obtaining first time enrichment culture to sludge pH；
(2) second of enrichment culture: the acclimation sludge after taking first time enrichment culture 4% is inoculated into raw dirt by volume
In mud, the Na of 4g/L is added2S2O3With the FeSO of 4g/L4For substrate, enrichment culture at identical conditions, until pH value is down to
2.5 hereinafter, obtain the acclimation sludge after second of enrichment culture；
Second of enrichment culture is repeated at least once more, gained acclimation sludge mixed liquor is inoculum；
(3) bioleaching: using step (2) resulting inoculum, 4% be inoculated into primary sludge by volume, adds 4g/L
Na2S2O3With the FeSO of 4g/L4For substrate, initial pH value is adjusted to 5, leaching culture 4 days at a temperature of 30 DEG C, sulfur oxide sulphur bar
Heavy metal Cu separation in primary sludge is leached to water by the effects of bacterium and Thiobacillus ferrooxidans are restored by oxidation, acidification
Phase；
(4) sludge settling: the sludge settling after step (3) to be carried out to bioleaching obtains the sludge of low metal Cu content
With the sewage of high metal Cu content.
Na is added into resulting sewage after step (4) sludge settling2S carries out precipitated metal, is separated by solid-liquid separation, respectively obtains
Supernatant and solid heavy metals precipitating.
The primary sludge is the excess sludge that cyclic activated sludge system handles that city domestic sewage generates.
The aeration intensity of the leaching culture of step (3) is controlled at 1.5L/ (minL).
The speed of agitator of the leaching culture of step (3) is 250r/min.
After leaching culture 4 days, sludge pH is down to 2.0 or less.
Embodiment 3
A kind of method that bioleaching removes heavy metal Cu in sludge from wastewater treatment plant comprising following steps:
(1) first time enrichment culture: taking the primary sludge of sewage treatment plant, and the Na of 5g/L is added into primary sludge2S2O3With
The FeSO of 5g/L4For substrate, intrinsic Thiobacillus thioxidans and Thiobacillus ferrooxidans, enrichment culture in enrichment culture primary sludge
2.5 are down to hereinafter, acclimation sludge after obtaining first time enrichment culture to sludge pH；
(2) second of enrichment culture: the acclimation sludge after taking first time enrichment culture 6% is inoculated into raw dirt by volume
In mud, the Na of 5g/L is added2S2O3With the FeSO of 5g/L4For substrate, enrichment culture at identical conditions, until pH value is down to
2.5 hereinafter, obtain the acclimation sludge after second of enrichment culture；
Second of enrichment culture is repeated at least once more, gained acclimation sludge mixed liquor is inoculum；
(3) bioleaching: using step (2) resulting inoculum, 6% be inoculated into primary sludge by volume, adds 5g/L
Na2S2O3With the FeSO of 5g/L4For substrate, initial pH value is adjusted to 7, leaching culture 4 days at a temperature of 25 DEG C, sulfur oxide sulphur bar
Heavy metal Cu separation in primary sludge is leached to water by the effects of bacterium and Thiobacillus ferrooxidans are restored by oxidation, acidification
Phase；
(4) sludge settling: the sludge settling after step (3) to be carried out to bioleaching obtains the sludge of low metal Cu content
With the sewage of high metal Cu content.
Na is added into resulting sewage after step (4) sludge settling2S carries out precipitated metal, is separated by solid-liquid separation, respectively obtains
Supernatant and solid heavy metals precipitating.
The primary sludge is the excess sludge that cyclic activated sludge system handles that city domestic sewage generates.
The aeration intensity of the leaching culture of step (3) is controlled at 1.2L/ (minL).
The speed of agitator of the leaching culture of step (3) is 200r/min.
After leaching culture 4 days, sludge pH is down to 2.0 or less.
Control experiment 1: by the substrate Na in embodiment 32S2O3Substrate S is replaced with, remaining condition is constant.
Control experiment 2: by the substrate FeSO in embodiment 34Remove, does not add FeSO4Substrate, remaining condition are constant.
Control experiment 3: by the substrate Na in embodiment 32S2O3Remove, does not add Na2S2O3Substrate, remaining condition are constant.
The removal effect of the heavy metal Cu of each embodiment of table 1 and each control experiment different disposal method compares
As it can be seen from table 1 with Na2S2O3And FeSO4Removal rate for the heavy metal of substrate is substantially better than with S and FeSO4
For the removal rate of the heavy metal of substrate；With Na2S2O3And FeSO4For the heavy metal of substrate removal rate be substantially better than respectively with
Na2S2O3Or FeSO4For the removal rate of the heavy metal of substrate.The removal rate of heavy metal is in addition to related with substrate, also with being enriched with number
Etc. closely bound up.
Claims (5)
1. a kind of method of heavy metal Cu in bioleaching removal sludge from wastewater treatment plant, which is characterized in that it includes such as
Lower step:
(1) first time enrichment culture: taking the primary sludge of sewage treatment plant, and the Na of 3~5g/L is added into primary sludge2S2O3With 4~
The FeSO of 6g/L4For substrate, intrinsic Thiobacillus thioxidans and Thiobacillus ferrooxidans in enrichment culture primary sludge, enrichment training
It supports to sludge pH and is down to 2.5 hereinafter, acclimation sludge after obtaining first time enrichment culture；
(2) second of enrichment culture: the acclimation sludge after taking first time enrichment culture 4~6% is inoculated into primary sludge by volume
In, add the Na of 3~5g/L2S2O3With the FeSO of 4~6g/L4For substrate, enrichment culture at identical conditions, until pH value
2.5 are down to hereinafter, obtaining the acclimation sludge after second of enrichment culture；
Second of enrichment culture is repeated at least once more, gained acclimation sludge mixed liquor is inoculum；
(3) bioleaching: using step (2) resulting inoculum, 4~6% be inoculated into primary sludge by volume, adds 3~5g/L
Na2S2O3With the FeSO of 4~6g/L4For substrate, initial pH value is adjusted to 5~7, at a temperature of 20~30 DEG C leaching culture 3~
4 days, Thiobacillus thioxidans and Thiobacillus ferrooxidans passed through oxidation, reduction, acidification, by the heavy metal Cu in primary sludge
Separation is leached to water phase；
(4) sludge settling: the sludge settling after step (3) to be carried out to bioleaching obtains the sludge and height of low metal Cu content
The sewage of Ni metal content.
2. the method for heavy metal Cu in a kind of bioleaching removal sludge from wastewater treatment plant according to claim 1,
It is characterized by: adding Na into resulting sewage after step (4) sludge settling2S carries out precipitated metal, is separated by solid-liquid separation, respectively
Obtain supernatant and solid heavy metals precipitating.
3. the method for heavy metal Cu in a kind of bioleaching removal sludge from wastewater treatment plant according to claim 1,
It is characterized by: the aeration intensity of the leaching culture of step (3) is controlled at 1.0~1.5 L/ (min L).
4. the method for heavy metal Cu in a kind of bioleaching removal sludge from wastewater treatment plant according to claim 1,
It is characterized by: the speed of agitator of the leaching culture of step (3) is 150~250r/min.
5. the method for heavy metal Cu in a kind of bioleaching removal sludge from wastewater treatment plant according to claim 1,
It is characterized by: sludge pH is down to 2.0 or less after leaching culture 3~4 days.
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| CN106316025A (en) * | 2016-09-30 | 2017-01-11 | 天津城建大学 | Method for removing Zn in sludge by using anaerobic acidification method |
| CN106477839A (en) * | 2016-09-30 | 2017-03-08 | 天津城建大学 | The method that Cr and Cu in mud is removed using ferrous oxide acid Thiobacillus simultaneously |
| CN108423955B (en) * | 2018-03-26 | 2021-01-29 | 广州大学 | Process for removing heavy metal copper in municipal sludge |
| CN110129227B (en) * | 2019-05-16 | 2020-03-03 | 铁汉山艺环境建设有限公司 | Mixed microbial inoculum for removing heavy metals in industrial wastewater and sludge and application thereof |
| CN110373544B (en) * | 2019-07-25 | 2020-06-16 | 中国科学院过程工程研究所 | Device and method for gradient treatment of metal ions in heavy metal sludge by deep-sea microorganisms |
| CN111763648A (en) * | 2020-07-29 | 2020-10-13 | 中原工学院 | Acidophilic mixed strain and rapid preparation method and application thereof |
| CN112174463A (en) * | 2020-10-19 | 2021-01-05 | 广州大学 | Method for dosing thiobacillus thiooxidans energy substance for municipal sludge dehydration treatment |
| CN112551843B (en) * | 2020-12-16 | 2023-05-23 | 太原理工大学 | Method for improving sludge dewatering performance by combining bioleaching and ultrasonic |
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| JPH11156396A (en) * | 1997-07-18 | 1999-06-15 | Toray Ind Inc | Waste water treatment method and apparatus therefor |
| CN103086580A (en) * | 2012-11-21 | 2013-05-08 | 福建省亚热带植物研究所 | Method for quickly removing heavy metals in municipal sludge |
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