CN108569833A - A kind of method of Ciprofloxacin anaerobic degradation in promotion excess sludge - Google Patents
A kind of method of Ciprofloxacin anaerobic degradation in promotion excess sludge Download PDFInfo
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- CN108569833A CN108569833A CN201710132912.8A CN201710132912A CN108569833A CN 108569833 A CN108569833 A CN 108569833A CN 201710132912 A CN201710132912 A CN 201710132912A CN 108569833 A CN108569833 A CN 108569833A
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- ciprofloxacin
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- excess sludge
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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
- C02F11/04—Anaerobic treatment; Production of methane by such processes
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- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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- Organic Chemistry (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention belongs to environmental protection antibiotic difficult to degrade to pollute processing technology field, be related to a kind of method promoting Ciprofloxacin anaerobic degradation in excess sludge, and specific method includes the following steps：Excess sludge containing Ciprofloxacin is fitted into anaerobic reactor, biosurfactant and calper calcium peroxide are added into reactor, stirring keeps material mixing in reactor uniform, while controlling fermentation temperature.The present invention can be effectively facilitated the degradation of Ciprofloxacin in sludge, alleviate pollution of the Ciprofloxacin to environment, land use is carried out for excess sludge after Anaerobic Treatment to lay the foundation, while there is positive guidance and reference to how efficiently to remove other antibiotic contaminations in excess sludge.
Description
Technical field
Present invention relates generally to Solid Waste Treatment technical field, refers in particular to Ciprofloxacin in a kind of promotion excess sludge and detest
The method of oxygen degradation.
Technical background
Antibiotic ciprofloxacin is a kind of important emerging pollutant at present.Ciprofloxacin is third generation quinolones antibacterial
There is drug broad spectrum antibiotic activity, bactericidal effect to wait points well, good antibacterial action is all had to a variety of bacteriums.As one
Kind Common drugs are widely used.It is very big by one since metabolism amount of the antibiotic ciprofloxacin in human body, livestock body is limited
Part is not degraded effectively when being excreted in a manner of excreta by human body, and without the Ciprofloxacin by metabolism
Enter sewerage system mostly and eventually enters into urban sewage treatment system.Have document show municipal wastewater treatment plant water inlet,
Ciprofloxacin is detected in water outlet and excess sludge, can be discharged with excess sludge by the Ciprofloxacin that sludge is adsorbed, portion
Branch enters soil in the form of fertilizer, remaining may carry out landfill disposal after treatment.Although Ciprofloxacin is in environment
In concentration it is relatively low, but China it is annual excess sludge production it is huge, by the end of the end of the year 2013, sludge yield is up to 30,000,000 tons
(with 80% moisture content), the processing for excess sludge, it is many states to carry out land use after anaerobic sludge digestion pretreatment
A kind of technological means that family area uses, but Ciprofloxacin is difficult degradation in the natural environment, while when it is long in the environment
Between accumulate, organism in environment can be made to generate drug resistance, while will produce resistant gene.Therefore promote the ring in excess sludge
Third husky star effectively degradation is for controlling its potential pollution, it is ensured that excess sludge is of great significance by safe utilization.
Calper calcium peroxide can slow oxygen release, it is nontoxic, have application in building, chemical industry, water process etc..In acidity
Under the conditions of can generate H2O2, Fe2+In the presence of can discharge the very strong hydroxyl radical free radical of high activity, oxidisability (OH), be one
Kind embryonic stem-like cells.Therefore it can promote the decomposition of organic substance with strong oxidizing property.
Alkyl glycosides (APG for short) is synthesized by renewable resource natural fat alcohol and glucose, is a kind of performance peace
Full new non-ionic surfactants have good surface-active, good ecological safety and compatibility, are generally acknowledged
" green " functional surfactant.
Biosurfactant APG can promote sludge to dissolve out, and then promote releasing by Ciprofloxacin that sludge is adsorbed
It puts, to increasing calper calcium peroxide, microorganism and the touch opportunity of Ciprofloxacin, the strong positive using calper calcium peroxide and microorganism
Biodegradability promotes the degradation of Ciprofloxacin.
Do not promote the report of the degradation of Ciprofloxacin in sludge with calper calcium peroxide and biosurfactant favorably also at present.
Invention content
The object of the present invention is to provide a kind of Ciprofloxacin anaerobic degradation methods in promotion excess sludge, realize Ciprofloxacin
Efficient degradation, carry out land use after Anaerobic Treatment for excess sludge and lay the foundation.
1. a kind of method for promoting excess sludge anaerobic fermentation to degrade antibiotic ciprofloxacin star, which is characterized in that including
Following steps：
Excess sludge containing Ciprofloxacin is added in anaerobic reactor, add thereto biosurfactant and
Calper calcium peroxide, control fermentation process pH are alkalinity, and stirring keeps material mixing in reactor uniform, entire reaction process control reaction
Temperature.
2. according to the method described in claim 1, it is characterized in that, sludge is derived from Ciprofloxacin pharmaceutical factory in the step
The sludge that secondary settling tank is discharged in sewage treatment plant of area.
3. according to the method described in claim 2, it is characterized in that, sludge in the step is placed in 4 DEG C of incubators
After natural sedimentation for 24 hours, removes supernatant and obtain the excess sludge.
4. according to the method described in claim 1, it is characterized in that, biosurfactant is APG. in the step
5. according to the method described in claim 1, it is characterized in that, in the step calper calcium peroxide dosage be 0.05~
0.35g/g TSS；It is preferred that dosage is 0.10~0.20g/g TSS.
6. according to the method described in claim 1, it is characterized in that, biosurfactant additive amount is in the step
0.1~0.5g/g TSS；It is preferred that dosage is 0.2~0.4g/g TSS.
7. method according to any one of claim 1 to 6, which is characterized in that anaerobic fermentation is whole in the step
The pH controls of a process are 8.5~11.0；Preferable ph is 9.5~10.5.
8. method according to any one of claim 1 to 6, which is characterized in that anaerobic fermentation in the step
Temperature is 25~45 DEG C, and fermentation period is 8-15 days；It is preferred that run time is 10 days.
9. method according to any one of claim 1 to 6, which is characterized in that the step anaerobic fermentation stirs
Mix rotating speed is 105~125r/min；It is preferred that mixing speed is 115r/min.
10. method according to any one of claim 1 to 6, which is characterized in that the step anaerobic fermentation starts
Reactor carries out logical operating under nitrogen before, it is ensured that reactor is in anaerobism.
Calper calcium peroxide dosage and the preferred range of ratios of mud dry weight are (0.10~0.20)：1, it is found through overtesting, when
The ratio of calper calcium peroxide dosage and mud dry weight is more than 0.2:When 1, the process of sludge anaerobic fermentation and acid production can be inhibited.Therefore it examines
Consider the bioactivity of sludge anaerobic fermentation process, dosage ratio of the present invention is 0.10~0.20：1.
Biosurfactant dosage and the preferred range of ratios of mud dry weight are (0.2~0.4)：1, although the surface
The ratio of activating agent dosage and mud dry weight is in (0.1~0.5)：It is right in sludge anaerobic fermentation process to promote in the range of 1
The degradation efficiency of hard-degraded substance Ciprofloxacin.It is contemplated that the relationship of cost and efficiency, dosage ratio of the present invention
It is 0.2~0.4：1.
The present invention promotes sludge middle ring third in sludge anaerobic fermentation process husky using calper calcium peroxide and biosurfactant
The mechanism of the degradation of star is as follows：
A Ciprofloxacin major reason difficult to degrade in sludge anaerobic fermentation process is its third generation as synthesis
Carbostyril family antibacterial drugs have broad spectrum antibiotic activity, and bactericidal effect is good, almost have to the germy antibacterial activity of institute stronger
Inhibiting effect, while Ciprofloxacin is attracted to the surface of sludge in excess sludge, it is difficult to be discharged into zymotic fluid, also has more
Few chance is degraded.Therefore, by Ciprofloxacin from desorption in excess sludge, be discharged into zymotic fluid, and utilize peroxidating
The strong oxidizing property degradation Ciprofloxacin of calcium is the effective ways for the degradation rate for improving Ciprofloxacin.
The invention has the advantages that：
1. in sludge alkalinity fermentation process, improving Ciprofloxacin in excess sludge using biosurfactant APG and desorbing
Attached, increase Ciprofloxacin, which is discharged into zymotic fluid, to be measured.APG not only has solubilization simultaneously, but also is easy in the environment micro-
Biodegradation not will produce secondary pollution.
2. calper calcium peroxide belongs to strong oxidizer, there is powerful degradation capability, have good degradation small Ciprofloxacin
Group, there is important guidance and reference to how efficiently to remove other antibiotic contaminations in sludge.
Description of the drawings
The attached drawing for constituting the part of the present invention is used to provide further understanding of the present invention, schematic reality of the invention
Example and its explanation are applied for explaining the present invention, is not constituted improper limitations of the present invention.
Fig. 1 is the degradation schematic diagram for promoting anaerobic fermentation process Ciprofloxacin in embodiment 1.
Specific embodiment
Below in conjunction with specific preferred embodiment, the invention will be further described, but not thereby limiting the invention
Protection domain.
Specific implementation mode
With reference to Fig. 1：The degradation schematic diagram and example for promoting anaerobic fermentation process Ciprofloxacin further illustrate this hair
It is bright.
Instrument and material used in following embodiment are commercially available.It is chosen in the following examples of the present invention and contains Ciprofloxacin
Mud sample be derived from the sewage plant near certain pharmaceutical factory to illustrate the effect that is reached of the present invention.Anaerobism is anti-at typical condition
It answers the extension of device run time that can improve degradation effect, but can also increase operating cost simultaneously, run time is short, can reduce
The factors such as the characteristics of degradation effect, comprehensive Ciprofloxacin, the following embodiments of the present invention select the run time of anaerobic reactor for
10 days.
Embodiment 1：
Sample containing Ciprofloxacin is added in the anaerobic reactor conical flask for being 1000ml to volume, reactor pH is adjusted to
9.5, inflated with nitrogen realizes anaerobic environment, seals reactor, the speed of agitator of anaerobic fermentation 10 days, anaerobic fermentation is 115r/
Min, control anaerobic reactor temperature are 35 ± 0.5 DEG C.By microbial action abundant in basic treatment and anaerobic reactor,
Ciprofloxacin in degradation sludge.Ciprofloxacin degradation efficiency is 28.3%.
Embodiment 2：
Sample containing Ciprofloxacin is added in the anaerobic reactor conical flask for being 1000ml to volume, reactor pH is adjusted to
10.5, inflated with nitrogen realizes anaerobic environment, seals reactor, the speed of agitator of anaerobic fermentation 10 days, anaerobic fermentation is 115r/
Min, control anaerobic reactor temperature are 35 ± 0.5 DEG C.By microbial action abundant in basic treatment and anaerobic reactor,
Ciprofloxacin in degradation sludge.Ciprofloxacin degradation efficiency is 36.8%.
Embodiment 3：
Sample containing Ciprofloxacin is added in the anaerobic reactor conical flask for being 1000ml to volume, reactor pH is adjusted to
10, and calper calcium peroxide is added by the concentration of 0.1g/g TSS into reactor, add APG, nitrogen charging by the concentration of 0.2g/g TSS
Gas realizes anaerobic environment, seals reactor, the speed of agitator of anaerobic fermentation 10 days, anaerobic fermentation is 115r/min, and control is detested
Oxygen reactor temperature is 35 ± 0.5 DEG C.By microbial action abundant in basic treatment and anaerobic reactor, in sludge of degrading
Ciprofloxacin.Ciprofloxacin degradation efficiency is 52.7%.
Embodiment 4：
Sample containing Ciprofloxacin is added in the anaerobic reactor conical flask for being 1000ml to volume, reactor pH is adjusted to
10, and calper calcium peroxide is added by the concentration of 0.2g/g TSS into reactor, add APG, nitrogen charging by the concentration of 0.2g/g TSS
Gas realizes anaerobic environment, seals reactor, the speed of agitator of anaerobic fermentation 10 days, anaerobic fermentation is 115r/min, and control is detested
Oxygen reactor temperature is 35 ± 0.5 DEG C.By microbial action abundant in basic treatment and anaerobic reactor, in sludge of degrading
Ciprofloxacin.Ciprofloxacin degradation efficiency is 69.3%.
Claims (10)
1. a kind of method for promoting excess sludge anaerobic fermentation to degrade antibiotic ciprofloxacin star, which is characterized in that including following
Step：
Excess sludge containing Ciprofloxacin is added in anaerobic reactor, adds biosurfactant and peroxide thereto
Change calcium, control fermentation process pH is alkalinity, and stirring keeps material mixing in reactor uniform, entire reaction process control reaction temperature
Degree.
2. according to the method described in claim 1, it is characterized in that, sludge is derived from the dirt of Ciprofloxacin pharmacy plant area in the step
The sludge that secondary settling tank is discharged in water treatment plant.
3. according to the method described in claim 2, it is characterized in that, sludge in the step is placed in 4 DEG C of incubators natural
After precipitating for 24 hours, removes supernatant and obtain the excess sludge.
4. according to the method described in claim 1, it is characterized in that, biosurfactant is APG in the step.
5. according to the method described in claim 1, it is characterized in that, in the step calper calcium peroxide dosage be 0.05~
0.35g/g TSS。
6. according to the method described in claim 1, it is characterized in that, biosurfactant additive amount is 0.1 in the step
~0.5g/g TSS.
7. method according to any one of claim 1 to 6, which is characterized in that the entire mistake of anaerobic fermentation in the step
The pH controls of journey are 8.5~11.0.
8. method according to any one of claim 1 to 6, which is characterized in that the temperature of anaerobic fermentation in the step
It it is 25~45 DEG C, fermentation period is 8-15 days, and preferably run time is 10 days.
9. method according to any one of claim 1 to 6, which is characterized in that the stirring of the step anaerobic fermentation turns
Speed is 105~125r/min.
10. method according to any one of claim 1 to 6, which is characterized in that before the step anaerobic fermentation starts
Reactor carries out logical operating under nitrogen, it is ensured that reactor is in anaerobism.
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| CN201710132912.8A CN108569833A (en) | 2017-03-07 | 2017-03-07 | A kind of method of Ciprofloxacin anaerobic degradation in promotion excess sludge |
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| CN201710132912.8A CN108569833A (en) | 2017-03-07 | 2017-03-07 | A kind of method of Ciprofloxacin anaerobic degradation in promotion excess sludge |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113072276A (en) * | 2021-04-01 | 2021-07-06 | 湖南大学 | Method for degrading tetracycline in sludge and increasing yield of fermented short-chain fatty acid by using calcium peroxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880259A (en) * | 2012-12-19 | 2014-06-25 | 同济大学 | Method for promoting hydrolysis of sludge by using calcium peroxide and increasing effect of anaerobic digestion of sludge |
| CN104310739A (en) * | 2014-10-20 | 2015-01-28 | 同济大学 | Method for promoting anaerobic degradation of polycyclic aromatic hydrocarbons in sludge |
| CN104909533A (en) * | 2015-07-08 | 2015-09-16 | 安徽东华环境市政工程有限责任公司 | Method for degrading fluoroquinolone antibiotics in sludge through pyrohydrolysis pretreatment and anaerobic digestion |
-
2017
- 2017-03-07 CN CN201710132912.8A patent/CN108569833A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880259A (en) * | 2012-12-19 | 2014-06-25 | 同济大学 | Method for promoting hydrolysis of sludge by using calcium peroxide and increasing effect of anaerobic digestion of sludge |
| CN104310739A (en) * | 2014-10-20 | 2015-01-28 | 同济大学 | Method for promoting anaerobic degradation of polycyclic aromatic hydrocarbons in sludge |
| CN104909533A (en) * | 2015-07-08 | 2015-09-16 | 安徽东华环境市政工程有限责任公司 | Method for degrading fluoroquinolone antibiotics in sludge through pyrohydrolysis pretreatment and anaerobic digestion |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113072276A (en) * | 2021-04-01 | 2021-07-06 | 湖南大学 | Method for degrading tetracycline in sludge and increasing yield of fermented short-chain fatty acid by using calcium peroxide |
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