CN109354349A - Sludge pre-treatment method and sludge anaerobic fermentation and acid production method - Google Patents
Sludge pre-treatment method and sludge anaerobic fermentation and acid production method Download PDFInfo
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- CN109354349A CN109354349A CN201810303950.XA CN201810303950A CN109354349A CN 109354349 A CN109354349 A CN 109354349A CN 201810303950 A CN201810303950 A CN 201810303950A CN 109354349 A CN109354349 A CN 109354349A
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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
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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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- 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
- C02F11/06—Treatment of sludge; Devices therefor by oxidation
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
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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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Abstract
A kind of sludge pre-treatment method and sludge anaerobic fermentation and acid production method, the sludge pre-treatment method include: persulfate to be added into sludge, and be uniformly mixed and obtain mixing sludge；And ultrasonication is carried out to gained mixing sludge.Further, the present invention provides a kind of sludge anaerobic fermentation and acid production methods, carry out anaerobic fermentation again after carrying out pretreatment above-mentioned to sludge.The present invention is cracked using high-level oxidation technology combining ultrasonic wave reinforcement sludge wadding body, greatly improve sludge disintegration degree, improve the biodegradability energy of sludge, more abundant substrate is provided for subsequent anaerobic fermentation hydrolysis stage, to greatly improve the volatilization acid yield in the subsequent anaerobic fermentation process of sludge.
Description
Technical field
The present invention relates to Disposal Technology of Residual Sludge fields more particularly to a kind of sludge pre-treatment method and sludge anaerobic to send out
Ferment produces sour method.
Background technique
Recently as the raising of sewage treatment plant's efficiency, the sludge rate of recovery rises, and sustained production increases.China cities and towns
The yield of sludge is about 30,000,000 tons (in terms of moisture content 80%), wherein up to 80% sludge does not obtain at appropriate processing
It sets, so that the nutriments serious waste such as the organic matter wherein contained, the energy, nitrogen phosphorus.At the sludge that China mainly uses at present
The method of setting is that landfill and building materials utilize, wherein can really realize the accounting of safe disposal less than 20%.In world's model
In enclosing, anaerobic digestion techniques have good prospect in terms of Treatment of Sludge, and small with sludge yield, low energy consumption for processing, can incite somebody to action
Sludge stabilizing and the advantages that generate clean energy resource gas while improving the dewatering of sludge.Hydrolysis stage is that sludge anaerobic disappears
The problems such as rate-limiting step of change will cause retention time and grow (20-50 days), degradation efficiency low (20-50%).Therefore by sludge into
So that the nutriment in sludge discharges, raising hydrolysis efficiency makes it easier to utilize in anaerobic digestion process for row pretreatment
It is necessary.
The sludge pre-treatment techniques developed at present mainly have: heat treatment, chemical treatment, mechanical treatment etc..Numerous pre-
In processing method, ultrasound pretreatment can produce sonochemical effect, high mechanical force, fuel factor to in sludge wadding body and sludge
Microorganism wall generates considerable damage, dissolves out cytoplasm and enzyme, promotes the biodegradability energy of sludge.In the alternation of ultrasonic field
In acoustic pressure, some micro-bubbles contained in liquid can shrink rapidly with the vibration of ultrasonic wave, be closed, increase, rupture
Process, release big energy, destroy the structure of sludge EPS and zoogloea, promote sludge solution wadding.But ultrasound pretreatment is dirty
Mud is again there is energy consumption height, and equipment is perishable, the shortcomings such as operating cost height.
Summary of the invention
In view of this, the main purpose of the present invention is to provide a kind of sludge pre-treatment method and sludge anaerobic fermentation and acid productions
Method, at least partly solve at least one of above-mentioned the technical issues of referring to.
To achieve the above object, technical scheme is as follows:
As one aspect of the present invention, a kind of pair of sludge is provided and carries out pretreated method, comprising the following steps:
(1) persulfate is added into sludge, and is uniformly mixed and is obtained mixing sludge；
(2) ultrasonication is carried out to the resulting mixing sludge of step (1).
As another aspect of the present invention, a kind of method of sludge anaerobic fermentation and acid production is provided, comprising the following steps:
(I) method pre-processes sludge as described above；
(II) after sludge pretreated in step (I) being exposed nitrogen, constant-temperatureanaerobic anaerobic is fermented at 30~37 DEG C.
Based on the above-mentioned technical proposal, the present invention has following beneficial effect:
(1) present invention uses ultrasonic wave-coupled persulfate pretreating sludge, can more thorough breaking sludge sludge
Flocculation structure makes its partial size become smaller, and destroys its zoogloea and EPS structure attack function sludge microbe cell simultaneously, increases
Sludge disintegration effect, the SCOD in sludge supernatant are significantly raised；
(2) ultrasonic wave-coupled persulfate pretreating sludge is used, discharges the nutriment in sludge largely, is subsequent
Fermentation stage provides nutriment, can greatly enhance the effect of subsequent anaerobic digestion, shorten fermentation period, reactor is waved
Concentration of turning sour is obviously improved, and solves in traditional sludge fermentation that fermentation time is long, and rate of producing acid is low, and fermentation vat volume is huge
The problems such as big.
(3) present invention is ultrasonically treated using probe type ultrasonic wave transmitting device, acoustic wave energy can be made more to concentrate,
Energy output is more stable, and cavitation effect is more significant.
Detailed description of the invention
Fig. 1 is the ultrasonic cell disruption instrument structural schematic diagram that the embodiment of the present invention 1 uses；
Fig. 2 is the sludge anaerobic fermentation and acid production schematic device that the embodiment of the present invention 1 uses；
Fig. 3 is SCOD and fermentation time in sludge supernatant after pretreatment in the embodiment of the present invention 1 and comparative example 1
Relation curve；
Fig. 4 is volatile acid cumulative production in the embodiment of the present invention 1 and comparative example 1 with fermentation time relation curve.
In the figures above, appended drawing reference meaning is as follows:
1- energy converter；2- amplitude transformer；3- sample stage；
4- height adjustment device；5- sound proof box；6- controller；
7- temp probe；8- temp probe casing；9- rotor；
10- collection airbag；11- is into sample tap；12- heat-preservation fermentation tank；
13- leads to nitrogen mouth；14- constant temperature blender with magnetic force；15- temperature display alarm device.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, and reference
Attached drawing, the present invention is described in further detail.
Sludge hydrolytic is the rate-limiting step of sludge fermentation, and sludge is carried out pretreatment and destroys sludge wadding body, zoogloea, EPS
Etc. structures be improve sludge hydrolytic efficiency effective means.Using ultrasound pretreatment can produce sonochemical effect, high mechanical force,
Fuel factor promotes the biodegradability energy of sludge to generate huge destruction to microorganism wall in sludge wadding body and sludge.
In the alternation acoustic pressure of ultrasonic field, some micro-bubbles contained in liquid can shrink rapidly with the vibration of ultrasonic wave,
Closure increases, the process of rupture, as cavitation effect.
High-level oxidation technology can produce high mars free radical during the reaction, can attack sludge zoogloea, EPS, thin
The structures such as born of the same parents make sludge wadding body that considerable damage occur, and effect is rapidly, high-efficient, without secondary pollution, in terms of the Treatment of Sludge before
Scape is wide.Sodium peroxydisulfate is the oxidant in a kind of high-level oxidation technology, can be released by ultrasonic cavitation effect huge
Big energy is excited, generation high mars free radical, can the structures such as attack sludge zoogloea, EPS, cell, make sludge wadding body into
One step is destroyed, and effect is rapidly, high-efficient, without secondary pollution, more using energy caused by ultrasonic wave, is compensated for
Ultrasound pretreatment energy consumption is high, uneconomic defect.
Based on principles above, it can more realize that ultrasonic energy utilizes using ultrasonic wave-coupled persulfate, it is economical
Benefit and obtain better treatment effect.
Specifically, the invention discloses a kind of ultrasonic wave-coupled persulfates carries out pretreated method to sludge, including
Following steps:
Step 1: adding persulfate into sludge, and be uniformly mixed and obtain mixing sludge.
In this step, the excess sludge of secondary settling tank can be sieved and remove impurity removing, natural subsidence one day, excluded supernatant, mix
Sludge concentration is adjusted to 5~15g/L is spare after even, also can be used for this step without the excess sludge of settlement treatment certainly.
The persulfate used can be peroxy-monosulfate such as potassium hydrogen persulfate, hydrogen persulfate sodium or hydrogen persulfate ammonium etc., go back
It can be peroxydisulfate such as sodium peroxydisulfate, potassium peroxydisulfate or ammonium persulfate etc., the concentration in mixing sludge is 1~100mM/
L。
Step 2: ultrasonication is carried out to the resulting mixing sludge of step 1.
In this step, the time of ultrasonic treatment is 5~30min, and acoustic density is 1~6.5W/cm3, frequency of sound wave 20
~25kHz, the ultrasonic treatment can carry out in probe type ultrasonic device, be conducive to concentrate acoustic wave energy more, energy
Export more stable, cavitation effect is more significant, such as ultrasonic cell disruption instrument.
Preferably, ultrasonic treatment is carried out according to batch process.
The invention also discloses a kind of methods of sludge anaerobic fermentation and acid production, comprising the following steps:
Step I: sludge is pre-processed according to method described in step 1 as above and step 2, is not repeated herein.
Step II: exposing nitrogen for a period of time for sludge pretreated in step I, to remove oxygen therein, later,
Constant-temperatureanaerobic anaerobic is fermented at 30~37 DEG C, and fermentation time can be 3~20 days.
In order to verify beneficial effects of the present invention, specific embodiment and comparative example are exemplified below to technical side of the invention
Case is described further:
Embodiment 1
A method of using the anaerobic fermentation and acid production of the pretreated sludge of ultrasonic wave-coupled persulfate, specifically according to
What following steps carried out:
Step 1: experimentation is oxidation needed for high-level oxidation technology using sodium peroxydisulfate under the conditions of room temperature (25 DEG C)
Agent weighs 0.24g sodium peroxydisulfate and the municipal sewage plant 100ml returned sludge (sludge concentration 14g/L) in 100ml beaker
It is sufficiently mixed uniformly, obtains mixing sludge, i.e., control sodium peroxydisulfate concentration is 10mM/L.
Step 2: carrying out ultrasonic wave to the mixing sludge in step 1 using ultrasonic cell disruption instrument as shown in Figure 1
Processing.The sonicator be Xin Zhi company JY90-II model ultrasonic cell disruption instrument, comprising: controller 6, every
Height adjustment device 4, sample stage 3, amplitude transformer 2 and the energy converter 1 being arranged in speaker 5 and sound proof box 5, energy converter are connected to control
Device 6 processed.
The beaker for filling mixing sludge is placed on the sample stage 3 in the sound proof box 5 of ultrasonic cell disruption instrument, height is passed through
It spends regulating device 4 and adjusts sample stage 3 in appropriate height, select Φ 6mm model amplitude transformer 2 to work, make 2 end of amplitude transformer position
At away from the position beaker bottom 1.5cm.
Step 3: setting ultrasonic power 300W, ultrasonic time 10min, frequency of sound wave are on the panel of controller 6
25kHz, using service intermittent mode, ultrasonic 5s is spaced 3s, and work total time 16min, controls energy converter 1 by controller 6
It works with amplitude transformer 2, ultrasonication is carried out to mixing sludge, 8ml is sampled to after, is placed in centrifuge tube, 8000g centrifugation
10min carries out COD measurement after taking supernatant to cross 0.22 μm of filter membrane.
Step 4: using sludge anaerobic fermentation and acid production device as shown in Figure 2 to sludge pretreated in step 3 into
Row anaerobic fermentation.The sludge anaerobic fermentation and acid production device includes: constant temperature blender with magnetic force 14, is placed in constant temperature blender with magnetic force 14
Heat-preservation fermentation tank 12, the rotor 9 for the stirring being arranged in heat-preservation fermentation tank 12, the temperature being placed in temp probe casing 8
Probe 7, be arranged on heat-preservation fermentation tank 12 into sample tap 11 and logical nitrogen mouth 13, be connected to 12 gas outlet of heat-preservation fermentation tank
Collect airbag 10, wherein temp probe 7 is connected to temperature display alarm device 15, to supervise to the temperature in heat-preservation fermentation tank 12
Control.
Specifically, sludge after pretreatment in step 3 is placed in heat-preservation fermentation tank 12, it is logical by logical nitrogen mouth 13
Enter nitrogen 10min to remove the oxygen in sludge, anaerobic fermentation temperature is controlled at 35 DEG C by constant temperature blender with magnetic force 14, and even
Continuous stirring.Fermentation total time is 480h, is sampled respectively in 0h, 18h, 47h and 51h, sample volume 8ml, sampling is placed on
In centrifuge tube, 8000g is centrifuged 10min, after taking supernatant to cross 0.22 μm of filter membrane, carries out COD measurement.
Step 5: being sampled respectively in 0h, 48h, 96h, 312h and 480h, sample volume 8ml, sampling is placed on centrifugation
Guan Zhong, 8000g are centrifuged 10min, take 1ml after taking supernatant to cross 0.22 μm of filter membrane, are placed in chromatogram bottle, using liquid chromatogram measuring
Its volatile acid content.
Comparative example 1
Compared with Example 1, difference is only that, has only made ultrasonic pretreatment to sludge, without the mistake in step 1
Sodium sulphate adds step.
Fig. 3 is SCOD and fermentation time in sludge supernatant after pretreatment in the embodiment of the present invention 1 and comparative example 1
Relation curve, as seen from the figure, in embodiment 1, there is apparent increase in SCOD in preceding 18h sludge supernatant, and the later period slowly increases,
But it is constantly in higher level.Fig. 4 is volatile acid cumulative production in the embodiment of the present invention 1 and comparative example 1 with fermentation time relationship
Curve, as seen from the figure, in embodiment 1, Vfa Concentration is obviously increased, and extends ascendant trend is presented at any time.By
The result of comparative example 1 it is found that its SCOD amplitude of variation is unobvious, and in fermentation liquid Volatile fatty acid contents it is lower and with
Fermentation liquid Vfa Concentration is consistently lower than embodiment 1 in the extension presentation downward trend of time, SCOD and fermentation process.
Embodiment 2 to 5
It is similar with the method for embodiment 1, step 1 is carried out to step to sludge according to reagent shown in table 1, dosage and condition
Rapid three pretreatment, sampling carries out COD measurement after the pre-treatment, it is known that can be effectively increased using preprocess method of the invention
SCOD content is conducive to subsequent anaerobic fermentation processing.
In conclusion the present invention is cracked using high-level oxidation technology combining ultrasonic wave reinforcement sludge wadding body, greatly improve
Sludge disintegration degree, improves the biodegradability energy of sludge, provides more abundant bottom for subsequent anaerobic fermentation hydrolysis stage
Object effectively alleviates sludge anaerobic and disappears to greatly improve the volatilization acid yield in the subsequent anaerobic fermentation process of sludge
It is limited as caused by hydrolysis stage during change, improves anaerobic sludge digestion efficiency, more realize the resource of sludge
Change and utilizes.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
Describe in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in protection of the invention
Within the scope of.
Claims (10)
1. a kind of pair of sludge carries out pretreated method, comprising the following steps:
(1) persulfate is added into sludge, and is uniformly mixed and is obtained mixing sludge；
(2) ultrasonication is carried out to the resulting mixing sludge of step (1).
2. the concentration of the sludge is 5~15g/L the method according to claim 1, wherein in step (1),
Concentration of the persulfate in the mixing sludge is 1~100mM/L, preferably 10mM/L.
3. the method according to claim 1, wherein the persulfate includes peroxy-monosulfate in step (1)
And peroxydisulfate, the peroxy-monosulfate are selected from potassium hydrogen persulfate, hydrogen persulfate sodium or hydrogen persulfate ammonium, the peroxy-disulfuric acid
Salt is selected from sodium peroxydisulfate, potassium peroxydisulfate or ammonium persulfate.
4. the method according to claim 1, wherein in step (1), the sludge by secondary settling tank excess sludge
It is obtained after the adjusting of sieving, sedimentation and concentration.
5. the method according to claim 1, wherein in step (2), the time of the ultrasonic treatment is 5~
30min, preferably 10min, acoustic density are 1~6.5W/cm3, preferably 3W/cm3, frequency of sound wave is 20~25kHz, preferably
For 25kHz.
6. the method according to claim 1, wherein the ultrasonication is in probe type ultrasonic in step (2)
It is carried out in wave apparatus.
7. according to the method described in claim 6, it is characterized in that, the probe type ultrasonic device is ultrasonic cell-break
Instrument, the ultrasonic cell disruption instrument include amplitude transformer, which is located at away from the sludge bottom position 1.5cm.
8. according to the method described in claim 6, it is characterized in that, the ultrasonication is carried out according to batch process.
9. a kind of method of sludge anaerobic fermentation and acid production, comprising the following steps:
(I) sludge is pre-processed according to the method as described in claim 1 to 8 any one；
(II) after sludge pretreated in step (I) being exposed nitrogen, constant-temperatureanaerobic anaerobic is fermented at 30~37 DEG C.
10. according to the method described in claim 9, it is characterized in that, fermentation temperature is 35 DEG C in step (II)；Fermentation time is
3~20 days.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110467332A (en) * | 2019-09-17 | 2019-11-19 | 北京林业大学 | A kind of efficient sludge conditioning and dewatering |
| CN110747237A (en) * | 2019-11-14 | 2020-02-04 | 湖南大学 | Method for promoting dehydration of excess sludge and simultaneously producing fatty acid |
| CN112744994A (en) * | 2020-12-31 | 2021-05-04 | 安徽中环环保科技股份有限公司 | Device and method for hydrolysis acidification pretreatment of excess sludge |
| CN113248089A (en) * | 2021-06-25 | 2021-08-13 | 山东建筑大学 | Residual sludge phosphorus digestion and dissolution coupled phosphate recovery device and sludge treatment method |
| CN113248097A (en) * | 2021-05-26 | 2021-08-13 | 北京科技大学 | Excess sludge pretreatment method |
| CN114804565A (en) * | 2022-04-29 | 2022-07-29 | 青岛理工大学 | Low-temperature anaerobic fermentation method for high-solid-content sludge |
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| CN106734053A (en) * | 2016-11-18 | 2017-05-31 | 浙江工商大学 | A kind of method for accelerating anaerobic fermentation of kitchen waste aerogenesis |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110467332A (en) * | 2019-09-17 | 2019-11-19 | 北京林业大学 | A kind of efficient sludge conditioning and dewatering |
| CN110747237A (en) * | 2019-11-14 | 2020-02-04 | 湖南大学 | Method for promoting dehydration of excess sludge and simultaneously producing fatty acid |
| CN112744994A (en) * | 2020-12-31 | 2021-05-04 | 安徽中环环保科技股份有限公司 | Device and method for hydrolysis acidification pretreatment of excess sludge |
| CN112744994B (en) * | 2020-12-31 | 2021-10-22 | 安徽中环环保科技股份有限公司 | Device and method for hydrolysis acidification pretreatment of excess sludge |
| CN113248097A (en) * | 2021-05-26 | 2021-08-13 | 北京科技大学 | Excess sludge pretreatment method |
| CN113248089A (en) * | 2021-06-25 | 2021-08-13 | 山东建筑大学 | Residual sludge phosphorus digestion and dissolution coupled phosphate recovery device and sludge treatment method |
| CN114804565A (en) * | 2022-04-29 | 2022-07-29 | 青岛理工大学 | Low-temperature anaerobic fermentation method for high-solid-content sludge |
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