CN108455794A - A kind of electrolysis/hydrolysis/DMBR Combined Treatments reactor and technique - Google Patents
A kind of electrolysis/hydrolysis/DMBR Combined Treatments reactor and technique Download PDFInfo
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- CN108455794A CN108455794A CN201810189264.4A CN201810189264A CN108455794A CN 108455794 A CN108455794 A CN 108455794A CN 201810189264 A CN201810189264 A CN 201810189264A CN 108455794 A CN108455794 A CN 108455794A
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
-
- 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
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1268—Membrane bioreactor systems
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/2806—Anaerobic processes using solid supports for microorganisms
Abstract
The invention discloses a kind of electrolysis/hydrolysis/DMBR Combined Treatments reactor and techniques, the reactor includes high water tank, high water tank is connected with electrolytic cell, hydrolysis acidification pool and DMBR reactors in turn by pipeline, and peristaltic pump is both provided on the pipeline between high water tank and electrolytic cell, between electrolytic cell and hydrolysis acidification pool；Setting is provided with peristaltic pump there are two pipeline on each pipeline between hydrolysis acidification pool and DMBR reactors；Membrane module and aeration plate are provided in DMBR reactors, membrane module is connected with pressure gauge and peristaltic pump in turn by pipeline；Aeration plate is connected with spinner flowmeter and air pump in turn by pipeline.After the combined process of waste water of the present invention, the removal rate of COD and TOC are respectively 91.1% and 89.6%.
Description
Technical field
The invention belongs to technical field of waste water processing, specifically, it is anti-to be related to a kind of electrolysis/hydrolysis/DMBR Combined Treatments
Answer device and technique.
Background technology
China is paper industry big country, while being also that paper-making industrial waste water discharges big country.Paper waste is contained due to its COD
Amount is high, and pollutant component is complex, and the factors such as difficult become one of environmental pollution prevention and control and processing thorny problem.Dissolving
Property organic matter (Dissolved Organic Matter, DOM) is the important component of organic matter in paper waste.DOM exists
Transport And Transformation in processing paper waste technique has the removal of pollutant and biodegradable great influence.Existing rank
Section mainly has physical-chemical process, biochemical process, physical chemistry bioid student's federation for the processing method of paper waste both at home and abroad
It is the methods of legal.
Bioreactor of dynamic membrane (DMBR) is a kind of dirt being combined dynamic membrane filtering technology and biological treatment
Water treatment technology, film base material use microgrid material that is cheap and having larger aperture, pass through the shape in activated sludge filter process
At bio-dynamic membrane realize and be similar to the filter effects of microfiltration membranes.DMBR is due to its low cost, and water outlet water is big and water quality is excellent
The advantages that good, is favored by water treatment work person both domestic and external.It is useless using electrolysis-hydrolysis acidification-DMBR combination processing papermaking at present
The research report of water is fewer, wherein the transportion and transformation about DOM is more rarely reported.
Invention content
In view of this, the present invention provides a kind of electrolysis/hydrolysis/DMBR Combined Treatments reactor and techniques.
In order to solve the above-mentioned technical problem, the invention discloses a kind of electrolysis/hydrolysis/DMBR Combined Treatment reactors, packets
High water tank is included, the high water tank is connected with electrolytic cell, hydrolysis acidification pool and DMBR reactors, the height in turn by pipeline
It is both provided with peristaltic pump on pipeline between position water tank and electrolytic cell, between electrolytic cell and hydrolysis acidification pool；The hydrolysis acidification
Setting is provided with peristaltic pump there are two pipeline on each pipeline between pond and DMBR reactors；Setting in the DMBR reactors
There are membrane module and aeration plate, the membrane module to be connected with pressure gauge and peristaltic pump in turn by pipeline；The aeration plate passes through pipe
Road is connected with spinner flowmeter and air pump in turn.
Optionally, setting is arranged between the electrolytic zinc-coated steel sheet there are two the electrolytic zinc-coated steel sheet that is oppositely arranged on the electrolytic cell bottom
There is agitating device.
Optionally, the material of the electrolytic zinc-coated steel sheet is aluminium or iron；The distance between electrolytic zinc-coated steel sheet is 4cm.
Optionally, the electrolyte concentration of the electrolytic cell is 0.8g/L, current density 0.8ma/cm2；Electrolyte is
Anhydrous sodium sulfate.
Optionally, elastic filler and agitating device are provided in the hydrolysis acidification pool, the agitating device is arranged in water
Solve the center of acidification pool.
Optionally, the dischargeable capacity of the hydrolysis acidification pool and DMBR reactors is respectively 16.5L and 33L.
Optionally, the hydraulic detention time of the DMBR reactors is 12H, and return sludge ratio 200%, dissolved oxygen is
0.2~0.3mg/L, sludge concentration are 5000~6000mg/L.
Optionally, the film base material of the membrane module is the nylon cloth of 300 mesh, and the filter area of membrane module is 0.052m2。
The invention also discloses a kind of electrolysis/hydrolysis/DMBR combined treatment process, include the following steps：
Step 1 pours into seed sludge in the DMBR reactors of electrolysis/hydrolysis/DMBR Combined Treatment reactors, and sludge is heavy
The 1/3 of reactor is accounted for after drop, and sludge acclimatization liquid is added to DMBR reactor dischargeable capacitys；Continuous aeration for 24 hours after, stand 30min,
Supernatant is discharged, then proceedes to that sludge acclimatization liquid is added；Reaction initial stage using low concentration sludge acclimatization liquid into
Row domestication, gradually increases sewage load again after pending raising with obvious effects；After the domestication of 15~20d, removal rate is substantially steady
It is scheduled on 90% or more；After system run all right, elastic filler, such circular flow, until dirty are put into hydrolysis acidification pool
Mud concentration desired value 6000mg/L；After operation one month, filler surface increasingly generates one layer of biomembrane, and sludge grain size reaches
Biofilm requirement, i.e., carry out biofilm to membrane module, and reactor enters formal startup stage；
Step 2, after reactor formally starts, will after paper waste enter high water tank, paper waste through peristaltic pump into
Enter electrolytic cell and reacts；
Step 3, the waste water after electrolysis are further purified after wriggling pumping action into hydrolysis acidification pool, and electrolytic cell goes out
Water is by the bottom of hydrolysis acidification pool 1 even into in pond；
Step 4, the water outlet after hydrolysis acidification pool hydrolyzes are entered by peristaltic pump in DMBR reactors, the pollution in waste water
Object is further consumed by the microorganism in DMBR reactors；Agitating device, DMBR reactor bottoms are equipped in hydrolysis acidification pool
It equipped with aeration plate, is equipped with membrane module in DMBR inside reactors and connects pressure gauge, pressure gauge is pressure vacuum gauge, and pressure gauge is real
When monitor transmembrane pressure variation, when TMP reaches 25kPa, membrane module is out of service and carries out physical cleaning.
Optionally, sludge acclimatization liquid is made of following components：12~15g of industrial glucose, 0.5~1g of ammonium chloride,
10~12g of 0.1~0.2g of potassium dihydrogen phosphate and sodium bicarbonate, surplus are water, are 25L with upper volume total amount；The dirt of low concentration
The standard of mud domestication liquid is：COD is 350mg/L, ammonia nitrogen 8mg/L, phosphate 0.5mg/L, total nitrogen 18mg/L, total phosphorus
For 1.5mg/L, the standard that treatment effect significantly improves is：The removal rate of the pollutants such as COD, ammonia nitrogen, phosphate, total phosphorus, total nitrogen
95% or more；Electric current is 1A, electrolysis time 1H, electrolyte concentration 0.8g/L, current density 0.8ma/ in electrolytic cell
cm2；Electrolyte is anhydrous sodium sulfate；The hydraulic detention time of DMBR reactors is 12H, return sludge ratio 200%, dissolved oxygen
For 0.2~0.3mg/L, sludge concentration is 5000~6000mg/L；The film base material of membrane module is the nylon cloth of 300 mesh, membrane module
Filter area be 0.052m2。
Compared with prior art, the present invention can be obtained including following technique effect：
1) after the combined process of waste water of the present invention, the removal rate of COD and TOC are respectively 91.1% and 89.6%.
2) UV-vis spectrum and molecular weight distribution show after hydrolysis acidification pool acts on, larger molecular organics difficult to degrade
It is converted into degradable small organic molecule.
3) the DOM fluorescence spectras of each sample point show to mainly contain three characteristic fluorescence peaks, respectively peak A in DOM
(high excitation wavelength tryptophan), peak B (ultraviolet region fulvic acid) and peak C (visible region fulvic acid).In hydrolysis acidification pool, by
It is significantly increased in the effect peak A intensity of hydrolysis acidification bacterium.Three fluorescence parameter fluorescence index (FI), biological source index (HIX) and
It is mainly due to micro- life that the value of humification index (BIX), which shows DOM in electrolysis/hydrolysis/DMBR combined treatment process of the present invention,
The metabolism of object and generate.
Certainly, it implements any of the products of the present invention it is not absolutely required to while reaching all the above technique effect.
Description of the drawings
Attached drawing described herein is used to provide further understanding of the present invention, and constitutes the part of the present invention, this hair
Bright illustrative embodiments and their description are not constituted improper limitations of the present invention for explaining the present invention.In the accompanying drawings：
Fig. 1 is the structural schematic diagram of electrolysis/hydrolysis of the present invention/DMBR Combined Treatment reactors；
Fig. 2 is the variation of different sample point dissolubility COD and TOC of the invention；
Fig. 3 is the UV-vis spectrum of different sample point DOM of the invention；
Fig. 4 is the DOM mass profiles of different sample points of the invention；
Fig. 5 is the three-dimensional fluorescence figure of different sample point DOM of the invention.
Specific implementation mode
Carry out the embodiment that the present invention will be described in detail below in conjunction with embodiment, thereby to the present invention how application technology hand
Section solves technical problem and reaches the realization process of technical effect to fully understand and implement.
The invention discloses a kind of electrolysis/hydrolysis/DMBR Combined Treatment reactors, as shown in Figure 1, including high water tank
10, the high water tank 10 is connected with electrolytic cell 11, hydrolysis acidification pool 12 and DMBR reactors 13, the height in turn by pipeline
It is both provided with peristaltic pump 1 on pipeline between position water tank 10 and electrolytic cell 11, between electrolytic cell 11 and hydrolysis acidification pool 12；Institute
Pipeline there are two being arranged between hydrolysis acidification pool 12 and DMBR reactors 13 is stated, peristaltic pump 1 is provided on each pipeline；It is described
It is provided with membrane module 5 and aeration plate 7 in DMBR reactors 13, the membrane module 5 is connected with pressure gauge 6 and compacted in turn by pipeline
Dynamic pump 1；The aeration plate 7 is connected with spinner flowmeter 8 and air pump 9 in turn by pipeline.
Optionally, setting is there are two the electrolytic zinc-coated steel sheet 2 that is oppositely arranged on 11 bottom of the electrolytic cell, between the electrolytic zinc-coated steel sheet 2
It is provided with agitating device 4.
Optionally, the material of the electrolytic zinc-coated steel sheet 2 is aluminium or iron；The distance between electrolytic zinc-coated steel sheet 2 is 4cm.
Optionally, the electrolyte concentration of the electrolytic cell 11 is 0.8g/L, current density 0.8ma/cm2；Electrolyte
For anhydrous sodium sulfate.
Optionally, elastic filler 3 and agitating device 4 are provided in the hydrolysis acidification pool 12, the agitating device 4 is arranged
At the center of hydrolysis acidification pool 12.
Optionally, the dischargeable capacity of the hydrolysis acidification pool 12 and DMBR reactors 13 is respectively 16.5L and 33L.
Optionally, the hydraulic detention time of the DMBR reactors 13 is 12H, return sludge ratio 200%, dissolved oxygen
For 0.2~0.3mg/L, sludge concentration is 5000~6000mg/L.
Optionally, the film base material of the membrane module 5 is the nylon cloth of 300 mesh, and the filter area of membrane module 5 is 0.052m2。
Electrolysis/hydrolysis/DMBR Combined Treatments reactor of the present invention is by inlet tank, electrolytic cell, hydrolysis acidification pool and DMBR
Four parts form, and elastic filler is fixed in hydrolysis acidification pool.The dischargeable capacity of hydrolysis acidification pool 12 and DMBR reactors 13 point
It Wei not 16.5L and 33L.Electrolytic cell and hydrolysis acidification pool are equipped with agitating device 4, and 13 bottom of DMBR reactors is equipped with aeration plate 7 simultaneously
To being aerated in pond, DO values are 2~3mg/L, return sludge ratio 200%.The waterpower of hydrolysis acidification pool 12 and aerobic tank is stopped
The time (Hydraulic Retention Time, HRT) is stayed to be followed successively by as 6H and 18H.Experiment is derived from Hefei City with seed sludge
Activated sludge in Economic Development Zone Guo Zhen sewage treatment plants oxidation ditch aerobic section, bored exposure start to tame into reactor afterwards for 24 hours.It is dirty
Mud settling property is good, a concentration of 5000~6000mg/L.
The invention also discloses a kind of electrolysis/hydrolysis/DMBR combined treatment process, include the following steps：
Step 1 pours into seed sludge (being derived from Hefei sewage plant) in the DMBR reactors 13 of group technology, and sludge is heavy
The 1/3 of reactor is accounted for after drop, and sludge acclimatization liquid is added to 13 dischargeable capacity of DMBR reactors；Continuous aeration for 24 hours after, stand
Supernatant is discharged in 30min, then proceedes to that sludge acclimatization liquid is added；Sludge acclimatization liquid is made of following components：Technical grade grape
12~15g of sugar, 10~12g of 0.5~1g of ammonium chloride, 0.1~0.2g of potassium dihydrogen phosphate and sodium bicarbonate, surplus is water, with upper body
Product total amount is 25L；It is tamed using the sludge acclimatization liquid of low concentration in the initial stage of reaction, wherein low concentration
The standard of sludge acclimatization liquid is：COD is 350mg/L, ammonia nitrogen 8mg/L, phosphate 0.5mg/L, total nitrogen 18mg/L, always
Phosphorus is 1.5mg/L；(removal rate of the pollutants such as COD, ammonia nitrogen, phosphate, total phosphorus, total nitrogen exists for pending raising with obvious effects
95% or more) gradually increase sewage load after again, after the domestication of 15~20d, removal rate is basically stable at 90% or more.It is being
Unite it is stable after, be put into elastic filler 3 in hydrolysis acidification pool 12, such circular flow, until sludge concentration desired value
6000mg/L；After operation one month, filler surface increasingly generates one layer of biomembrane, and sludge grain size reaches biofilm requirement, i.e.,
Biofilm is carried out to membrane module 5, reactor enters formal startup stage；
Step 2, after reactor formally starts, will after paper waste enter high water tank 10, paper waste is through peristaltic pump 1
Into electrolytic cell 11 and react.Electrolytic zinc-coated steel sheet 2 is equipped in electrolytic cell 11, the consumable material of electrolytic zinc-coated steel sheet is aluminium and iron.It is electric in electrolytic cell
Stream is 1A, electrolysis time 1H, and the spacing between electrolytic zinc-coated steel sheet 2 is 4cm, electrolyte concentration 0.8g/L, and current density is
0.8ma/cm2.The electrolyte that the present invention is taken is anhydrous sodium sulfate.
Step 3, the waste water after electrolysis are further purified after the effect of peristaltic pump 1 into hydrolysis acidification pool 12, are electrolysed
Pond 11 is discharged the bottom by hydrolysis acidification pool 12 even into in pond.
Step 4, the water outlet after the hydrolysis of hydrolysis acidification pool 12 are entered by peristaltic pump 1 in DMBR reactors 13, in waste water
Pollutant further consumed by the microorganism in DMBR reactors 13.Agitating device, DMBR are equipped in hydrolysis acidification pool 12
13 bottom of reactor be equipped with aeration plate 7, hydraulic detention time 12H, return sludge ratio 200%, dissolved oxygen be 0.2~
0.3mg/L, sludge concentration are 5000~6000mg/L.It is internally provided with membrane module 5 in DMBR reactors 13 and connects vacuum pressure
Table, film base material are the nylon cloth of 300 mesh, and the filter area of membrane module 5 is 0.052m2.Pressure vacuum gauge can monitor cross-film in real time
The variation of pressure difference (TMP), when TMP reaches 25kPa or so, membrane module is out of service and carries out physical cleaning.
Embodiment 1
A kind of electrolysis/hydrolysis/DMBR Combined Treatment reactors, including high water tank 10, the high water tank 10 pass through pipe
Road is connected with electrolytic cell 11, hydrolysis acidification pool 12 and DMBR reactors 13 in turn, between the high water tank 10 and electrolytic cell 11,
Peristaltic pump 1 is both provided on pipeline between electrolytic cell 11 and hydrolysis acidification pool 12；The hydrolysis acidification pool 12 and DMBR reactions
Setting is provided with peristaltic pump 1 there are two pipeline on each pipeline between device 13；It is provided with membrane module in the DMBR reactors 13
5 and aeration plate 7, the membrane module 5 pressure gauge 6 and peristaltic pump 1 are connected in turn by pipeline；The aeration plate 7 passes through pipeline
It is connected with spinner flowmeter 8 and air pump 9 in turn.
Optionally, setting is there are two the electrolytic zinc-coated steel sheet 2 that is oppositely arranged on 11 bottom of the electrolytic cell, between the electrolytic zinc-coated steel sheet 2
It is provided with agitating device 4.
Optionally, the material of the electrolytic zinc-coated steel sheet 2 is aluminium or iron；The distance between electrolytic zinc-coated steel sheet 2 is 4cm.
Optionally, the electrolyte concentration of the electrolytic cell 11 is 0.8g/L, current density 0.8ma/cm2；Electrolyte
For anhydrous sodium sulfate.
Optionally, elastic filler 3 and agitating device 4 are provided in the hydrolysis acidification pool 12, the agitating device 4 is arranged
At the center of hydrolysis acidification pool 12.
Optionally, the dischargeable capacity of the hydrolysis acidification pool 12 and DMBR reactors 13 is respectively 16.5L and 33L.
Optionally, the hydraulic detention time of the DMBR reactors 13 is 12H, return sludge ratio 200%, dissolved oxygen
For 0.2~0.3mg/L, sludge concentration is 5000~6000mg/L.
Optionally, the film base material of the membrane module 5 is the nylon cloth of 300 mesh, and the filter area of membrane module 5 is 0.052m2。
Embodiment 2
A kind of electrolysis/hydrolysis/DMBR combined treatment process, includes the following steps：
Step 1 pours into seed sludge (being derived from Hefei sewage plant) in the reactor of group technology, is accounted for after sludge settling
Sludge acclimatization liquid is added to reactor dischargeable capacity in the 1/3 of reactor；Continuous aeration for 24 hours after, stand 30min, be discharged supernatant
Liquid then proceedes to that sludge acclimatization liquid is added；Sludge acclimatization liquid is made of following components：12~15g of industrial glucose, chlorination
10~12g of 0.5~1g of ammonium, 0.1~0.2g of potassium dihydrogen phosphate and sodium bicarbonate, surplus are water, are 25L with upper volume total amount；
The initial stage of reaction is tamed using the sludge acclimatization liquid of low concentration, wherein the mark of the sludge acclimatization liquid of low concentration
Standard is：COD is 350mg/L, ammonia nitrogen 8mg/L, phosphate 0.5mg/L, total nitrogen 18mg/L, total phosphorus 1.5mg/L；It waits for
Treatment effect gradually increases sewage load again after significantly improving.After the domestication of 18d, removal rate is basically stable at 90% or more.
After system run all right, elastic filler 3, such circular flow are put into hydrolysis acidification pool 12, until sludge concentration is expected
Value 6000mg/L；After operation one month, filler surface increasingly generates one layer of biomembrane, and sludge grain size reaches biofilm requirement,
Biofilm is carried out to membrane module 5, reactor enters formal startup stage；
Step 2, after reactor formally starts, will after paper waste enter high water tank 10, paper waste is through peristaltic pump 1
Into electrolytic cell 11 and react.Electrolytic zinc-coated steel sheet 2 is equipped in electrolytic cell 11, the consumable material of electrolytic zinc-coated steel sheet is aluminium and iron.It is electric in electrolytic cell
Stream is 1A, electrolysis time 1H, and the spacing between electrolytic zinc-coated steel sheet 2 is 4cm, electrolyte concentration 0.8g/L, and current density is
0.8ma/cm2.The electrolyte that the present invention is taken is anhydrous sodium sulfate.
Step 3, the waste water after electrolysis are further purified after the effect of peristaltic pump 1 into hydrolysis acidification pool 12, are electrolysed
Pond 11 is discharged the bottom by hydrolysis acidification pool 12 even into in pond.
Step 4, the water outlet after the hydrolysis of hydrolysis acidification pool 12 are entered by peristaltic pump 1 in DMBR reactors 13, in waste water
Pollutant further consumed by the microorganism in DMBR reactors 13.Agitating device, DMBR are equipped in hydrolysis acidification pool 12
13 bottom of reactor be equipped with aeration plate 7, hydraulic detention time 12H, return sludge ratio 200%, dissolved oxygen 0.25mg/L,
Sludge concentration is 5500mg/L.It is internally provided with membrane module 5 in DMBR reactors 13 and connects pressure vacuum gauge, film base material 300
The filter area of purpose nylon cloth, membrane module 5 is 0.052m2.Pressure vacuum gauge can monitor the change of transmembrane pressure (TMP) in real time
Change, when TMP reaches 25kPa or so, membrane module is out of service and carries out physical cleaning.
Embodiment 3
A kind of electrolysis/hydrolysis/DMBR combined treatment process, includes the following steps：
Step 1 pours into seed sludge (being derived from Hefei sewage plant) in the reactor of group technology, is accounted for after sludge settling
Sludge acclimatization liquid is added to reactor dischargeable capacity in the 1/3 of reactor；Continuous aeration for 24 hours after, stand 30min, be discharged supernatant
Liquid then proceedes to that sludge acclimatization liquid is added；Sludge acclimatization liquid is made of following components：12~15g of industrial glucose, chlorination
10~12g of 0.5~1g of ammonium, 0.1~0.2g of potassium dihydrogen phosphate and sodium bicarbonate, surplus are water, are 25L with upper volume total amount；
The initial stage of reaction is tamed using the sludge acclimatization liquid of low concentration, wherein the mark of the sludge acclimatization liquid of low concentration
Standard is：COD is 350mg/L, ammonia nitrogen 8mg/L, phosphate 0.5mg/L, total nitrogen 18mg/L, total phosphorus 1.5mg/L；It waits for
Treatment effect gradually increases sewage load again after significantly improving.After the domestication of 15~20d, removal rate is basically stable at 90%
More than.After system run all right, elastic filler 3, such circular flow, until sludge concentration are put into hydrolysis acidification pool 12
Desired value 6000mg/L；After operation one month, filler surface increasingly generates one layer of biomembrane, and sludge grain size reaches biofilm
It is required that carrying out biofilm to membrane module 5, reactor enters formal startup stage；
Step 2, after reactor formally starts, will after paper waste enter high water tank 10, paper waste is through peristaltic pump 1
Into electrolytic cell 11 and react.Electrolytic zinc-coated steel sheet 2 is equipped in electrolytic cell 11, the consumable material of electrolytic zinc-coated steel sheet is aluminium and iron.It is electric in electrolytic cell
Stream is 1A, electrolysis time 1H, and the spacing between electrolytic zinc-coated steel sheet 2 is 4cm, electrolyte concentration 0.8g/L, and current density is
0.8ma/cm2.The electrolyte that the present invention is taken is anhydrous sodium sulfate.
Step 3, the waste water after electrolysis are further purified after the effect of peristaltic pump 1 into hydrolysis acidification pool 12, are electrolysed
Pond 11 is discharged the bottom by hydrolysis acidification pool 12 even into in pond.
Step 4, the water outlet after the hydrolysis of hydrolysis acidification pool 12 are entered by peristaltic pump 1 in DMBR reactors 13, in waste water
Pollutant further consumed by the microorganism in DMBR reactors 13.Agitating device, DMBR are equipped in hydrolysis acidification pool 12
13 bottom of reactor be equipped with aeration plate 7, hydraulic detention time 12H, return sludge ratio 200%, dissolved oxygen 0.2mg/L,
Sludge concentration is 6000mg/L.It is internally provided with membrane module 5 in DMBR reactors 13 and connects pressure vacuum gauge, film base material 300
The filter area of purpose nylon cloth, membrane module 5 is 0.052m2.Pressure vacuum gauge can monitor the change of transmembrane pressure (TMP) in real time
Change, when TMP reaches 25kPa or so, membrane module is out of service and carries out physical cleaning.
Embodiment 4
A kind of electrolysis/hydrolysis/DMBR combined treatment process, includes the following steps：
Step 1 pours into seed sludge (being derived from Hefei sewage plant) in the reactor of group technology, is accounted for after sludge settling
Sludge acclimatization liquid is added to reactor dischargeable capacity in the 1/3 of reactor；Continuous aeration for 24 hours after, stand 30min, be discharged supernatant
Liquid then proceedes to that sludge acclimatization liquid is added；Sludge acclimatization liquid is made of following components：12~15g of industrial glucose, chlorination
10~12g of 0.5~1g of ammonium, 0.1~0.2g of potassium dihydrogen phosphate and sodium bicarbonate, surplus are water, are 25L with upper volume total amount；
The initial stage of reaction is tamed using the sludge acclimatization liquid of low concentration, wherein the mark of the sludge acclimatization liquid of low concentration
Standard is：COD is 350mg/L, ammonia nitrogen 8mg/L, phosphate 0.5mg/L, total nitrogen 18mg/L, total phosphorus 1.5mg/L；It waits for
Treatment effect gradually increases sewage load again after significantly improving.After the domestication of 15~20d, removal rate is basically stable at 90%
More than.After system run all right, elastic filler 3, such circular flow, until sludge concentration are put into hydrolysis acidification pool 12
Desired value 6000mg/L；After operation one month, filler surface increasingly generates one layer of biomembrane, and sludge grain size reaches biofilm
It is required that carrying out biofilm to membrane module 5, reactor enters formal startup stage；
Step 2, after reactor formally starts, will after paper waste enter high water tank 10, paper waste is through peristaltic pump 1
Into electrolytic cell 11 and react.Electrolytic zinc-coated steel sheet 2 is equipped in electrolytic cell 11, the consumable material of electrolytic zinc-coated steel sheet is aluminium and iron.It is electric in electrolytic cell
Stream is 1A, electrolysis time 1H, and the spacing between electrolytic zinc-coated steel sheet 2 is 4cm, electrolyte concentration 0.8g/L, and current density is
0.8ma/cm2.The electrolyte that the present invention is taken is anhydrous sodium sulfate.
Step 3, the waste water after electrolysis are further purified after the effect of peristaltic pump 1 into hydrolysis acidification pool 12, are electrolysed
Pond 11 is discharged the bottom by hydrolysis acidification pool 12 even into in pond.
Step 4, the water outlet after the hydrolysis of hydrolysis acidification pool 12 are entered by peristaltic pump 1 in DMBR reactors 13, in waste water
Pollutant further consumed by the microorganism in DMBR reactors 13.Agitating device, DMBR are equipped in hydrolysis acidification pool 12
13 bottom of reactor be equipped with aeration plate 7, hydraulic detention time 12H, return sludge ratio 200%, dissolved oxygen 0.3mg/L,
Sludge concentration is 5000mg/L.It is internally provided with membrane module 5 in DMBR reactors 13 and connects pressure vacuum gauge, film base material 300
The filter area of purpose nylon cloth, membrane module 5 is 0.052m2.Pressure vacuum gauge can monitor the change of transmembrane pressure (TMP) in real time
Change, when TMP reaches 25kPa or so, membrane module is out of service and carries out physical cleaning.
It is illustrated with reference to specific experimental data：
In testing below, the sludge acclimatization liquid that step 1 uses is made of following components：12~15g of industrial glucose,
10~12g of 0.5~1g of ammonium chloride, 0.1~0.2g of potassium dihydrogen phosphate and sodium bicarbonate, surplus are water, are with upper volume total amount
25L；Paper waste in step 2 is made of following components：0.7~0.8g of humic acid, 0.6~0.7g of lignin, crystallite are fine
Tie up element 0.5~0.6g, 0.5~0.6g of xylan, 15~18g of diatomite, 18~20g of industrial glucose, ammonium chloride 1~
1.5g, 0.2~0.3g of potassium dihydrogen phosphate, sodium bicarbonate 15g, surplus are water, are 25L with upper volume total amount；Dynamic film bio is anti-
Device influent quality is answered to be shown in Table 1.
1 bioreactor of dynamic membrane influent quality characteristic of table
Institute's water sampling of the present invention is high water tank 10, electrolytic cell 11, hydrolysis acidification pool 12, DMBR reactors 13 and water outlet
Place, number is 1,2,3,4 and 5 respectively.After each sampled point takes water sample, by water sample after 0.45 μm of membrane filtration
Water sample water analysis is completed in 24 hours.COD is measured using rapid-digestion spectrophotometry；TOC is surveyed using LiquiTOC instrument
It is fixed；UV-vis spectrum are measured using UV-1950 two-beam ultraviolet-uisible spectrophotometers, and scanning wavelength is 190~600nm, scanning
Between be divided into 1nm；Molecular weight distribution is measured using waters1525 gel permeation chrommatographs, Ultrahydrogel gel chromatographic columns (5 μm,
4.6 × 250mm), 35 DEG C, flow velocity 1.0ml/min of column temperature, mobile phase is PBS buffer solutions, detector waters2414, sample introduction
Amount is 0.1ml；Fluorescence spectra use Hitachi's F-7000 fluorescent spectrophotometer assay, excitation wavelength scanning range be 300~
550nm, launch wavelength scanning range are 200~450nm；Sweep speed is 2400nmmin-1；Slit width is 5nm；Band logical：
ExFor 10nm, EmFor 10nm.
1, in sewage disposal process pollutant concentration variation：
Waste water is pumped into electrolytic cell by inlet tank through peristaltic pump, and the removal rate of COD and TOC is respectively after electrolysis
51.9% and 52.3%.Waste water enters hydrolysis acidification pool after electrolysis water outlet, as seen from Figure 2, after hydrolysis acidification pool is handled,
COD and TOC is above electrolytic cell water outlet, but ascensional range is little.This is because having a large amount of hydrolysis acid in hydrolysis acidification pool
Change bacterium and acidogenic bactria, insoluble organic matter are converted into DOM after hydrolysis acidification bacterium hydrolysis.Meanwhile difficult for biological degradation
Macromolecular substances are converted into biodegradable small-molecule substance after hydrolysis acidification pool is handled.Therefore, hydrolysis acidification pool goes out
COD the and TOC values of water can increase.Enter aerobic tank after hydrolysis acidification pool water outlet, after aerobic tank acts on, COD and TOC's goes
Except rate is respectively 82.7% and 83.6%.This illustrates the complicated organic matters of script in waste water to be broken down into simple, stabilization
Compound, removal is decomposed by the microorganisms in aerobic tank.Reactor is respectively 91.1% He to the removal rate of COD and TOC
89.6%.
2, in sewage disposal process DOM molecular vibrational temperature signature analysis：
Fig. 3 is the UV-vis spectrograms of each sampled point DOM.As can be seen from Figure, the sample that each sampled point is taken
Waveform is more similar, and as λ ＞ 450nm, sample absorbance is nearly all intended to zero.All there are one most at 200nm for 5 samples
Big absorption peak contains monocyclic aromatic or conjugated double bond substance in sample component.The intensity of maximum absorption band is with waste water
It is continuously decreased in processing procedure, and certain blue shift has occurred.Meanwhile in UV-vis collection of illustrative plates, E254/E365With 275~
The ratio between 295nm and 350~400nm wave band slopes (SR) it can be used for characterizing the molecular mass size of DOM.E254/ E365It is bigger,
Small molecule ratio then in water is higher；SRHigher, DOM molecular weight is lower, shows that the reactivity that DOM is biodegradable is lower.
As can be seen from Table 2, the E of sample point 1254/E365Value is 1.74, and it is 2.16 that the value, which increases, after electrolysis is handled, through hydrolysis
It is 2.58 that the value, which increases, after acidification pool processing.This demonstrate macromolecular substances in paper waste are more, through electrolysis and hydrolysis acidification
After the processing of pond, macromolecular substances difficult to degrade are converted into more degradable small-molecule substance.Due to containing in hydrolysis acidification pool
More hydrolysis acidification bacterium, the metabolites such as protein and coenzyme increase after the metabolism of hydrolysis acidification bacterium, this is further
The effect for showing hydrolysis acidification is to convert organic matter difficult to degrade to degradable organic matter.E300/E400It can be used for table
Degree of humification is levied, the value is bigger, then it is lower to represent degree of humification.As can be seen from Table 2, the E in waste water300/E400By
Original 1.79 increase to 5.18 after electrolysis-hydrolysis acidification-DMBR process.This demonstrate dissolubilities in paper waste
The degree of humification of organic matter substantially reduces, and improves to class humic acid and class fulvic acid substance removal effect.E445/E665It can use
The extent of polymerization of carbon skeleton in phenyl ring is characterized, the value is bigger, then the degree of polymerization for representing carbon skeleton in phenyl ring is smaller.By in table 2
It can be seen that E445/E665Value increase 7 by 1.94, show with the carbon skeleton in the phenyl ring in the processing procedure of waste water
The degree of polymerization degree of polymerization is smaller and smaller.
The UV-vis absorption values of the different sample point DOM of table 2
Fig. 4 is different sample point DOM graph of molecular weight distribution, can further prove the conclusion that UV-vis is obtained.It is sampling
Point 1 goes out, and molecular weight distribution accounts for the 20.7% of total molecular weight distribution in the substance of 0.1~1MDa.Through electricity it can be seen from Fig. 4
Small molecule proportion increases after solution processing but increase ratio is smaller, has original 27.9% less than the small-molecule substance of 100Da
Increase to 30.7%.And small molecule proportion increases to 41.3% after hydrolysis acidification pool is handled.This and COD, TOC, E254/
E365And SREquivalent trend is consistent.
3, in sewage disposal process DOM fluorescence spectrum map analysis：
The fluorescence spectra of 3.1 different sample points
The fluorescence spectra of each sample point is as shown in Figure 5.Occur three apparent characteristic fluorescence peaks in Fig. 5 altogether, respectively
High excitation wavelength Tryptophan fluorescence peak (peak A, ExFor 270~280nm, EmFor 320~350nm), ultraviolet region fulvic acid fluorescence
Peak (peak B, ExFor 240~270nm, EmFor 370~440nm) and visible region fulvic acid fluorescence peak (peak C, ExFor 310~
360nm, EmFor 370~450nm).A intensity in peak increases at sample point 2 it can be seen from Fig. 5, at sample point 3, peak A
Intensity significantly increase, this is because in hydrolysis acidification pool due to hydrolysis acidification bacterium and anaerobic bacteria under the action of, be partly dissolved
Property the hydrolyzed acidification of protein to produce the substance of a large amount of class tryptophan class, to result in the tryptophane in water body
Increase.And after entering the ponds DMBR, due to the metabolism of aerobic microbiological, a part of tryptophan substance is consumed
Degradation, so the intensity of fluorescence peak significantly weakens.And the intensity of tryptophan further decreases and shows the ponds DMBR in sample 5
In the substance of membrane module tryptophan one kind have certain crown_interception.In sample 2, peak B has the tendency that into peak.This is because
After electrolysis is handled, the biodegradable macromolecular that is difficult in waste water is destroyed, and small-molecule substance content increases, in hydrolysis acidification
Peak B intensity reaches maximum in pond.With the progress of reaction, peak B intensity reduces, and fulvic acid is degraded to other substances.
3.2 fluorescence parameters are analyzed
Reactor in the process of running the fluorescence intensity at the DOM characteristic fluorescences peak of each sample point, fluorescence peak center,
Characteristic fluorescence peak intensity summation, fluorescence index (FI), humification index (HIX) and biological source index (BIX) are shown in Table 3.According to glimmering
The center of photopeak and the variation of intensity can reflect the variation of the dissolved organic matter of each sample point.By can be in table 3
Find out, for waste water after electrolysis/hydrolysis acidification/DMBR process, peak A, peak B, peak C fluorescence intensities have larger decrease.
Peak A obtains fluorescence intensity and is reduced to 659.7 by 1547；The fluorescence intensity of peak B is reduced to 736.2 by 1806；The intensity of peak C by
893.6 are reduced to 286.5.Certain blue shift all has occurred compared with sample point 1 for the center at the characteristic fluorescence peak of peak A, peak B, peak C
Or red shift.The reason of the reason of blue shift results in the structure of substance with oxidation, and to have occurred certain variation related, red shift
It is related with carbonyl, amido, hydroxyl and the increase of carboxyl in fluorophor.
FI is commonly used to humic-like substance source and characteristic in characterization DOM, such as fulvic acid, humic acid.As FI ＞ 1.9,
Show that the humic-like substance in sample is mainly derived from the metabolism of microorganism and generates；Then show in sample as FI ＜ 1.4
Humic-like substance be mainly derived from Lu Yuan output.As can be seen from Table 3, ranging from the 1.5~2.49 of FI values, average value are
2.05.Therefore deduce that the class fulvic acid during process waste water is mainly generated due to the metabolism of microorganism
HIX usually can be used for characterizing the humified degree or maturity of DOM.As HIX ＜ 3, then represent in DOM with biological source as
It is leading.As can be seen from Table 3, the value is 1.13~1.46 in wastewater treatment process, average value 1.26, so DOM master
If being generated due to the metabolism of microorganism.BIX commonly used to characterization bacteria metabolism and the organic matter that generates with it is outer
Proportion between the organic matter of source.By that can be obtained in table 3, ranging from the 1.34~1.76 of BIX, average value 1.63.As BIX ＞
When 1.0, the source of organic matter generates for microbial activities.It therefore deduces that, DOM is mainly by microorganism in group technology
Activity and generate.
Fluorescent characteristic in the different sample point DOM of table 3
Above description has shown and described several preferred embodiments of invention, but as previously described, it should be understood that invention is not
It is confined to form disclosed herein, is not to be taken as excluding other embodiments, and can be used for various other combinations, modification
And environment, and can be carried out by the above teachings or related fields of technology or knowledge in the scope of the invention is set forth herein
Change.And changes and modifications made by those skilled in the art do not depart from the spirit and scope of invention, then should all be weighed appended by invention
In the protection domain that profit requires.
Claims (10)
1. a kind of electrolysis/hydrolysis/DMBR Combined Treatment reactors, which is characterized in that including high water tank (10), the high position water
Case (10) is connected with electrolytic cell (11), hydrolysis acidification pool (12) and DMBR reactors (13), the high position water in turn by pipeline
It is both provided with peristaltic pump on pipeline between case (10) and electrolytic cell (11), between electrolytic cell (11) and hydrolysis acidification pool (12)
(1)；Setting is provided with wriggling there are two pipeline on each pipeline between the hydrolysis acidification pool (12) and DMBR reactors (13)
It pumps (1)；Be provided with membrane module (5) and aeration plate (7) in the DMBR reactors (13), the membrane module (5) by pipeline according to
It is secondary to be connected with pressure gauge (6) and peristaltic pump (1)；The aeration plate (7) is connected with spinner flowmeter (8) and sky in turn by pipeline
Air pump (9).
2. electrolysis/hydrolysis according to claim 1/DMBR Combined Treatment reactors, which is characterized in that the electrolytic cell
(11) setting is provided with agitating device (4) there are two the electrolytic zinc-coated steel sheet (2) that is oppositely arranged between the electrolytic zinc-coated steel sheet (2) on bottom.
3. electrolysis/hydrolysis according to claim 2/DMBR Combined Treatment reactors, which is characterized in that the electrolytic zinc-coated steel sheet
(2) material is aluminium or iron；The distance between electrolytic zinc-coated steel sheet (2) is 4cm.
4. electrolysis/hydrolysis according to claim 1/DMBR Combined Treatment reactors, which is characterized in that the electrolytic cell
(11) electrolyte concentration is 0.8g/L, current density 0.8ma/cm2；Electrolyte is anhydrous sodium sulfate.
5. electrolysis/hydrolysis according to claim 1/DMBR Combined Treatment reactors, which is characterized in that the hydrolysis acidification
Elastic filler (3) and agitating device (4) are provided in pond (12), the agitating device (4) is arranged in hydrolysis acidification pool (12)
Center.
6. electrolysis/hydrolysis according to claim 1/DMBR Combined Treatment reactors, which is characterized in that the hydrolysis acidification
The dischargeable capacity of pond (12) and DMBR reactors (13) is respectively 16.5L and 33L.
7. electrolysis/hydrolysis according to claim 1/DMBR Combined Treatment reactors, which is characterized in that the DMBR reactions
The hydraulic detention time of device (13) is 12H, and return sludge ratio 200%, dissolved oxygen is 0.2~0.3mg/L, and sludge concentration is
5000~6000mg/L.
8. electrolysis/hydrolysis according to claim 1/DMBR Combined Treatment reactors, which is characterized in that the membrane module
(5) film base material is the nylon cloth of 300 mesh, and the filter area of membrane module (5) is 0.052m2。
9. a kind of electrolysis/hydrolysis/DMBR combined treatment process, which is characterized in that include the following steps：
Step 1 pours into seed sludge in the DMBR reactors (13) of electrolysis/hydrolysis/DMBR Combined Treatment reactors, and sludge is heavy
The 1/3 of reactor is accounted for after drop, and sludge acclimatization liquid is added to DMBR reactors (13) dischargeable capacity；Continuous aeration for 24 hours after, stand
Supernatant is discharged in 30min, then proceedes to that sludge acclimatization liquid is added；It is tamed and dociled using the sludge of low concentration in the initial stage of reaction
Change liquid to be tamed, gradually increases sewage load after pending raising with obvious effects again；After the domestication of 15~20d, removal rate
It is basically stable at 90% or more；After system run all right, it is put into elastic filler (3) in hydrolysis acidification pool (12), is so followed
Inscription of loop, until sludge concentration desired value 6000mg/L；After operation one month, filler surface increasingly generates one layer of biomembrane, and
And sludge grain size reaches biofilm requirement, i.e., carries out biofilm to membrane module (5), reactor enters formal startup stage；
Step 2, after reactor formally starts, will after paper waste enter high water tank (10), paper waste is through peristaltic pump (1)
Into electrolytic cell (11) and react；
Step 3, the waste water after electrolysis are further purified after peristaltic pump (1) effect into hydrolysis acidification pool (12), are electrolysed
Pond (11) is discharged the bottom by hydrolysis acidification pool (12) even into in pond；；
Step 4, the water outlet after hydrolysis acidification pool (12) hydrolysis are entered by peristaltic pump (1) in DMBR reactors (13), waste water
In pollutant further consumed by the microorganism in DMBR reactors (13)；Stirring dress is equipped in hydrolysis acidification pool (12)
It sets, DMBR reactors (13) bottom is equipped with aeration plate (7), is internally provided with membrane module (5) in DMBR reactors (13) and connects pressure
Power table (6), pressure gauge (6) are pressure vacuum gauge, and pressure gauge (6) monitors the variation of transmembrane pressure in real time, when TMP reaches 25kPa
When, membrane module is out of service and carries out physical cleaning.
10. electrolysis/hydrolysis/DMBR combined treatment process according to claim 9, which is characterized in that sludge acclimatization liquid is
It is made of following components：12~15g of industrial glucose, 0.5~1g of ammonium chloride, 0.1~0.2g of potassium dihydrogen phosphate and bicarbonate
10~12g of sodium, surplus are water, are 25L with upper volume total amount；The standard of the sludge acclimatization liquid of low concentration is：COD is 350mg/
L, ammonia nitrogen 8mg/L, phosphate 0.5mg/L, total nitrogen 18mg/L, total phosphorus 1.5mg/L, the mark that treatment effect significantly improves
Standard is：The removal rate of the pollutants such as COD, ammonia nitrogen, phosphate, total phosphorus, total nitrogen is 95% or more；Electrolytic cell (11) interior electric current is
1A, electrolysis time 1H, electrolyte concentration 0.8g/L, current density 0.8ma/cm2；Electrolyte is anhydrous sodium sulfate；
The hydraulic detention time of DMBR reactors (13) is 12H, and return sludge ratio 200%, dissolved oxygen is 0.2~0.3mg/L, sludge
A concentration of 5000~6000mg/L；The film base material of membrane module (5) is the nylon cloth of 300 mesh, and the filter area of membrane module (5) is
0.052m2。
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