CN110526527A - A kind of biomembrane biochemistry reaction system and process for purifying waste water based on ozone - Google Patents
A kind of biomembrane biochemistry reaction system and process for purifying waste water based on ozone Download PDFInfo
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- CN110526527A CN110526527A CN201910922384.5A CN201910922384A CN110526527A CN 110526527 A CN110526527 A CN 110526527A CN 201910922384 A CN201910922384 A CN 201910922384A CN 110526527 A CN110526527 A CN 110526527A
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 314
- 239000002351 wastewater Substances 0.000 title claims abstract description 118
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000008569 process Effects 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 title claims description 52
- 239000001301 oxygen Substances 0.000 claims abstract description 163
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 163
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 162
- 238000005273 aeration Methods 0.000 claims abstract description 69
- 238000012545 processing Methods 0.000 claims abstract description 38
- 238000005949 ozonolysis reaction Methods 0.000 claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 claims abstract description 24
- 238000006385 ozonation reaction Methods 0.000 claims abstract description 23
- 239000007789 gas Substances 0.000 claims description 116
- 239000003054 catalyst Substances 0.000 claims description 97
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 94
- 238000009826 distribution Methods 0.000 claims description 30
- 238000000354 decomposition reaction Methods 0.000 claims description 24
- 239000005416 organic matter Substances 0.000 claims description 20
- 238000012856 packing Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 230000015556 catabolic process Effects 0.000 claims description 13
- 238000006731 degradation reaction Methods 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000002905 metal composite material Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 35
- 238000000746 purification Methods 0.000 abstract description 7
- 238000004065 wastewater treatment Methods 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 description 34
- 230000003647 oxidation Effects 0.000 description 33
- 230000000694 effects Effects 0.000 description 26
- 230000002779 inactivation Effects 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 230000008859 change Effects 0.000 description 9
- 238000012546 transfer Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000000428 dust Substances 0.000 description 8
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 150000002391 heterocyclic compounds Chemical class 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- -1 Hydroxyl radical free radical Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 238000011001 backwashing Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000004936 stimulating effect Effects 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
Classifications
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biodiversity & Conservation Biology (AREA)
- Microbiology (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention belongs to field of waste water treatment, in particular to a kind of biomembrane biochemistry system and process for purifying waste water based on ozone.Ozone reactor, the ozone reactor is by carrying out purified treatment to waste water using ozone；Oxygen-enriched aeration biological me.mbrane bioreactor, the oxygen-enriched aeration biological me.mbrane bioreactor are connected to the ozone generator, for carrying out deep purifying processing to purified waste water and discharging；Ozonolysis reactions device, the ozonolysis reactions device are connected to the ozone generator, the oxygen-enriched aeration biological me.mbrane bioreactor respectively, for that will resolve into oxygen by the complete ozone of unreacted after the ozone reactor.The present invention provides a kind of low energy consumption, high efficiency, economic waste water advanced purifying process: catalytic ozonation series connection fixed biofilm biochemical reactor.It can make purification of waste water qualified discharge under lower energy consumption.
Description
Technical field
The invention belongs to field of waste water treatment, in particular to a kind of biomembrane biochemistry reaction system and waste water based on ozone
Purification and technique are used for deep-treating organic waste water.
Background technique
In order to cope with worsening ecological environment, country constantly promulgates more stringent environment protectment protection, to sewage
Also in the continuous improvement, and as rapid industrial development, industrial wastewater water are continuously increased, component is increasingly for the requirement of processing
Complexity, processing difficulty is also increasing, especially those hardly degraded organic substances or the organic pollutant to the toxic effect of biology
Processing problem cause people greatly to pay attention to, but these organic pollutants are not only difficult to biodegrade, it is also difficult to general
Oxidizing removal.
In order to achieve the purpose that deep-treating organic waste water, the mode for generalling use catalytic ozonation at present carries out sewage
Processing.Catalytic ozonation method is the high-level oxidation technology based on ozone, and principle is that ozone generates under the effect of the catalyst
Hydroxyl radical free radical OH, OH are that a kind of oxidisability is only second to F2Strong oxidizer, being capable of the efficient oxidation organic contamination difficult to degrade
Object.However existing technology the prior art has at least the following problems:
1) economy of catalytic ozonation technical application is lower.As generated channel, wall flow phenomenon in ozone reactor, lead
Cause ozone utilization rate low, poor processing effect；Tail gas ozone breaker, which needs to be heated at high temperature, could effectively destroy ozone, energy consumption compared with
It is high；Oxygen (tail oxygen) content is still up to 80% or more in tail gas after ozone decomposes, is all directly discharged into substantially because its is harmless
Atmosphere, to cause a large amount of wastes of energy.
2) catalytic ozonation for hardly degraded organic substance oxidation not fully, it is difficult to by the small-molecule substance after oxidation
Further oxidation, therefore simple catalytic ozonation has certain limitation for the processing of organic matter.
Patent CN201620061049.2 proposes a kind of wastewater treatment equipment of two-stage catalytic ozonation, and waste water passes through
Enter back into secondary ozone catalysis oxidation after level-one catalytic ozonation, direct emission atmosphere after ozone tail gas destroys, although this
Kind method improves the degree for the treatment of of Organic Pollutants in Wastewater, but not can solve the low problem of ozone utilization rate, and consumes
Oxygen amount and equipment investment cost are high.
To solve the problems, such as that ozone tail gas utilizes, patent CN205603366U is proposed the ozone tail of catalytic ozonation
After gas destroys, the recycling of upstream biochemical reactor is returned to, although reducing this method reduces the aeration quantity of upstream biochemical reaction
Power consumption, but not can solve the processing problem of waste water small molecular organic matter after catalytic ozonation.
Summary of the invention
_ _ _ _ this patent is intended in view of the deficiencies of the prior art, provide a kind of low energy consumption, high efficiency, economical is waste water advanced
Purification process and biomembrane biochemistry reaction system and process for purifying waste water based on ozone, can make waste water under lower energy consumption
Purify qualified discharge.
I.e. by improving ozone oxidation reaction efficiency, while improving open loop chain rupture rate, the energy consumption of ozone oxidation is reduced；Have
Effect utilize catalytic ozonation technique ozone tail gas, to the tail gas through low energy consumption decomposition reaction processing after, as highly concentrated
Degree oxygen is aerated biomembrane biochemistry reactor, is oxygen-enriched biomembrane biochemistry by conventional biomembrane biochemistry reactor optimization
Reactor, lifting waste water treatment effect reduce wastewater treatment operating cost.
The present invention provides a kind of biomembrane biochemistry reaction system based on ozone, comprising:
Ozone reactor, the ozone reactor is by carrying out purified treatment to waste water using ozone；
Oxygen-enriched aeration biological me.mbrane bioreactor, the oxygen-enriched aeration biological me.mbrane bioreactor and the ozone generator
Connection, for carrying out deep purifying processing to purified waste water and discharging；
Ozonolysis reactions device, the ozonolysis reactions device are raw with the ozone generator, the oxygen-enriched aeration respectively
Object me.mbrane bioreactor connection, for oxygen will to be resolved by the complete ozone of unreacted after the ozone reactor.
In the technical program, by ozone (remaining is oxygen) mixed gas, ozone reactor is entered together with waste water, smelly
In oxygen reactor under the action of catalyst, aromatic hydrocarbon organic matter difficult to degrade is resolved into degradable by open loop and chain rupture in waste water
Organic matter, waste water after catalytic ozonation is discharged from ozone reactor, and it is biochemical to be then sent to oxygen-enriched aeration biological film
Reactor carries out further biochemical treatment, COD (COD) qualified discharge of waste water after purification.Catalytic ozonation reaction
The complete ozone tail gas of unreacted, which is collected, in device enters ozone decomposer, the ozone in tail gas is resolved into harmless oxygen, so
It mixes, send to oxygen-enriched aeration biological film with pressurized air after tail gas of this strand rich in oxygen is pressurized by tail gas conveying fan afterwards
Biochemical reactor aeration, can not only reduce air aeration amount, reduce energy consumption, while the oxygen transfer rate of oxygen-enriched aeration is fast, can
To improve the biochemical efficiency of organic matter.
Preferably, the ozone reactor is connected to ozone generator, and the ozone generator generates smelly for decomposing pure oxygen
Oxygen and oxygen mixed gas.
Preferably, the ozone reactor includes: reactor shell, is successively set upwards in the reactor enclosure body from bottom
It is equipped with ozone distributor, inlet distribution device, water conservancy diversion support ring, catalyst supporting plate, catalyst layer, catalyst pressing plate.
In the technical program, pure oxygen is introduced into ozone generator, it is mixed for 8~10% ozone and oxygen that ozone concentration occurs
It closes gas (abbreviation ozone), ozone is passed through the bottom of ozone reactor, by ozone distributor, reaches at ozone reactor interface
On uniform aeration.Waste water enters reactor lower part, is uniformly distributed on ozone reactor interface by inlet distribution device, together
When, the waste water of entrance by lower section it is ozonation aerated be stirred after, enter catalyst layer from the bottom to top, passed through in the form of trickle
Catalyst surface, in catalyst surface, ozone not only direct oxidation hardly degraded organic substance makes its open loop chain rupture, and anti-with water
It answers, releasing great amount of hydroxy group free radical OH, OH and can directly reacting with organic matter in water phase makes its degradation, and it is easy to be converted to
Short chain organic matter even final product water and the carbon dioxide of degradation.
Further, it is preferable that the lower surface of the water conservancy diversion support ring is inclined-plane, and the inner wall with the ozone reactor is in
120~160 ° of angles simultaneously enclose setting along the inner wall of the ozone reactor one.
It is guided to the ozone gas close to wall inside catalyst layer behind inclined-plane, without
Wall stream can be formed along wall.
Further, it is preferable that the catalyst supporting plate and the catalyst pressing plate are porous plate, aperture size is 2~
8mm prevents catalyst loss, and the loadings of catalyst are the 30~70% of the ozone reactor volume, catalyst loading
If being lower than 30%, the time of contact of waste water and catalyst is too small, and reaction is incomplete.If catalyst loading is higher than 70%, bed
Resistance increases, and is unfavorable for backwashing.
Preferably, the gas outlet of the ozone reactor is connected to the air inlet of demister, the water outlet of the demister
It is connected to the water return outlet of the ozone reactor, the air inlet of the gas outlet of the demister and the ozonolysis reactions device connects
Logical, the demister is for removing free water.
In the technical program, it is oxygen that ozone carries out the tail gas main component after catalysis oxidation in ozone reactor, this
Outside, also containing a small amount of unreacted ozone and a small amount of free water, so initially entering demisting after tail gas discharge ozone reactor
Device removes free water, enters back into ozone decomposer.
Preferably, it is set gradually from gas access to outlet inside the ozonolysis reactions device: gas distributor, catalysis
Agent lower supporting plate, ozone decomposition catalyst layer, catalyst upper backup pad.
In the technical program, removing in the ozone tail gas of free water is mainly oxygen and a small amount of unreacted ozone.Because
Ozone is to the toxic effect of microorganism, therefore it is necessary to which ozone layer destroying in ozone tail gas is decomposed into oxygen, just can enter biochemical benefit
With.
After ozone enters ozonolysis reactions device, ozone decomposition catalyst surface is flowed through by gas distributor, in ozone
Decomposition catalyst surface is broken down into oxygen.
The catalyst upper backup pad, catalyst lower supporting plate are preferably porous fixation clip, prevent catalyst loss.
Preferably, set gradually upwards from bottom in the oxygen-enriched aeration biological me.mbrane bioreactor gas distribution pipe, water distributor,
Biofilm packing layer；
The entrance connection setting blowdown pipe of the gas distribution pipe.
In the technical program, the air introduced from the oxygen and blowdown pipe that ozone reactor decomposites is mixed into oxygen-enriched
Air.Waste water after ozone oxidation is decomposed enters the oxygen-enriched aeration biological me.mbrane bioreactor from water distributor, with the richness
Oxygen air after evenly mixing, is contacted with the biofilm packing loaded in the oxygen-enriched aeration biological me.mbrane bioreactor reactor,
Water and carbon dioxide, discharged wastewater met the national standard are degraded to by further deep biochemical.
Preferably, the spacing of the gas distribution pipe and oxygen-enriched aeration biological me.mbrane bioreactor bottom is h1, the cloth
Water pipe and the gas distribution pipe are at a distance of h2, and the biofilm packing layer and oxygen-enriched aeration biological me.mbrane bioreactor bottom are apart
h3；Wherein h1:h2:h3 is (3~10): (2~5): (6~15)；Wherein h1 is preferably 300~1000mm；H2 is preferably 200~
500mm；H3 is preferably 600~1500mm；Water distributor is arranged above gas distribution pipe, can use the air-flow of gas distribution pipe out will
Waste water mixes rapidly, improves mass-transfer efficiency.
The filler filling ratio of the biofilm packing layer is the 30~50% of pool capacity, and the oxygen-enriched aeration biological film is biochemical
Oxygen-rich concentration in reactor in air is 23~28%.
In the technical program, water distributor is arranged above gas distribution pipe, can use the air-flow of gas distribution pipe out for waste water
Mixing rapidly improves mass-transfer efficiency.If the filler filling ratio of biofilm packing layer is too low, contact of the waste water with biofilm packing
Time is short, and poor processing effect, ratio is too high, and the sludge that biofilm packing generates backwashes difficult.
If oxygen-rich concentration is too high, aeration quantity is small, then is unfavorable for gas-liquid mixed mass transfer, conversely, oxygen-rich concentration is too low, then rises not
To oxygen-enriched effect.The COD volumetric loading of reactor is up to 2~3kg/m3/ d, biochemical efficiency are higher than 90%.
Preferably, the gas outlet of the ozonolysis reactions device is connected to dust collector, and the dust collector is connected to institute
State gas distribution pipe.
In the technical program, the dust collector is used to remove the dust in purified gas, so that it is guaranteed that being passed through
Gas in gas distribution pipe it is pure, gas distribution pipe will not be blocked, it is longer using the time.
The process for purifying waste water of the present invention also provides a kind of biomembrane biochemistry reaction system based on ozone:
The ozone and waste water for entering ozone reactor simultaneously, in the ozone reactor under the action of catalyst, waste water
In aromatic hydrocarbon organic matter difficult to degrade by open loop and chain rupture, resolve into easily biodegradable organics；
Waste water after catalytic ozonation, containing easily biodegradable organics is discharged from the ozone reactor, and send
Deep purifying processing is carried out to oxygen-enriched aeration biological me.mbrane bioreactor, deep purifying treated waste water reaches the chemistry of waste water
It is discharged after oxygen demand standard；
The complete ozone tail gas of unreacted enters ozonolysis reactions device in the ozone reactor, decomposes in the ozone
Ozone in the ozone tail gas is resolved under the action of ozone decomposition catalyst harmless oxygen in reactor, then will be decomposed
Harmless oxygen mixes with air afterwards, send to the oxygen-enriched aeration biological me.mbrane bioreactor and is aerated.
Preferably, the pressure in the ozone reactor is -1~5KPa, and temperature is 20~50 DEG C；Ozone adds concentration
For 5~60mg/L；The liquid hourly space velocity (LHSV) of reaction is 0.5~3h-1；
The catalyst uses metal-supported catalyst.
The ozone and oxygen mixed gas that ozone concentration is 8~10% occur in the technical program, in ozone generator, this
Concentration in range, which can be improved, changes the dissolution equilibrium of ozone in water, increase the concentration of ozone in water, and then improve smelly
The effect of oxygen oxidation.If ozone concentration is excessively high, not only energy consumption consumption is excessive, but also is limited by the limitation of ozone generator；It is on the contrary
Ozone concentration is too low, then can reduce ozone oxidation effect.
If the temperature in the technical program in ozone reactor is excessively high, it is unfavorable for the dissolution of ozone in water, conversely, warm
Spend low, then reactivity is weaker.Ozone dosage is related to COD in waste water, and COD high, then ozone dosage is big, and COD is low, then
Ozone dosage is small.The liquid hourly space velocity (LHSV) of reaction is 0.5~3h-1, and air speed is too high, and conversion ratio is low, and air speed is too high, and cost of investment is big
And it is unobvious to promote effect to conversion ratio.The technical solution can make open loop chain rupture rate be higher than 80%, and wastewater biodegradability (B/C) is big
In 0.5.
Without pressurization and heating in purification process, energy consumption is reduced.
Preferably, the catalyst layer uses metal-supported catalyst, including；
Catalyst activity component is transition-metal Fe, two or more the compounding in Ti, Mn, Ni, Cu, V, Co,
Or the two or more of above-mentioned metal oxide are compounded；
Auxiliary agent is the oxide of Ru, Zr；
Carrier is aluminium oxide or silica or active carbon.It is a small amount of with Ru, Zr etc. by introducing in technical solution of the present invention
Modifying agent of the solid solution, oxide made of one or more of transition metal element as catalyst carrier improves catalyst
Generate the probability of oxidation state metal direct oxidation organic matter.
Catalyst can not only be in catalyst surface catalysis oxidation decomposing organic matter, and it is higher certainly to pass through stimulating activity
By base, the oxidation operation being catalyzed indirectly in water phase by free radical is decomposed, to improve the catalytic efficiency of catalyst.
Preferably, in the ozonolysis reactions device:
The air speed of reaction: 500~5000h-1, temperature: room temperature, pressure: -1~5KPa.
Ozone is decomposed without pressurization and heating in the technical program, and low energy consumption.Ozone decomposition efficiency is greater than 99%.It decomposes
Afterwards, the ozone content in tail gas is less than 0.1mg/L.
Preferably, in the ozonolysis reactions device:
The ozone decomposition catalyst uses metal composite oxide, the i.e. oxide two of Fe, Mn, Ti, Cu, Co, Mg, K
Kind or two or more compound systems；
Further, it is preferable that the content range of reactive metal oxides component are as follows: manganese oxide: 10~40%, iron oxide:
20~60%.Magnesia: 0~3%, titanium oxide: 2~10%, cobalt oxide: 0~5%, potassium oxide: 0~2%.
Iron oxide, titanium oxide and manganese oxide are major catalyst in the technical program, remaining is catalyst promoter, for improving
Degrading activity of the catalyst to ozone.
A kind of biomembrane biochemistry reaction system and process for purifying waste water based on ozone provided by the invention can bring with
It is lower at least one the utility model has the advantages that
1) present invention provides a kind of low energy consumption, high efficiency, economic waste water advanced purifying process: catalytic ozonation series connection
Fixed biofilm biochemical reactor.It can make purification of waste water and qualified discharge under lower energy consumption.
2) efficient ozone aoxidizes: by the way that water conservancy diversion support ring is arranged in ozone catalytic catalyst reactor layer lower part, improving
Mixture homogeneity and mass-transfer efficiency between gas-liquid two-phase avoid the wall flow phenomenon of ozone gas, reduce the loss of ozone, improve
Ozone utilization rate and organic matter treatment effeciency.
3) normal temperature and pressure ozone layer destroying technology, avoids tail gas heating, reduces the energy consumption of ozone destruct device.
4) ozone tail gas improves dissolved oxygen into fixed biofilm biochemical reactor, accelerates oxygen transfer rate and biochemistry
Reaction speed and reaction efficiency have stronger anti impulsion load performance, and reduce blast aeration energy consumption.
Detailed description of the invention
Below by clearly understandable mode, preferred embodiment is described with reference to the drawings, to above-mentioned characteristic of the invention, skill
Art feature, advantage and its implementation are further described.
Fig. 1 is a kind of biomembrane biochemistry reaction system schematic device based on ozone；
Drawing reference numeral explanation:
Ozone generator 1, ozone reactor 2, demister 3, ozonolysis reactions device 4, oxygen-enriched aeration biological film are biochemical anti-
Answer device 5, ozone distributor 21, inlet distribution device 22, water conservancy diversion support ring 23, catalyst supporting plate 24, catalyst layer 25, catalyst
Pressing plate 26, gas distribution pipe 61, water distributor 62, blowdown pipe 63, biofilm packing layer 64.
Specific embodiment
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, Detailed description of the invention will be compareed below
A specific embodiment of the invention.It should be evident that drawings in the following description are only some embodiments of the invention, for
For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings other
Attached drawing, and obtain other embodiments.To make simplified form, only schematically showing and phase of the present invention in each figure
The part of pass, they do not represent its practical structures as product.
Embodiment 1
The invention discloses a kind of biomembrane biochemistry reaction system based on ozone, as shown in Figure 1, comprising:
Ozone reactor 2, ozone reactor 2 is by carrying out purified treatment to waste water using ozone；
Oxygen-enriched aeration biological me.mbrane bioreactor 5, oxygen-enriched aeration biological me.mbrane bioreactor 5 are connected to ozone generator 1,
For carrying out deep purifying processing to purified waste water and discharging；
Ozonolysis reactions device 4, ozonolysis reactions device 4 are biochemical anti-with ozone generator 1, oxygen-enriched aeration biological film respectively
Device 5 is answered to be connected to, for oxygen will to be resolved by the complete ozone of unreacted after ozone reactor 2.
By ozone (remaining is oxygen) mixed gas in the present embodiment, ozone reactor 2 is entered together with waste water, in ozone
In reactor 2 under the action of catalyst, aromatic hydrocarbon organic matter difficult to degrade is resolved into degradable by open loop and chain rupture in waste water
Organic matter, the waste water after catalytic ozonation are discharged from ozone reactor 2, and it is biochemical anti-to be then sent to oxygen-enriched aeration biological film
Device 5 is answered to carry out further biochemical treatment, chemical oxygen demand of waste water (COD) qualified discharge after purification.Catalytic ozonation reactor
The interior complete ozone tail gas of unreacted, which is collected, enters ozone decomposer, the ozone in tail gas is resolved into harmless oxygen, then
It mixes, send raw to oxygen-enriched aeration biological film with pressurized air after tail gas of this strand rich in oxygen is pressurized by tail gas conveying fan
Change reactor 5 to be aerated, can not only reduce air aeration amount, reduces energy consumption, while the oxygen transfer rate of oxygen-enriched aeration is fast, it can be with
Improve the biochemical efficiency of organic matter.
Embodiment 2
As shown in Figure 1, the present embodiment is on the basis of embodiment 1, ozone reactor 2 is connected to ozone generator 1, ozone hair
Raw device 1 generates ozone and oxygen mixed gas for decomposing pure oxygen.
Ozone reactor 2 includes: reactor shell, is disposed with ozone distributor upwards from bottom in reactor enclosure body
21, inlet distribution device 22, water conservancy diversion support ring 23, catalyst supporting plate 24, catalyst layer 25, catalyst pressing plate 26.
The lower surface of water conservancy diversion support ring 23 is inclined-plane, and the inner wall with ozone reactor 2 is in 120~160 ° of angles and along smelly
The inner wall one of oxygen reactor 2 encloses setting.So that the ozone gas of close wall is guided in catalyst layer 25 behind inclined-plane
Portion, without forming wall stream along wall.
Catalyst supporting plate 24 and catalyst pressing plate 26 are porous plate, and aperture size is 2~8mm, prevent catalyst loss,
The loadings of catalyst are the 30~70% of 2 volume of ozone reactor, if catalyst loading is lower than 30%, waste water and catalyst
Time of contact it is too small, reaction is incomplete.If catalyst loading is higher than 70%, bed resistance increases, and is unfavorable for backwashing.
In the present embodiment, pure oxygen is introduced into ozone generator 1, it is mixed for 8~10% ozone and oxygen that ozone concentration occurs
It closes gas (abbreviation ozone), ozone is passed through the bottom of ozone reactor 2, by ozone distributor 21, reaches in ozone reactor 2
Uniform aeration on interface.Waste water enters reactor lower part, is uniformly distributed in 2 interface of ozone reactor by inlet distribution device 22
On, meanwhile, the waste water of entrance by lower section it is ozonation aerated be stirred after, enter catalyst layer 25, from the bottom to top with trickle
Form passes through catalyst surface, and in catalyst surface, ozone not only direct oxidation hardly degraded organic substance makes its open loop chain rupture, and
And reacted with water, releasing great amount of hydroxy group free radical OH, OH and can directly reacting with organic matter in water phase makes its degradation, turns
Chemical conversion is easy short chain organic matter even final product water and the carbon dioxide of degradation.
Embodiment 3
As shown in Figure 1, the present embodiment is on the basis of embodiment 2, the gas outlet of ozone reactor 2 and demister 3 into
Port connection, the water outlet of demister 3 are connected to the water return outlet of ozone reactor 2, and the gas outlet of demister 3 and ozone decompose instead
The air inlet of device 4 is answered to be connected to, demister 3 is for removing free water.
Specifically, the gas outlet of ozonolysis reactions device 4 is connected to dust collector, dust collector is connected to gas distribution pipe 61,
Dust collector is used to remove the dust in purified gas, so that it is guaranteed that the gas being passed through in gas distribution pipe 61 is pure, no
Gas distribution pipe 61 can be blocked, it is longer using the time.
In the present embodiment, the tail gas main component after catalytic ozonation reaction is oxygen, in addition, also containing on a small quantity not
The ozone of reaction and a small amount of free water, so initially entering demister 3 after tail gas discharge ozone reactor 2 removes free water, then
Into ozonolysis reactions device 4.
Embodiment 4
As shown in Figure 1, the present embodiment is on the basis of embodiment 1, from gas access to out inside ozonolysis reactions device 4
Mouth is set gradually: gas distributor, catalyst lower supporting plate, ozone decomposition catalyst layer, catalyst upper backup pad, the device knot
Composition is not shown on the diagram.Remove mainly oxygen and on a small quantity unreacted ozone in the ozone tail gas of free water.Because of ozone
To the toxic effect of microorganism, therefore it is necessary to which ozone layer destroying in ozone tail gas is decomposed into oxygen, biochemical utilization just can enter.
In the present embodiment, after ozone enters ozonolysis reactions device 4, ozone decomposition catalyst is flowed through by gas distributor
Surface is broken down into oxygen on ozone decomposition catalyst surface.
Catalyst upper backup pad, catalyst lower supporting plate are preferably porous fixation clip, prevent catalyst loss.
Embodiment 5
As shown in Figure 1, the present embodiment, on the basis of Examples 1 to 4, oxygen-enriched aeration biological me.mbrane bioreactor 5 is interior certainly
Bottom sets gradually gas distribution pipe 61, water distributor 62, biofilm packing layer 64 upwards, and 61 inlet of gas distribution pipe and blowdown pipe 63 export
Place's connection.
The air introduced from the oxygen that ozone reactor 2 decomposites and blowdown pipe 63 is mixed into the present embodiment oxygen-enriched
Air.Waste water after ozone oxidation is decomposed enters oxygen-enriched aeration biological me.mbrane bioreactor 5 from water distributor 62, with oxygen-enriched sky
Gas after evenly mixing, is contacted with biofilm packing layer 64, is degraded to water and carbon dioxide, wastewater to reach standard by further deep biochemical
Discharge.
Embodiment 6
As shown in Figure 1, the present embodiment is on the basis of embodiment 5, gas distribution pipe 61 and oxygen-enriched aeration biological membrane bio-reaction
The spacing of 5 bottom of device is h1, water distributor 62 and gas distribution pipe 61 at a distance of h2, and biofilm packing layer 64 and oxygen-enriched aeration biological film are biochemical
5 bottom of reactor is at a distance of h3；Wherein h1:h2:h3 is (3~10): (2~5): (6~15)；Wherein h1 be preferably 300~
1000mm；H2 is preferably 200~500mm；H3 is preferably 600~1500mm；Water distributor is arranged above gas distribution pipe, Ke Yili
Waste water is mixed rapidly with the air-flow that gas distribution pipe comes out, improves mass-transfer efficiency.
The filler filling ratio of biofilm packing layer 64 is the 30~50% of pool capacity, if the filler of biofilm packing layer loads
Ratio is too low, and the time of contact of waste water and biofilm packing is short, and poor processing effect, ratio is too high, the dirt that biofilm packing generates
Mud backwash is difficult.Oxygen-rich concentration in oxygen-enriched aeration biological me.mbrane bioreactor 5 in air is 23~28%, if oxygen-rich concentration
Too high, aeration quantity is small, then is unfavorable for gas-liquid mixed mass transfer, conversely, oxygen-rich concentration is too low, does not then have oxygen-enriched effect.Reactor
COD volumetric loading up to 2~3kg/m3/ d, biochemical efficiency are higher than 90%.
Embodiment 7
The process for purifying waste water of the invention also discloses a kind of biomembrane biochemistry reaction system based on ozone, such as Fig. 1 institute
Show:
The ozone and waste water for entering ozone reactor 2 simultaneously, in ozone reactor 2 under the action of catalyst, in waste water
Aromatic hydrocarbon organic matter difficult to degrade resolves into easily biodegradable organics by open loop and chain rupture；
Waste water after catalytic ozonation, containing easily biodegradable organics is discharged from ozone reactor 2, and send to richness
Oxygen aeration and biological me.mbrane bioreactor 5 carries out deep purifying processing, and the chemistry that deep purifying treated waste water reaches waste water needs
It is discharged after oxygen amount standard；
The complete ozone tail gas of unreacted enters ozonolysis reactions device 4 in ozone reactor 2, in ozonolysis reactions device
Ozone in ozone tail gas is resolved into harmless oxygen, then will be harmless after decomposition in 4 under the action of ozone decomposition catalyst
Oxygen mixes with air, and send to oxygen-enriched aeration biological me.mbrane bioreactor 5 and is aerated.
Specifically, the pressure in ozone reactor 2 is micro-positive pressure, -1~5KPa；Temperature in ozone reactor 2 is 20~
50℃；The concentration that adds of ozone is 5~60mg/L；The liquid hourly space velocity (LHSV) of reaction is 0.5~3h-1.
If the temperature in the present embodiment in ozone reactor 2 is excessively high, it is unfavorable for the dissolution of ozone in water, conversely, warm
Spend low, then reactivity is weaker.Ozone dosage is related to COD in waste water, and COD high, then ozone dosage is big, and COD is low, then
Ozone dosage is small.The liquid hourly space velocity (LHSV) of reaction is 0.5~3h-1, and air speed is too high, and conversion ratio is low, and air speed is too high, and cost of investment is big
And it is unobvious to promote effect to conversion ratio.The technical solution can make open loop chain rupture rate be higher than 80%, and wastewater biodegradability (B/C) is big
In 0.5.
The ozone and oxygen mixed gas that ozone concentration is 8~10%, the concentration within the scope of this occur in ozone generator 1
It can be improved and change the dissolution equilibrium of ozone in water, increase the concentration of ozone in water, and then improve the effect of ozone oxidation.
If ozone concentration is excessively high, not only energy consumption consumption is excessive, but also is limited by the limitation of ozone generator 1；Otherwise ozone concentration is too low,
Ozone oxidation effect can then be reduced.
Embodiment 8
As shown in Figure 1, the present embodiment, on the basis of embodiment 7, catalyst layer 25 uses metal load type to be catalyzed
Agent, including；
Catalyst activity component is transition-metal Fe, two or more the compounding in Ti, Mn, Ni, Cu, V, Co,
Or the two or more of above-mentioned metal oxide are compounded；
Auxiliary agent is the oxide of Ru, Zr；
Carrier is aluminium oxide or silica or active carbon.
It is a small amount of to be dissolved made of one or more of transition metal elements such as Ru, Zr introducing in the present embodiment
Modifying agent of the oxide body as catalyst carrier improves the probability that catalyst generates oxidation state metal direct oxidation organic matter.
Catalyst can not only be in catalyst surface catalysis oxidation decomposing organic matter, and it is higher certainly to pass through stimulating activity
By base, the oxidation operation being catalyzed indirectly in water phase by free radical is decomposed, to improve the catalytic efficiency of catalyst.
Embodiment 9
As shown in Figure 1, the present embodiment is on the basis of embodiment 7, in ozonolysis reactions device 4:
The air speed of reaction: 500~5000h-1, temperature: room temperature, pressure: micro-positive pressure, -1~5KPa.
Ozone is decomposed without pressurization and heating in the present embodiment, and low energy consumption.Ozone decomposition efficiency is greater than 99%.After decomposition,
Ozone content in tail gas is less than 0.1mg/L.
Embodiment 10
As shown in Figure 1, the present embodiment, on the basis of embodiment 7, ozone decomposition catalyst uses metal composite oxide,
That is two or more compound system of the oxide of Fe, Mn, Ti, Cu, Co, Mg, K；
The content range of reactive metal oxides component are as follows: manganese oxide: 10~40%, iron oxide: 20~60%.Oxidation
Magnesium: 0~3%, titanium oxide: 2~10%, cobalt oxide: 0~5%, potassium oxide: 0~2%.
Iron oxide, titanium oxide and manganese oxide are major catalyst in the present embodiment, remaining is catalyst promoter, are urged for improving
Degrading activity of the agent to ozone.
Embodiment 11
Present embodiment discloses actual use catalytic ozonation series connection fixed biofilm biochemical reactor device, such as Fig. 1
It is shown, the following processing carried out in the process and effect achieved:
Inlet wastewater: refinery(waste) water after two sections of biochemistry；COD 180mg/L, predominantly Hete rocyclic derivatives and condensed-nuclei aromatics, B/
C:0.1.
Ozone Oxidation Treatment: generating concentration first in ozone generator 1 is 8~10% ozone, then by the smelly of 40mg/L
Oxygen and waste water are sent into ozone reactor 2 together, and liquid hourly space velocity (LHSV) in ozone reactor 2 is arranged in 1.2h-1, PH:8 uses
Catalyst activity metal component is MnO240%, Fe2O340%, CuO 20%, carrier Al2O3, auxiliary agent RuO2, after reaction
The COD of waste water is 80mg/L, and B/C value is 0.62,1.28kw/ tons of water of energy consumption.
The processing of tail gas ozone layer destroying: the tail gas generated in ozone reactor 2 is first passed through the water removal of demister 3, then is passed through smelly
Oxygen decomposition reactor 4 carries out 99% inactivation at normal temperatures and pressures and the ozone tail gas after inactivation is passed through oxygen-enriched aeration biological life again
Change reactor as oxygen source, ton water consumption is 0.0004KWh.
The processing of biomembrane deep biochemical: the waste water after reaction is passed through oxygen-enriched aeration biological biochemical reactor and carries out oxygen-enriched exposure
(oxygen-enriched 25%) biochemical treatment, the condition in oxygen-enriched aeration biological biochemical reactor are dissolved oxygen in water 4.5mg/L, PH:8, warp to gas
COD value of waste water after crossing depth purified treatment is 18mg/L, ton water consumption 0.5KWh.
11 total energy consumption of embodiment: 1.7804KW/ tons, COD degradation efficiency: 90%, ozone utilization rate: greater than 90%.
Comparative example 1
Comparative example 1 is device used in conventional treatment sewage.
Inlet wastewater: petrochemical wastewater after two sections of biochemistry: COD 180mg/L, predominantly Hete rocyclic derivatives and condensed-nuclei aromatics, B/
C: less than 0.1.
Ozone Oxidation Treatment: sending the ozone of 40mg/L and waste water into ozone reactor 2 together, by ozone reactor 2
Interior liquid hourly space velocity (LHSV) is arranged in 1.2h-1, PH:8, the COD value of the waste water after reaction is 120mg/L, and B/C value is 0.48, energy consumption
1.6kw/ tons of water.
The processing of tail gas ozone layer destroying: reactor temperature is arranged 350 DEG C, pressure is micro-positive pressure (attached heat recovery dress
Set), tail gas ozone qualified discharge (ozone concentration < 0.1ppm) after 99% inactivation, ton water consumption is 0.002KWh.
The processing of biomembrane deep biochemical: the waste water after reaction is passed through and carries out biomembrane deep biochemical processing processing, air
Being aerated routine biochemistry condition is dissolved oxygen in water 3mg/L, PH:8, is 40mg/L, ton by deep purifying treated COD value of waste water
Water consumption 0.7KW.
The total energy consumption of comparative example 1: 2.302KW/ tons, COD degradation efficiency: 78%, ozone utilization rate: less than 30%.
By the comparison of embodiment 11 and comparative example 1 as it can be seen that the total energy consumption of embodiment 11 is significantly lower than comparative example 1, and degrades
More efficient, the utilization rate of ozone also dramatically increases.
Embodiment 12
Embodiment 12 is one embodiment of the present invention, as shown in Figure 1:
Inlet wastewater: refinery(waste) water after two sections of biochemistry；COD:180mg/L, predominantly Hete rocyclic derivatives and condensed-nuclei aromatics, B/
C:0.1.
Ozone Oxidation Treatment: generating concentration first in ozone generator 1 is 8~10% ozone, then by the smelly of 40mg/L
Oxygen and waste water are sent into ozone reactor 2 together, and liquid hourly space velocity (LHSV) in ozone reactor 2 is arranged in 0.8h-1, PH:8 uses
Catalyst activity metal component is MnO240%, Fe2O330%, NiO 20%, CuO10%, carrier Al2O3, auxiliary agent RuO2,
The COD of waste water after reaction is 82mg/L, and B/C value is 0.60,1.28kw/ tons of water of energy consumption.
The processing of tail gas ozone layer destroying: the tail gas generated in ozone reactor 2 is first passed through the water removal of demister 3, then is passed through smelly
Oxygen decomposition reactor 4 carries out 99% inactivation at normal temperatures and pressures and the ozone tail gas after inactivation is passed through oxygen-enriched aeration biological life again
Change reactor as oxygen source, ton water consumption is 0.0004KWh.
The processing of biomembrane deep biochemical: the waste water after reaction is passed through and carries out biomembrane deep biochemical processing processing, air
Being aerated routine biochemistry condition is dissolved oxygen in water 5mg/L, PH:8, is 16mg/L, ton by deep purifying treated COD value of waste water
Water consumption 0.5KWh.
The present embodiment total energy consumption: 1.7804KW/ tons, COD degradation efficiency: 91%, ozone utilization rate: greater than 90%.
Embodiment 13
Embodiment 13 is one embodiment of the present invention, as shown in Figure 1:
Inlet wastewater: oil refining wastewater after two sections of biochemistry；COD 120mg/L, predominantly heterocyclic compound and condensed-nuclei aromatics.B/
C:0.05.
Ozone Oxidation Treatment: generating concentration first in ozone generator 1 is 8~10% ozone, then by the smelly of 35mg/L
Oxygen and waste water are sent into ozone reactor 2 together, and liquid hourly space velocity (LHSV) in ozone reactor 2 is arranged in 0.8h-1, PH:7.5, use
Catalyst activity metal component be MnO240%, Fe2O340%, Co3O420%, carrier Al2O3, auxiliary agent RuO2, after reaction
Waste water COD be 67mg/L, B/C value be 0.59,1.12kw/ tons of water of energy consumption.
The processing of tail gas ozone layer destroying: the tail gas generated in ozone reactor 2 is first passed through the water removal of demister 3, then is passed through smelly
Oxygen decomposition reactor 4 carries out 99% inactivation at normal temperatures and pressures and the ozone tail gas after inactivation is passed through oxygen-enriched aeration biological life again
Change reactor as oxygen source, ton water consumption is 0.0004KWh.
The processing of biomembrane deep biochemical: the waste water after reaction is passed through oxygen-enriched aeration biological biochemical reactor and carries out oxygen-enriched exposure
Gas (oxygen-enriched 26%) biochemical treatment, the condition in oxygen-enriched aeration biological biochemical reactor are dissolved oxygen in water 5.5mg/L, PH:7.5,
It is 13mg/L, ton water consumption 0.48KWh by deep purifying treated COD value of waste water.
The present embodiment total energy consumption: 1.6004KW/ tons, COD degradation efficiency: 89%, ozone utilization rate: greater than 90%.
Embodiment 14
Embodiment 14 is one embodiment of the present invention, as shown in Figure 1:
Inlet wastewater: oil refining wastewater after two sections of biochemistry；COD 150mg/L, predominantly heterocyclic compound and condensed-nuclei aromatics, B/
C:0.05.
Ozone Oxidation Treatment: generating concentration first in ozone generator 1 is 8~10% ozone, then by the smelly of 50mg/L
Oxygen and waste water are sent into ozone reactor 2 together, and liquid hourly space velocity (LHSV) setting in ozone reactor 2 is used in 0.8h-1, PH:7.5
Catalyst activity metal component be MnO240%, Fe2O340%, carrier Al2O3, auxiliary agent RuO2, waste water after reaction
COD is 68mg/L, and B/C value is 0.58,1.6kw/ tons of water of energy consumption.
The processing of tail gas ozone layer destroying: the tail gas generated in ozone reactor 2 is first passed through the water removal of demister 3, then is passed through smelly
Oxygen decomposition reactor 4 carries out 99% inactivation at normal temperatures and pressures and the ozone tail gas after inactivation is passed through oxygen-enriched aeration biological life again
Change reactor as oxygen source, ton water consumption is 0.0004KWh.
The processing of biomembrane deep biochemical: the waste water after reaction is passed through oxygen-enriched aeration biological biochemical reactor and carries out oxygen-enriched exposure
(oxygen-enriched 27%) biochemical treatment, the condition in oxygen-enriched aeration biological biochemical reactor are dissolved oxygen in water 6mg/L, PH:7.5, warp to gas
COD value of waste water after crossing depth purified treatment is 15mg/L, ton water consumption 0.46KWh.
The present embodiment total energy consumption: 2.0604KW/ tons, COD degradation efficiency: 90%, ozone utilization rate: greater than 90%.
Embodiment 15
Embodiment 15 is one embodiment of the present invention, as shown in Figure 1:
Inlet wastewater: wastewater from chemical industry after two sections of biochemistry；COD 120mg/L, predominantly heterocyclic compound.B/C: less than 0.1.
Ozone Oxidation Treatment: generating concentration first in ozone generator 1 is 8~10% ozone, then by the smelly of 35mg/L
Oxygen and waste water are sent into ozone reactor 2 together, and liquid hourly space velocity (LHSV) setting in ozone reactor 2 is used in 0.8h-1, PH:7.5
Catalyst activity metal component be MnO240%, Fe2O340%, CuO 10%, TiO210%, carrier is active carbon, and auxiliary agent is
ZrO2, the COD of the waste water after reaction is 50mg/L, and B/C value is 0.70,1.12kw/ tons of water of energy consumption.
The processing of tail gas ozone layer destroying: the tail gas generated in ozone reactor 2 is first passed through the water removal of demister 3, then is passed through smelly
Oxygen decomposition reactor 4 carries out 99% inactivation at normal temperatures and pressures and the ozone tail gas after inactivation is passed through oxygen-enriched aeration biological life again
Change reactor as oxygen source, ton water consumption is 0.0004KWh.
The processing of biomembrane deep biochemical: the waste water after reaction is passed through oxygen-enriched aeration biological biochemical reactor and carries out oxygen-enriched exposure
(oxygen-enriched 26%) biochemical treatment, the condition in oxygen-enriched aeration biological biochemical reactor are dissolved oxygen in water 6mg/L, PH:7.5, warp to gas
COD value of waste water after crossing depth purified treatment is 8mg/L, ton water consumption 0.48KWh.
The present embodiment total energy consumption: 1.6004KW/ tons, COD degradation efficiency: 93%, ozone utilization rate: greater than 90%.
Embodiment 16
Embodiment 16 is one embodiment of the present invention, as shown in Figure 1:
Inlet wastewater: wastewater from chemical industry after two sections of biochemistry；COD 120mg/L, predominantly heterocyclic compound.B/C: less than 0.1.
Ozone Oxidation Treatment: generating concentration first in ozone generator 1 is 8~10% ozone, then by the smelly of 30mg/L
Oxygen and waste water are sent into ozone reactor 2 together, and liquid hourly space velocity (LHSV) setting in ozone reactor 2 is used in 0.8h-1, PH:8.5
Catalyst activity metal component be MnO240%, CuO 40%, V2O520%, carrier Al2O3, auxiliary agent ZrO2, after reaction
Waste water COD be 60mg/L, B/C value be 0.70,0.96kw/ tons of water of energy consumption.
The processing of tail gas ozone layer destroying: the tail gas generated in ozone reactor 2 is first passed through the water removal of demister 3, then is passed through smelly
Oxygen decomposition reactor 4 carries out 99% inactivation at normal temperatures and pressures and the ozone tail gas after inactivation is passed through oxygen-enriched aeration biological life again
Change reactor as oxygen source, ton water consumption is 0.0004KWh.
The processing of biomembrane deep biochemical: the waste water after reaction is passed through oxygen-enriched aeration biological biochemical reactor and carries out oxygen-enriched exposure
(oxygen-enriched 24%) biochemical treatment, the condition in oxygen-enriched aeration biological biochemical reactor are dissolved oxygen in water 4mg/L, PH:8.5, warp to gas
COD value of waste water after crossing depth purified treatment is 12mg/L, ton water consumption 0.5KWh.
The present embodiment total energy consumption: 1.4604KW/ tons, COD degradation efficiency: 90%, ozone utilization rate: greater than 90%.
Embodiment 17
Embodiment 17 is one embodiment of the present invention, as shown in Figure 1:
Inlet wastewater: wastewater from chemical industry after two sections of biochemistry；COD 150mg/L, predominantly heterocyclic compound, B/C: less than 0.1.
Ozone Oxidation Treatment: generating concentration first in ozone generator 1 is 8~10% ozone, then by the smelly of 40mg/L
Oxygen and waste water are sent into ozone reactor 2 together, and liquid hourly space velocity (LHSV) setting in ozone reactor 2 is used in 0.5h-1, PH:8.5
Catalyst activity metal component be MnO250%, Fe2O330%, V2O520%, carrier is silica, auxiliary agent ZrO2, instead
The COD of waste water after answering is 67mg/L, and B/C value is 0.69,1.28kw/ tons of water of energy consumption.
The processing of tail gas ozone layer destroying: the tail gas generated in ozone reactor 2 is first passed through the water removal of demister 3, then is passed through smelly
Oxygen decomposition reactor 4 carries out 99% inactivation at normal temperatures and pressures and the ozone tail gas after inactivation is passed through oxygen-enriched aeration biological life again
Change reactor as oxygen source, ton water consumption is 0.0004KWh.
The processing of biomembrane deep biochemical: the waste water after reaction is passed through oxygen-enriched aeration biological biochemical reactor and carries out oxygen-enriched exposure
(oxygen-enriched 26%) biochemical treatment, the condition in oxygen-enriched aeration biological biochemical reactor are dissolved oxygen in water 6mg/L, PH:8.5, warp to gas
COD value of waste water after crossing depth purified treatment is 13mg/L, ton water consumption 0.48KWh.
The present embodiment total energy consumption: 1.7604KW/ tons, COD degradation efficiency: 91%, ozone utilization rate: greater than 90%.
It should be noted that above-described embodiment can be freely combined as needed.The above is only preferred implementations of the invention
Mode, it is noted that for those skilled in the art, without departing from the principle of the present invention, also
Several improvements and modifications can be made, these modifications and embellishments should also be considered as the scope of protection of the present invention.
Claims (10)
1. a kind of biomembrane biochemistry reaction system based on ozone characterized by comprising
Ozone reactor, the ozone reactor is by carrying out purified treatment to waste water using ozone；
Oxygen-enriched aeration biological me.mbrane bioreactor, the oxygen-enriched aeration biological me.mbrane bioreactor and the ozone generator connect
Logical, the oxygen-enriched aeration biological me.mbrane bioreactor is used to carry out deep purifying processing to purified waste water and discharge；
Ozonolysis reactions device, the ozonolysis reactions device respectively with the ozone generator, the oxygen-enriched aeration biological film
Biochemical reactor connection, the ozonolysis reactions device after the ozone reactor for that will divide the complete ozone of unreacted
Solution is at oxygen.
2. a kind of biomembrane biochemistry reaction system based on ozone as described in claim 1, which is characterized in that the ozone is anti-
The device is answered to include:
Reactor shell, the reactor enclosure body is interior to be disposed with ozone distributor, inlet distribution device, water conservancy diversion from bottom upwards
Support ring, catalyst supporting plate, catalyst layer, catalyst pressing plate.
3. a kind of biomembrane biochemistry reaction system based on ozone as claimed in claim 2, it is characterised in that:
The water conservancy diversion support ring along the ozone reactor inner wall one enclose be arranged, water conservancy diversion support ring lower surface be inclined-plane and
It is in 120~160 ° of angles with the ozone reactor inner wall；
The catalyst supporting plate and the catalyst pressing plate are porous plate, and aperture size is 2~8mm, the loadings of catalyst
It is the 30~70% of the ozone reactor volume.
4. a kind of biomembrane biochemistry reaction system based on ozone as claimed in claim 3, it is characterised in that:
Gas distribution pipe, water distributor, biofilm packing are set gradually upwards from bottom in the oxygen-enriched aeration biological me.mbrane bioreactor
Layer；
Connection setting blowdown pipe at the air inlet of the gas distribution pipe.
The spacing of the gas distribution pipe and oxygen-enriched aeration biological me.mbrane bioreactor bottom is h1, the water distributor and the cloth
Tracheae is at a distance of h2, and the biofilm packing layer and oxygen-enriched aeration biological me.mbrane bioreactor bottom are at a distance of h3；Wherein h1:
H2:h3 is (3~10): (2~5): (6~15)；
The filler filling ratio of the biofilm packing layer is the 50% of pool capacity, in the oxygen-enriched aeration biological me.mbrane bioreactor
Oxygen-rich concentration in air is 23~28%.
5. a kind of biomembrane biochemistry reaction system based on ozone as claimed in claim 4, it is characterised in that:
The gas outlet of the ozone reactor is connected to the air inlet of demister, and the water outlet of the demister and the ozone are anti-
The water return outlet of device is answered to be connected to, the gas outlet of the demister is connected to the air inlet of the ozonolysis reactions device, the demisting
Device is for removing free water.
6. a kind of process for purifying waste water of the biomembrane biochemistry reaction system based on ozone, it is characterised in that:
The ozone and waste water for entering ozone reactor simultaneously, it is difficult in waste water in the ozone reactor under the action of catalyst
The aromatic hydrocarbon organic matter of degradation resolves into easily biodegradable organics by open loop and chain rupture；
Waste water after catalytic ozonation, containing easily biodegradable organics is discharged from the ozone reactor, and send to richness
Oxygen aeration and biological me.mbrane bioreactor carries out deep purifying processing, and deep purifying treated waste water reaches the chemical oxygen demand of waste water
It is discharged after amount standard；
The complete ozone tail gas of unreacted enters ozonolysis reactions device in the ozone reactor, in the ozonolysis reactions
Ozone in the ozone tail gas resolves into harmless oxygen, then nothing after decomposing in device under the action of ozone decomposition catalyst
Harmful oxygen mixes with air, and send to the oxygen-enriched aeration biological me.mbrane bioreactor and is aerated.
7. a kind of process for purifying waste water of the biomembrane biochemistry reaction system based on ozone as claimed in claim 6, feature
It is:
Pressure in the ozone reactor is -1~5KPa, and temperature is 20~50 DEG C；The concentration that adds of ozone is 5~60mg/
L；The liquid hourly space velocity (LHSV) of reaction is 0.5~3h-1；
The catalyst uses metal-supported catalyst.
8. a kind of process for purifying waste water of the biomembrane biochemistry reaction system based on ozone as claimed in claim 7, feature
It is；
The metal-supported catalyst active component be transition-metal Fe, two kinds or two kinds in Ti, Mn, Ni, Cu, V, Co with
On compounding or the two or more of above-mentioned metal oxide compounded；
Auxiliary agent is the oxide of Ru, Zr；
Carrier is aluminium oxide or silica or active carbon.
9. a kind of process for purifying waste water of the biomembrane biochemistry reaction system based on ozone as claimed in claim 6, feature
It is:
The air speed reacted in the ozonolysis reactions device: 500~5000h-1, temperature: room temperature, pressure: -1~5KPa.
10. a kind of process for purifying waste water of the biomembrane biochemistry reaction system based on ozone as claimed in claim 6, feature
It is:
The ozone decomposition catalyst use metal composite oxide, i.e., two kinds of the oxide of Fe, Mn, Ti, Cu, Co, Mg, K or
Two or more compound systems；
Reactive metal oxides are as follows: manganese oxide: 10~40%, iron oxide: 20~60%, magnesia: 0~3%, titanium oxide: 2~
10%, cobalt oxide: 0~5%, potassium oxide: 0~2%.
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| CN201921624202.8U Active CN211111579U (en) | 2019-03-30 | 2019-09-27 | Biomembrane biochemical reaction system based on ozone |
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| CN111533319A (en) * | 2020-05-20 | 2020-08-14 | 北方工业大学 | Device and method for treating COD (chemical oxygen demand) in desulfurization wastewater by ozone oxidation method |
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| CN109824215A (en) * | 2019-03-30 | 2019-05-31 | 上海蓝科石化环保科技股份有限公司 | A kind of biomembrane biochemistry reaction system and process for purifying waste water based on ozone |
| CN110639346A (en) * | 2019-11-05 | 2020-01-03 | 张智军 | Gas treatment device |
| CN116903149A (en) * | 2023-06-09 | 2023-10-20 | 德威华泰科技股份有限公司 | Method for treating biochemical tail water by using biochemical and ozone oxidation coupling reactor device |
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| CN109824215A (en) | 2019-05-31 |
| CN211111579U (en) | 2020-07-28 |
| CN110526527B (en) | 2024-09-06 |
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