CN110523223A - A kind of advanced oxidization method of the organic compounds containing bio-refractory - Google Patents
A kind of advanced oxidization method of the organic compounds containing bio-refractory Download PDFInfo
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Abstract
A kind of advanced oxidization method of the organic compounds containing bio-refractory, is related to the advanced oxidization method of bio-refractory organic matter.The multi-stage countercurrent of the organic compounds containing bio-refractory absorbs；Ultraviolet light catalyzing reaction unit, internally provided with vacuum ultraviolet lamp are set between the last one absorption plant and penultimate absorption plant；It will enter in the biological oxidation apparatus added with denitrifying bacterium by the liquid pump that partially absorbs in first absorption plant, while addition contains nitrate or dilute nitric acid solution into biological oxidation apparatus；Or it will enter in the biological oxidation apparatus added with denitrifying bacterium by the liquid pump that partially absorbs in first absorption plant, while Containing Sulfate Reducing Bacteria and sulfate liquor are added into biological oxidation apparatus；The water outlet of biological oxidation apparatus is introduced into the absorbing liquid of first absorption plant；The air tube that biological oxidation apparatus generates is introduced into the air inlet of ultraviolet light catalyzing reaction unit.
Description
Technical field
The present invention relates to the advanced oxidization methods of bio-refractory organic matter, contain bio-refractory particularly with regard to one kind
The advanced oxidization method of organic compounds.
Background technique
Volatile organic matter is O in atmosphere3It is the key points and difficulties of air contaminant treatment with the important as precursors object of PM2.5.
A large amount of volatile organic matters are assembled in air is also easy to cause Urban Rain first rain COD concentration height in the process, with nitrogen and phosphorus one
Act the important pollution sources for becoming the environment such as river, lake, soil.
Bio-refractory organic matter such as aromatic hydrocarbon, polycyclic aromatic hydrocarbon, aliphatic hydrocarbon, persistence organic pollutant etc. enter soil or
After water body, due to bio-refractory, it is long to influence the period, influences difficult elimination, treatment cost is high.
The optimal administering method containing volatile organic compounds is exactly combustion method, regardless of organic matter, as long as warm
It spends sufficiently high, carbon dioxide and water can be completely decomposed into, combustion method has directly burning or catalysis burning or adsorption/desorption after-burning
Technologies or the technical combinations such as burning.Often concentration is lower for general organic compounds containing bio-refractory, higher cost of burning.
Biological treatment is the effective ways that most organic matter can be directly converted into water and carbon dioxide except combustion method.It is right
It is preferable in water-soluble easily biological-degradable organic matter effect, and the biological treatment of bio-refractory organic matter there are many technologies and at
This difficult point.In soil pollution and the reparation of underground water pollution, bio-refractory organic matter be also it is equally extremely difficult, given birth to
Object hardly degraded organic substance polluted drinking water is easy to cause health problem, and organic matter containing bio-refractory also causes to administer and set in waste water
It is abnormal to apply operation.
Often effect is poor using biological treatment for organic compounds containing bio-refractory, and Aerobic Process for Treatment causes organic matter with exposure
Gas is again introduced into atmosphere, and Anaerobic Treatment often can not decompose because microbial activity is suppressed or reenter atmosphere with gas is produced.
Why difficult bio-refractory organic matter is is utilized by microorganism, is that substance water solubility is poor, and has bio-toxicity, uses
For extraordinary strain often because of surrounding material diversity, the dominant microflora period for cultivating special bacteria is longer more difficult.
Using biological treatment organic compounds containing bio-refractory, if the waste water or percolate that generate are without further locating
Reason, is directly discharged into city sewer, can be again introduced into atmosphere in the duct, or even jeopardize pipe safety, and uncontrolled contains
Volatile organic matter can also be again introduced into atmosphere in the aerobic aeration environment of sewage plant；It is polluted if being directly discharged into external environment
Surface water, underground water or soil.
Organic matter containing bio-refractory generally uses high-level oxidation technology in drinking water, waste water, such as Fenton oxidation, ozone oxygen
The one or several kinds technical combinations such as change, ferrate oxidation.Organic matter containing bio-refractory such as dioxin etc. is using work in exhaust gas
Property charcoal absorption.Organic matter containing bio-refractory often uses gas phase extracting, thermal desorption, solidification stabilization, chemical leaching, spy in soil
The methods of kind bacterium or technical combinations.
Often concentration is lower for organic compounds containing bio-refractory, and air quantity is larger, and land occupation low using biological treatment efficiency
Area is big, and often investment and O&M cost are high for burning.Become using the high-level oxidation technologies such as low-temperature plasma and UV photodissociation technology
Popular selection but there are removal efficiency, lower energy consumption is high and is also easy to produce secondary pollution problems.UV photodissociation-biological treatment
Technical combinations are generated and are widely applied therewith.
Chinese patent CN105498478B is effectively combined gas phase photolysis with liquid phase photochemical catalytic oxidation, by adding in the liquid phase
Enter catalyst, so that volatile organic matter enters in liquid phase after photodissociation and the reaction such as catalysis oxidation, ozone oxidation occurs, finally
Realize the degradation of organic exhaust gas efficient stable.Chinese patent CN207614645U combines ultraviolet advanced oxidation and hydrogen peroxide technology to control
Manage organic exhaust gas.Chinese patent CN109268851A combines catalytic combustion technology using ultraviolet photolysis, with the electrodeless purple of microwave-driven
Outer light source, and the heat source as catalysis burning have degradation efficiency high.Chinese patent CN109351187A bears fenton catalyst
It is loaded in nano carbon microsphere mass transfer particle surface, nanoparticle accelerates mass transfer rate of the gaseous pollutant to Fenton reagent, nanoparticle
The catalyst on surface accelerates the degradation of pollutant in Fenton reagent, forms the coupling effect of particle reinforced mass transfer and catalysis reaction,
Improve the efficiency of Fenton's reaction degradation gaseous volatile organic matter.
The advantages of organic constituents are more in organic exhaust gas, can play various technologies using technical combinations inhibits respective
Disadvantage can effectively promote the removal rate of organic exhaust gas and reduce investment O&M cost.Traditional active carbon (or zeolite) absorption
Desorption-catalysis burning combination technique solves the problems, such as large-wind-volume low-concentration, and emerging ultraviolet light-active carbon adsorption is able to solve secondary
Pollution problem.The present invention is based on ultraviolet photolysis technologies and biological oxidation technical combinations, organic with ultraviolet degradation bio-refractory
Object handles easily biological-degradable organic matter with biological oxidation, and condition license can also degrade the total nitrogen of the waste water containing nitrate nitrogen simultaneously.
Summary of the invention
It is an object of the invention to play the advantage of different high-level oxidation technologies, high-level oxidation technology is combined to mention
The efficiency for rising oxidation technology, for handling organic compounds containing bio-refractory, investment cost is relatively fewer, operation and maintenance are simple
It is single, a kind of advanced oxidization method of the relatively high organic compounds containing bio-refractory for the treatment of effeciency.
The present invention the following steps are included:
1) multi-stage countercurrent of the organic compounds containing bio-refractory absorbs；
In step 1), exhaust gas or soil, water that the organic compounds containing bio-refractory can generate for technical process
The exhaust gas that the extracting of the gas phases such as body generates；The hardly degraded organic substance of the organic compounds containing bio-refractory can be aromatic hydrocarbon, more
Cycloaromatics, aliphatic hydrocarbon, persistence organic pollutant etc.；The tool that the multi-stage countercurrent of the organic compounds containing bio-refractory absorbs
Body method can are as follows:
Open the water circulating pump and blower in exhaust gas absorption device；Absorbing liquid starts as water, in the last one absorption plant
Middle supplement, and successively adverse current finally enters first absorption dress to a absorption plant last, penultimate absorption plant
In setting；Organic compounds containing bio-refractory are after multiple absorption plants, containing organic in the absorbing liquid of first absorption plant
Object concentration highest, and mostly water soluble organic substance, the last one absorption plant are minimum containing organic concentration；Absorption plant can set 2
~5；The pH of absorbing liquid maintains 6~9.
2) ultraviolet light catalyzing reaction unit is set between the last one absorption plant and penultimate absorption plant,
Internally provided with vacuum ultraviolet lamp；
For organic compounds containing bio-refractory after the absorbing liquid of penultimate absorption plant absorbs, exhaust gas is mainly difficult
It is dissolved in the organic matter of water, exhaust gas enters the last one absorption plant after ultraviolet light catalyzing reaction unit, and arranges through exhaust tube
Enter atmosphere.
3) life added with denitrifying bacterium will be entered by the liquid pump that partially absorbs in first absorption plant in step 1)
In object oxidation unit, while addition contains nitrate or dilute nitric acid solution into biological oxidation apparatus；Or
The biology added with denitrifying bacterium will be entered by the liquid pump that partially absorbs in first absorption plant in step 1)
In oxidation unit, while Containing Sulfate Reducing Bacteria and sulfate liquor are added into biological oxidation apparatus；
In step 3), the hydraulic detention time of the biological oxidation apparatus is 6~36h；The nitrate, which can be used, to be come
Derived from containing nitrate wastewater.
4) water outlet of the biological oxidation apparatus in step 3) is introduced into the absorbing liquid of first absorption plant；
In step 4), the water outlet of the biological oxidation apparatus by step 3) is introduced into the suction of first absorption plant
The specific method received in liquid can are as follows: after biological oxidation apparatus, oxidation operation is absorbing liquid by denitrifying bacterium using nitrate
Carbon dioxide and water, nitrate are reduced to nitrogen by organic matter；The concentration of organic matter in the solution reduces, and is recycled to first suction
Continue to use as absorbing liquid in receiving apparatus.
5) air tube that biological oxidation apparatus generates is introduced into the air inlet of ultraviolet light catalyzing reaction unit.
In step 5), the air tube that the biological oxidation apparatus generates is introduced into ultraviolet light catalyzing reaction unit
Air inlet in specific method can are as follows: in the production gas of biological oxidation apparatus contain part biological hardly degraded organic substance, together into
Enter ultraviolet light catalyzing reaction unit further to aoxidize, and returns to first step by step after the water in the last one absorption plant absorbs
In a absorption plant.
The present invention is suitable for the improvement of the organic exhaust gas containing bio-refractory, in conjunction with ultraviolet catalytic oxidation and microbiological oxidation
Technology, by the direct microbiological oxidation of water soluble organic substance, not soluble in water and bio-refractory organic matter passes through ultraviolet catalytic
It is converted into water soluble organic substance after oxidation and biology is degradable.After being absorbed due to water soluble organic substance, organic matter is dense in exhaust gas
Degree is mostly difficult water soluble organic substance, into ultraviolet light catalyzing device after be able to ascend oxidation efficiency, exhaust gas is again through the last one
Absorption plant can absorb the water soluble organic substance and secondary pollution generated in ultraviolet light catalyzing reaction unit, after absorption,
Absorbing liquid adverse current enters penultimate absorption plant, promotes waste gas absorption efficiency.Water soluble organic substance is due to biological oxidation
Device oxidation concentration reduction can continue to serve as absorbing liquid.
Detailed description of the invention
Fig. 1 is the process flow diagram of the embodiment of the present invention.
Specific embodiment
Following embodiment will the present invention is further illustrated in conjunction with attached drawing.
Referring to Fig. 1, the embodiment of the present invention includes following steps:
1) multi-stage countercurrent of the organic compounds containing bio-refractory absorbs, method particularly includes:
Open the water circulating pump and blower in exhaust gas absorption device；Absorbing liquid starts as water, in the last one absorption plant
Middle supplement, and successively adverse current finally enters first absorption dress to a absorption plant last, penultimate absorption plant
In setting；Organic compounds containing bio-refractory are after multiple absorption plants, containing organic in the absorbing liquid of first absorption plant
Object concentration highest, and mostly water soluble organic substance, the last one absorption plant are minimum containing organic concentration；Absorption plant sets 2~5
It is a；The pH of absorbing liquid maintains 6~9.
The organic compounds containing bio-refractory can be the gas phases extracting such as the exhaust gas of technical process generation or soil, water body
The exhaust gas of generation；The hardly degraded organic substance of the organic compounds containing bio-refractory can be aromatic hydrocarbon, polycyclic aromatic hydrocarbon, fat
Hydrocarbon, persistence organic pollutant etc.；
2) ultraviolet light catalyzing reaction unit is set between the last one absorption plant and penultimate absorption plant,
Internally provided with vacuum ultraviolet lamp:
For organic compounds containing bio-refractory after the absorbing liquid of penultimate absorption plant absorbs, exhaust gas is mainly difficult
It is dissolved in the organic matter of water, exhaust gas enters the last one absorption plant after ultraviolet light catalyzing reaction unit, and arranges through exhaust tube
Enter atmosphere.
3) life added with denitrifying bacterium will be entered by the liquid pump that partially absorbs in first absorption plant in step 1)
In object oxidation unit, while addition contains nitrate or dilute nitric acid solution into biological oxidation apparatus；Or
The biology added with denitrifying bacterium will be entered by the liquid pump that partially absorbs in first absorption plant in step 1)
In oxidation unit, while Containing Sulfate Reducing Bacteria and sulfate liquor are added into biological oxidation apparatus
The hydraulic detention time of the biological oxidation apparatus is 6~36h；The nitrate can be used from containing nitrate
Waste water；
4) water outlet of the biological oxidation apparatus in step 3) is introduced into the absorbing liquid of first absorption plant, specific side
Method are as follows: for absorbing liquid after biological oxidation apparatus, oxidation operation is carbon dioxide and water, nitric acid using nitrate by denitrifying bacterium
Salt is reduced to nitrogen by organic matter；The concentration of organic matter in the solution reduces, and is recycled in first absorption plant and continues conduct
Absorbing liquid uses.
5) air tube that biological oxidation apparatus generates is introduced into the air inlet of ultraviolet light catalyzing reaction unit, is had
Body method can are as follows: contains part biological hardly degraded organic substance in the production gas of biological oxidation apparatus, enters ultraviolet light catalyzing together
The further catalysis oxidation of reaction unit, and first absorption plant is returned step by step after the water in the last one absorption plant absorbs
In.
Specific embodiment is given below.
Embodiment 1
Certain organic exhaust gas main component is Tianna solution, containing organic matters such as acetate butyl, dimethylbenzene.Organic exhaust gas is through first
Absorption plant (cascade) absorbs, and using ultraviolet light catalyzing reaction unit, then passes through second absorption plant (spray column)
High altitude discharge after absorption.
First absorption plant and second absorption plant are absorbed with water, and water is supplemented from second absorption plant, adverse current
Into in first absorption plant.
Absorbing liquid in first absorption plant is introduced into biological oxidation apparatus, adds sodium nitrate solution.Biological oxidation dress
It sets and is inoculated with denitrifying bacterium.
The water outlet overflow of biological oxidation apparatus is into first absorption plant.
The air tube that biological oxidation apparatus generates is introduced into the admission line of ultraviolet light catalyzing reaction unit.
Embodiment 2
Certain organic exhaust gas main component is toluene, dimethylbenzene, ethylbenzene etc..Machine exhaust gas is inhaled through first absorption plant (cascade)
It receives, using ultraviolet light catalyzing reaction unit, the then high altitude discharge after the absorption of second absorption plant (spray column).
First absorption plant and second absorption plant are absorbed with water, and water is supplemented from second absorption plant, adverse current
Into in first absorption plant.
Absorbing liquid in first absorption plant is introduced into biological oxidation apparatus, adds sodium nitrate solution.Biological oxidation dress
It sets and is inoculated with denitrifying bacterium.
The water outlet overflow of biological oxidation apparatus is into first absorption plant.
The air tube that biological oxidation apparatus generates is introduced into the admission line of ultraviolet light catalyzing reaction unit.
Embodiment 3
Certain organic exhaust gas main component is acetone, ethyl alcohol, dimethylbenzene etc..Machine exhaust gas is inhaled through first absorption plant (cascade)
It receives, using ultraviolet light catalyzing reaction unit, the then high altitude discharge after the absorption of second absorption plant (spray column).
First absorption plant and second absorption plant are absorbed with water, and water is supplemented from second absorption plant, adverse current
Into in first absorption plant.
Absorbing liquid in first absorption plant is introduced into biological oxidation apparatus, adds metabisulfite solution.Biological oxidation dress
It sets and is inoculated with anti-sulfate reducing bacteria.
The water outlet overflow of biological oxidation apparatus is into first absorption plant.
The air tube that biological oxidation apparatus generates is introduced into the admission line of ultraviolet light catalyzing reaction unit.
Claims (9)
1. a kind of advanced oxidization method of organic compounds containing bio-refractory, it is characterised in that the following steps are included:
1) multi-stage countercurrent of the organic compounds containing bio-refractory absorbs；
2) ultraviolet light catalyzing reaction unit is set between the last one absorption plant and penultimate absorption plant, it is built-in
Vacuum UV lamp；
3) the biological oxygen added with denitrifying bacterium will be entered by the liquid pump that partially absorbs in first absorption plant in step 1)
During makeup is set, while addition contains nitrate or dilute nitric acid solution into biological oxidation apparatus；Or
The biological oxidation added with denitrifying bacterium will be entered by the liquid pump that partially absorbs in first absorption plant in step 1)
In device, while Containing Sulfate Reducing Bacteria and sulfate liquor are added into biological oxidation apparatus；
4) water outlet of the biological oxidation apparatus in step 3) is introduced into the absorbing liquid of first absorption plant；
5) air tube that biological oxidation apparatus generates is introduced into the air inlet of ultraviolet light catalyzing reaction unit.
2. a kind of advanced oxidization method of the organic compounds containing bio-refractory as described in claim 1, it is characterised in that in step
It is rapid 1) in, the organic compounds containing bio-refractory be technical process generate exhaust gas or soil, water body gas phase extracting generate
Exhaust gas.
3. a kind of advanced oxidization method of the organic compounds containing bio-refractory as described in claim 1, it is characterised in that in step
It is rapid 1) in, the hardly degraded organic substances of the organic compounds containing bio-refractory is aromatic hydrocarbon, polycyclic aromatic hydrocarbon, aliphatic hydrocarbon, persistently
Property organic pollutant.
4. a kind of advanced oxidization method of the organic compounds containing bio-refractory as described in claim 1, it is characterised in that in step
It is rapid 1) in, what the multi-stage countercurrents of the organic compounds containing bio-refractory absorbed method particularly includes:
Open the water circulating pump and blower in exhaust gas absorption device；Absorbing liquid starts to be mended in the last one absorption plant for water
It fills, and successively adverse current finally enters first absorption plant to a absorption plant last, penultimate absorption plant
In；Organic compounds containing bio-refractory contain organic matter after multiple absorption plants in the absorbing liquid of first absorption plant
Concentration highest, and mostly water soluble organic substance, the last one absorption plant are minimum containing organic concentration；Absorption plant sets 2~5
A, the pH of absorbing liquid maintains 6~9.
5. a kind of advanced oxidization method of the organic compounds containing bio-refractory as described in claim 1, it is characterised in that in step
It is rapid 2) in, it is described between the last one absorption plant and penultimate absorption plant be arranged ultraviolet light catalyzing react dress
It sets, internally provided with vacuum ultraviolet lamp method particularly includes: suction of the organic compounds containing bio-refractory through penultimate absorption plant
After receiving liquid absorption, exhaust gas is mainly the organic matter for being insoluble in water, and exhaust gas enters last after ultraviolet light catalyzing reaction unit
A absorption plant, and atmosphere is discharged into through exhaust tube.
6. a kind of advanced oxidization method of the organic compounds containing bio-refractory as described in claim 1, it is characterised in that in step
It is rapid 3) in, the hydraulic detention time of the biological oxidation apparatus is 6~36h.
7. a kind of advanced oxidization method of the organic compounds containing bio-refractory as described in claim 1, it is characterised in that in step
It is rapid 3) in, the nitrate derive from contain nitrate wastewater.
8. a kind of advanced oxidization method of the organic compounds containing bio-refractory as described in claim 1, it is characterised in that in step
It is rapid 4) in, the water outlet of the biological oxidation apparatus by step 3) is introduced into specific in the absorbing liquid of first absorption plant
Method are as follows: for absorbing liquid after biological oxidation apparatus, oxidation operation is carbon dioxide and water, nitre using nitrate by denitrifying bacterium
Hydrochlorate is reduced to nitrogen by organic matter；The concentration of organic matter in the solution reduces, and is recycled in first absorption plant and continues to make
For absorbing liquid use.
9. a kind of advanced oxidization method of the organic compounds containing bio-refractory as described in claim 1, it is characterised in that in step
It is rapid 5) in, the air tube that the biological oxidation apparatus generates is introduced into the air inlet of ultraviolet light catalyzing reaction unit
Method particularly includes: contain part biological hardly degraded organic substance in the production gas of biological oxidation apparatus, enters ultraviolet light catalyzing together
The further catalysis oxidation of reaction unit, and first absorption plant is returned step by step after the water in the last one absorption plant absorbs
In.
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| CN111744361A (en) * | 2020-07-08 | 2020-10-09 | 大连理工大学 | Device for advanced treatment of pyridine waste gas |
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| CN208449008U (en) * | 2018-03-19 | 2019-02-01 | 广州点蓝环保设备有限公司 | A kind of combined type organic waste-gas purification and recyclable device |
| CN108554172A (en) * | 2018-06-14 | 2018-09-21 | 杭州电子科技大学 | Dimethylamine exhaust gas controlling device and its technique in a kind of synthetic leather industry |
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| CN111744361A (en) * | 2020-07-08 | 2020-10-09 | 大连理工大学 | Device for advanced treatment of pyridine waste gas |
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