CN103435206A - Organic wastewater ozonation and ionizing radiation synergetic treatment method and treatment system - Google Patents
Organic wastewater ozonation and ionizing radiation synergetic treatment method and treatment system Download PDFInfo
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- CN103435206A CN103435206A CN2013103554226A CN201310355422A CN103435206A CN 103435206 A CN103435206 A CN 103435206A CN 2013103554226 A CN2013103554226 A CN 2013103554226A CN 201310355422 A CN201310355422 A CN 201310355422A CN 103435206 A CN103435206 A CN 103435206A
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Abstract
The invention relates to an organic wastewater ozonation and ionizing radiation synergetic treatment method which comprises conducting ozone aeration on the organic wastewater in an aeration tank, removing the ozone in the organic wastewater subjected to ozone aeration to get pre-treatment water, and conducting ionizing radiation treatment on the pre-treatment water. The invention further relates to an organic wastewater synergetic treatment system which comprises an ionizing radiation device, the aeration tank and an ozone consumption tank, and the ozone in the organic wastewater can be removed in the ozone consumption tank.
Description
Technical field
The invention belongs to environmental protection technical field, be specifically related to Synergistic method and treatment system that organic waste water is processed in a kind of ozone oxidation and ionizing rays.
Background technology
High-level oxidation technology (AOP) is an emerging in recent years class water technology, due to the generation of hydroxyl radical free radical, makes it have the advantages such as speed of response is fast, contaminant degradation is thorough.Be the common weakness of high-level oxidation technology but running cost is high, less economical, hindered its large-scale application.Therefore, large quantity research concentrates on high-level oxidation technology and traditional cheap water technology coupling, and the seeking of relative " synergistic effect ".
Ionizing Radiation belongs to the category of advanced oxidation, except having the advantages such as speed of response is fast, contaminant degradation is thorough, also without adding chemical reagent, has environment friendly.Yet, for the processing problem of a large amount of trade effluents, use separately Ionizing Radiation to have the problems such as required radiation quantity is large, energy consumption is high, be difficult to be applied to Industrial Wastewater Treatment.The ozone Oxidation Treatment technology is a kind of comparatively commonly used and relatively inexpensive wastewater processing technology.Advantage is to be swift in response, and technique is simple, there is no the secondary pollution problem.Yet, for organic wastewater with difficult degradation thereby, by the ozone individual curing, still be difficult to take effect.
At present, at O
3carry out ionizing rays under the condition existed, to " synergistic effect " of organic matter removal in water studied confirmation the (as Chinese patent application CN 101362619A).Yet the electron beam that the common applying electronic accelerator of actual ionizing rays engineering of water treatment produces carries out the irradiation water treatment.Rumbatron is very expensive, and the lower irradiator of its bundle should be avoided and O as far as possible
3deng corrosives, contact.Even additionally do not adding O
3situation under, when common ionizing rays is processed, still take the O produced as by product in the ionizing rays process
3extract the measure of processing out Deng gas.Visible, will additionally add O
3waste water carry out ionizing rays at radiation chamber, make O
3the mode of simultaneously waste water being processed with ionizing rays runs counter to reality.Therefore, how ozonation technology and ionizing rays are better remained further to be studied in conjunction with processing waste water.
Summary of the invention
In view of this, necessary provide a kind of can practical application by Synergistic method and the treatment system of the processing organic waste water of ionizing rays and the effective combination of ozone oxidation.
The Synergistic method of organic waste water is processed in a kind of ozone oxidation and ionizing rays, comprising: by organic waste water, in aeration tank, carry out ozonation aerated; Ozone in organic waste water after ozonation aerated is removed, obtained a pretreated water; And this pretreated water is carried out to the ionizing rays processing.
A kind of organic waste water coprocessing system, comprise ionizing rays device, aeration tank and ozone-depleting pond, and the ozone in this organic waste water is removed in this ozone-depleting pond.
Beneficial effect of the present invention is: by organic waste water is first passed through to ozone Oxidation Treatment, and the ozone in the organic waste water after making to process is removed, pass through again the ionizing rays radiotreatment, can realize selective destruction and/or the removal of Pre-Ozonation on Organic Matter matter or intermediate product, avoid containing the loss of equipment etc. under halved tie in radiation chamber of ozone waste water.Organic waste water is after the selectivity of ozone is processed, through the ionizing rays of non-selectivity, process again, on removal effect to organic pollutants, exist " synergistic effect ", make ionizing rays process required radiation dose less, reduce the radiation energy consumption, be applicable to being applied to the ionizing rays Industrial Wastewater Treatment.
The accompanying drawing explanation
Fig. 1 is the process schematic diagram that in the present invention, organic waste water is processed in a kind of ozone oxidation and ionizing rays.
Fig. 2 is to the treatment effect comparison diagram containing PVA waste water in embodiment 1.
Fig. 3 is to the treatment effect comparison diagram containing azoic dyestuff sodium p-nitrobenzene-azo-salicylate-GG waste water in embodiment 2.
The main element nomenclature
| The organic waste |
100 |
| Electron |
10 |
| Rumbatron | 12 |
| The lower power system of |
14 |
| |
16 |
| |
20 |
| The ozone-depleting |
30 |
| The |
40 |
| The waste water e Foerderanlage | 50 |
Following embodiment further illustrates the present invention in connection with above-mentioned accompanying drawing.
Embodiment
Below in conjunction with the accompanying drawings and the specific embodiments the Synergistic method of a kind of ozone oxidation provided by the invention and ionizing rays processing organic waste water is described in further detail.
Refer to Fig. 1, the invention provides the Synergistic method that organic waste water is processed in a kind of ozone oxidation and ionizing rays, it comprises the following steps:
S1 carries out ozonation aerated by organic waste water in aeration tank;
S2, remove the ozone in the organic waste water after ozonation aerated, obtains a pretreated water; And
S3, carry out the ionizing rays processing by this pretreated water.
The method is ozone oxidation-ionizing rays associated treatment organic waste water, namely organic waste water is first passed through to ozone Oxidation Treatment, treats that ozone exhausts, then processes by ionizing rays.This waste water is preferably the pbz polymer polymkeric substance or has the waste water of the organic hardly degraded organic substance of two keys and/or phenyl ring.
Particularly, in step S1, ozone can be passed into to this organic waste water, ozone can be provided by ozonizer, when in step S3, the ionizing rays process adopts rumbatron as irradiation source, the ozone in S1 also can be provided by the discarded ozone of the radiation chamber 16 interior extractions of ionizing rays device.Aeration tank and aerating system all adopt the material of anti-ozone oxidation preparation, and airtight.The ozone amount passed into and aeration time all can determine according to kind and the concentration of organic waste water.
In step S2, this organic waste water can carry out standing and reacting, treats that ozone exhausts voluntarily, can obtain pretreated water.Time of repose can be 6 hours to 24 hours.This organic waste water can be standing in aeration tank, also can pass in special-purpose ozone-depleting pond, carry out standing, thereby ozone in organic waste water is removed.This ozone-depleting pond adopts the material of anti-ozone oxidation preparation, is preferably closed structure.For raising the efficiency, also can, by bleeding or shortening the modes such as organic waste water hydraulic detention time (HRT), the ozone in organic waste water be removed.
In step S3, this pretreated water can pass into a radiation chamber, in this radiation chamber, accepts ionizing rays, last water outlet.This ionizing rays can be gamma Rays, electron beam irradiation or X-radiation.Wherein, gamma-rays can obtain by the gamma Rays device, be specially by
60co or
137the Cs radionuclide decay produces; When adopting gamma-rays to carry out radiation, the gamma-rays dose rate of this radiation zone can adopt ferrous sulfate dosimeter (Fricke quantimeter) to demarcate and monitoring.
Electron beam and X ray can obtain by rumbatron radiation devices 10.Rumbatron radiation devices 10 generally includes rumbatron 12, the lower power system 14 of bundle and Controlling System (not shown).Rumbatron 12 is for generation of electronics and make electronics accelerate and draw, form an electron beam irradiation district, the lower power system 14 of bundle is for pretreated water being transmitted to this electron beam irradiation district of process to accept electron beam irradiation, and Controlling System is for controlling lower power system 14 collaborative works of this rumbatron 12 and bundle.
When adopting electron beam to carry out radiation, can be further comprising the steps: by this pretreated water, with the continuous fluid form, the electron beam irradiation district by rumbatron 12 carries out electron beam irradiation.Pretreated water can descend the continuous electron beam irradiation district that passes through this rumbatron of power system 14 by bundle.Particularly, pretreated water passes through the electron beam irradiation district of this rumbatron 12 with the form of moisture film, basic vertical this water film surface of the radiation direction of this electron beam.Preferably, the water film thickness by the electron beam irradiation district is no more than the penetration range of electron beam in water.The doses of electron beam radiation rate of this radiation zone can adopt film dosage sheet (B3, GEX) to demarcate and monitoring.
Further, in this radiation chamber, can there is air, and the oxygen of electron beam irradiation also irradiate ambient air when irradiating pretreated water in, thereby ozone formed.The ozone that therefore, can further will produce at radiation chamber by an air extractor is from the interior extraction of radiation chamber 16.In addition, can be further by the ozone delivery device by the Ozone transfer extracted out to aeration tank, pass into organic waste water, reach the recycling of ozone.
The present invention further provides a kind of organic waste water coprocessing system 100, it comprises ionizing rays device (as rumbatron radiation devices 10), aeration tank 20 and ozone-depleting pond 30, between this aeration tank 20 and this ozone-depleting pond 30, and all by waste water e Foerderanlage 50, be connected between this ozone-depleting pond 30 and this ionizing rays device.This waste water e Foerderanlage 50 can comprise pipeline and water pump, makes organic waste water flow into this ozone-depleting pond 30 from this aeration tank 20, and flows into this ionizing rays device from this ozone-depleting pond 30.This organic waste water coprocessing system can further comprise ozone delivery device 40, and this ozone delivery device 40 will be delivered to this aeration tank 20 from the ozone of the radiation chamber 16 interior extractions of ionizing rays device.This ozone delivery device 40 can comprise air extractor (as vacuum fan) and gas pipe line.
Embodiment 1
Processing object in the present embodiment, for the organic waste water containing polyvinyl alcohol (PVA) 300 mg/L, belongs to organic wastewater with difficult degradation thereby, and total organic carbon (TOC) value is 185 mg/L.The TOC value adopts TOC analyser (TOC-V
cPH, Shimadzu) measure.Should be 1700 ± 200 containing the polymerization degree of PVA in PVA waste water, molecular weight be 66000 ~ 84600.The initial pH value of waste water adopts desk-top pH instrument to measure (FiveEasy, Mettler Toledo), and is regulated with sulphuric acid soln and sodium hydroxide solution.
The ozone of the present embodiment is provided by ozonizer (with woods science and technology, China), the high purity oxygen that the air inlet of ozonizer provides for oxygen canister (99.999%), and charge flow rate is controlled by gas meter.Oxygen is prepared ozone through ozonizer, and continuous ozone oxidation is carried out in the bottom, aeration tank that ozone passes into in-built quantitative PVA waste water through the stainless steel gas circuit, by glass material, prepared by aeration tank.The delivery rate of this covering device ozone is 0.26 mg/ (minmL), by iodimetry,iodometry, is demarcated.In test, keep delivery rate constant.Preferably, in the present embodiment, the aeration time of ozone is 20 min.
After ozonation aerated, waste water is transferred to the ozone-depleting pond, and sealing and standing makes ozone-depleting thorough more than 12 hours, obtain a pretreated water.Pretreated water is put into to radiation-resistant Glass Containers; This radiation-proof is placed in to the gamma Rays district and carries out gamma Rays, the gamma-rays dose rate of this radiation zone adopts ferrous sulfate dosimeter (Fricke quantimeter) quantitative.Preferably, in the present embodiment, the absorption dose of PVA waste water is the radiation dose that 6 kGy(namely accept on the irradiated material unit mass, the kGy=kJ/kg of unit).After irradiation, waste water is carried out to the TOC detection.
The contrast experiment 1
For investigating PVA waste water first through ozone oxidation, whether the combined treatment mode of carrying out again ionizing rays exists " synergistic effect " on the organic matter removal of PVA waste water, same PVA waste water has been carried out respectively: (1) independent ozone oxidation 20 min are also standing treats more than 12 hours that ozone-depleting is thorough, obtains water sample 1; (2) ionizing rays is processed 6 kGy and is obtained water sample 2 separately.Clearance addition by the TOC of the clearance of the TOC of water sample 1 and water sample 2.
If the first ozone oxidation of embodiment 1, the array mode of ionizing rays is greater than contrast experiment 1 ozone oxidation under similarity condition and ionizing rays respectively to PVA waste water TOC clearance sum to the clearance of PVA waste water TOC again, " synergistic effect " of " 1+1 > 2 " occur.
As shown in Figure 2, the first ozone oxidation of PVA waste water process at initial pH 3.0, pH 7.0 and pH 9.4, after ionizing rays combined treatment again, the TOC clearance is all managed gained TOC clearance sums 6%, 2%, 5% over two kinds of technical point other places, and has improved respectively 67%, 350% and 160%.Therefore, in initial pH 3.0 ~ 9.4 scopes, first ozone oxidation, then there be " synergistic effect " in the combined treatment PVA waste water of ionizing rays in the removal of TOC.
Embodiment 2
Processing object in the present embodiment is for being called for short AY-GG containing azoic dyestuff sodium p-nitrobenzene-azo-salicylate-GG(, and this Colour Index is encoded to C.I. 14025) organic waste water of 100 mg/L, belong to organic wastewater with difficult degradation thereby, total organic carbon (TOC) value is 62 mg/L.The TOC value adopts TOC analyser (TOC-V
cPH, Shimadzu) measure.The initial pH value of waste water adopts desk-top pH instrument to measure (FiveEasy, Mettler Toledo), and is regulated with sulphuric acid soln and sodium hydroxide solution.
The ozone source of the present embodiment is provided by ozonizer (with woods science and technology, China), the high purity oxygen that the air inlet of ozonizer provides for oxygen canister (99.999%), and charge flow rate is controlled by gas meter.Oxygen is prepared ozone through ozonizer, and continuous ozone oxidation is carried out in the bottom, aeration tank that ozone passes into in-built quantitative PVA waste water through the stainless steel gas circuit, by glass material, prepared by aeration tank.The delivery rate of this covering device ozone is 0.26 mg/ (minmL), by iodimetry,iodometry, is demarcated.In test, keep delivery rate constant.Preferably, in the present embodiment, the aeration time of ozone is 10 min.
After ozonation aerated, waste water is shifted and to put the ozone-depleting pond, and sealing and standing makes ozone-depleting thorough more than 12 hours, obtain a pretreated water.This pretreated water is put into to radiation-resistant Glass Containers; This radiation-proof is placed in to the gamma Rays district and carries out gamma Rays, the gamma-rays dose rate of this radiation zone adopts ferrous sulfate dosimeter (Fricke quantimeter) quantitative.Preferably, in the present embodiment, the absorption dose of AY-GG waste water is the radiation dose that 6 kGy(namely accept on the irradiated material unit mass, the kGy=kJ/kg of unit).After irradiation, waste water is carried out to the TOC detection.
The contrast experiment 2
For investigating AY-GG waste water first through ozone oxidation, whether the combined treatment mode of carrying out again ionizing rays exists " synergistic effect " on the organic matter removal of AY-GG waste water, same AY-GG waste water has been carried out respectively to (1) separately ozone oxidation 10 min standingly treat more than 12 hours that ozone-depleting is thorough, obtains water sample 1; (2) ionizing rays is processed 6 kGy and is obtained water sample 2 separately.Clearance addition by the TOC of the clearance of the TOC of water sample 1 and water sample 2.
If the first ozone oxidation of embodiment 2, the array mode of ionizing rays is greater than contrast experiment 2 ozone oxidation under similarity condition and ionizing rays respectively to AY-GG waste water TOC clearance sum to the clearance of AY-GG waste water TOC again, " synergistic effect " of " 1+1 > 2 " occur.
As shown in Figure 3, in the first ozone oxidation of AY-GG waste water process of initial pH 7.3 and pH 10.9, then, after the ionizing rays combined treatment, the TOC clearance reaches respectively 61% and 67%, all over two kinds of technical point other places reason gained TOC clearance sums 56% and 62%.Therefore, in initial pH 7.3 ~ 10.9 scopes, first ozone oxidation, then there be " synergistic effect " in the combined treatment AY-GG waste water of ionizing rays in the removal of TOC.
The contrast experiment 3
For the impact on organic matter removal of the sequencing of investigating organic waste water ozone oxidation and ionizing rays processing, AY-GG waste water to same initial pH 7.3 and initial pH 10.9, be respectively first and process 6 kGy by ionizing rays, then the organic waste water that will process through ionizing rays carries out ozonation aerated 10 minutes in aeration tank, and standing more than 12 hours, ozone in organic waste water after aeration is removed, the TOC clearance of gained difference 53% and 57% after processing, still be less than two kinds of technical point other places reason gained TOC clearance sums 56% and 62%.This result proves, this organic waste water first carries out the ionizing rays processing, then carries out ozone Oxidation Treatment, occurs " synergistic effect ".
At first the technical program carries out ozone oxidation by organic waste water, allows ozone selectively (first attack the functional groups such as two keys, phenyl ring) and destroys/remove organism in water, and allow ozone self be consumed.The pretreated waste water of ozone, then process through the non-selectivity of ionizing rays, the two " synergistic effect " on organic matter removal easily produced." synergistic effect " in the technical program is different from the mechanism of action of generation synergistic effect under ozone and ionizing rays in the past acts on simultaneously.The two does the used time " synergistic effect " simultaneously is mainly that collaborative increase due to the hydroxyl radical free radical yield produces.And first ozone oxidation, ionizing rays produces again " synergistic effect " are collaborative to organic removal approach in water due to the two.And, owing to adopting ionizing rays to process, with (discarding) ozone Oxidation Treatment, combine, make ionizing rays process required radiation dose less, reduced the radiation energy consumption, be more suitable for being applied to Industrial Wastewater Treatment.
In addition, those skilled in the art also can do other variations in spirit of the present invention, and certainly, the variation that these are done according to spirit of the present invention, within all should being included in the present invention's scope required for protection.
Claims (10)
1. the Synergistic method of organic waste water is processed in an ozone oxidation and ionizing rays, comprising:
By organic waste water, in aeration tank, carry out ozonation aerated;
Ozone in organic waste water after ozonation aerated is removed, obtained a pretreated water; And
This pretreated water is carried out to the ionizing rays processing.
2. the Synergistic method of organic waste water is processed in ozone oxidation as claimed in claim 1 and ionizing rays, it is characterized in that, this ionizing rays is gamma Rays, electron beam irradiation or X-radiation.
3. the Synergistic method of organic waste water is processed in ozone oxidation as claimed in claim 1 and ionizing rays, it is characterized in that the waste water that this organic waste water is pbz polymer polymkeric substance or hardly degraded organic substance.
4. the Synergistic method of organic waste water is processed in ozone oxidation as claimed in claim 1 and ionizing rays, it is characterized in that, the removal of this organic waste water is for to be removed by standing.
5. the Synergistic method of organic waste water is processed in ozone oxidation as claimed in claim 4 and ionizing rays, it is characterized in that, this standing time is 6 hours to 24 hours.
6. the Synergistic method of organic waste water is processed in ozone oxidation as claimed in claim 4 and ionizing rays, it is characterized in that, this organic waste water carries out standing in the ozone-depleting pond.
7. the Synergistic method of organic waste water is processed in ozone oxidation as claimed in claim 1 and ionizing rays, it is characterized in that, comprises this pretreated water is passed into to a radiation chamber, in this radiation chamber, accepts ionizing rays, last water outlet.
8. the Synergistic method of organic waste water is processed in ozone oxidation as claimed in claim 7 and ionizing rays, it is characterized in that, when this ionizing rays is electron beam irradiation, further comprise will produce at radiation chamber ozone extract out, and by the Ozone transfer extracted out to aeration tank.
9. an organic waste water coprocessing system, is characterized in that, comprises ionizing rays device, aeration tank and ozone-depleting pond, and the ozone in this organic waste water is removed in this ozone-depleting pond.
10. organic waste water coprocessing system as claimed in claim 9, is characterized in that, further comprises the ozone delivery device, and this ozone delivery device will be delivered to this aeration tank from the ozone of extracting out in the radiation chamber of this ionizing rays device.
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| CN105366759A (en) * | 2015-12-16 | 2016-03-02 | 中华人民共和国陕西出入境检验检疫局 | Degrading method for rhodamine B |
| CN105561517A (en) * | 2015-12-16 | 2016-05-11 | 中华人民共和国陕西出入境检验检疫局 | Degradation method of Sudan IV |
| CN106167328A (en) * | 2016-08-30 | 2016-11-30 | 中广核达胜加速器技术有限公司 | A kind of novel organic wastewater with difficult degradation thereby advanced treatment apparatus |
| CN109940027A (en) * | 2019-04-04 | 2019-06-28 | 广西南翔环保有限公司 | The method for handling discarded polymolecular organic drug using irradiation technique |
| CN113929245A (en) * | 2021-09-10 | 2022-01-14 | 中石化石油工程技术服务有限公司 | Method and system for recycling high-chlorine produced water of gas field |
| CN116002845A (en) * | 2023-02-22 | 2023-04-25 | 清华大学 | Pretreatment method and integral treatment process of coking wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109940027A (en) * | 2019-04-04 | 2019-06-28 | 广西南翔环保有限公司 | The method for handling discarded polymolecular organic drug using irradiation technique |
| CN113929245A (en) * | 2021-09-10 | 2022-01-14 | 中石化石油工程技术服务有限公司 | Method and system for recycling high-chlorine produced water of gas field |
| CN113929245B (en) * | 2021-09-10 | 2024-02-09 | 中国石油化工集团有限公司 | Method and system for recycling high-chlorine produced water of gas field |
| CN116002845A (en) * | 2023-02-22 | 2023-04-25 | 清华大学 | Pretreatment method and integral treatment process of coking wastewater |
| CN116002845B (en) * | 2023-02-22 | 2024-08-06 | 清华大学 | Pretreatment method and integral treatment process of coking wastewater |
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