CN103435206B - 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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- CN103435206B CN103435206B CN201310355422.6A CN201310355422A CN103435206B CN 103435206 B CN103435206 B CN 103435206B CN 201310355422 A CN201310355422 A CN 201310355422A CN 103435206 B CN103435206 B CN 103435206B
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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 the treatment system of a kind of ozone oxidation and ionizing rays process organic waste water.
Background technology
High-level oxidation technology (AOP) is a class water technology emerging in recent years, 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.But running cost is high, less economical is the common weakness of high-level oxidation technology, hinders it and applies on a large scale.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 the need to adding chemical reagent, has environment friendly.But, for the process problem of a large amount of trade effluent, be used alone Ionizing Radiation and there is the problems such as required radiation quantity is large, energy consumption is high, be difficult to be applied to Industrial Wastewater Treatment.Ozone Oxidation Treatment technology is a kind of comparatively conventional and relatively inexpensive wastewater processing technology.Advantage is swift in response, and technique is simple, does not have secondary pollution problem.But for organic wastewater with difficult degradation thereby, be still difficult to take effect by ozone individual curing.
At present, at O
3carry out ionizing rays under existent condition, to Organic substance in water remove " synergistic effect " studied confirm (as Chinese patent application CN 101362619A).But the electron beam that the usual applying electronic accelerator of actual ionizing rays engineering of water treatment produces carries out irradiation water treatment.Rumbatron is very expensive, and the lower irradiator of its bundle should be avoided and O as far as possible
3contact Deng corrosives.Even if additionally do not adding O
3when, still take the O produced as by product in ionizing rays process when common ionizing rays process
3deng the measure of gas pump-and-treat system.Visible, additionally will add O
3waste water carry out ionizing rays at radiation chamber, make O
3reality is run counter to the mode that waste water processes with ionizing rays simultaneously.Therefore, how ozonation technology and ionizing rays are better combined and process waste water and need to be studied further.
Summary of the invention
In view of this, necessary provide a kind of the Synergistic method of the process organic waste water that ionizing rays and ozone oxidation effectively can be combined of practical application and treatment system.
A Synergistic method for ozone oxidation and ionizing rays process organic waste water, comprising: carry out ozonation aerated in aeration tank by organic waste water; Ozone in organic waste water after ozonation aerated is removed, obtains a pretreated water; And this pretreated water is carried out ionizing rays process.
A kind of organic wastewater synergetic treatment system, comprise ionizing rays device, aeration tank and ozone-depleting pond, the ozone in this organic waste water is removed in this ozone-depleting pond.
Beneficial effect of the present invention is: by by organic waste water first through ozone Oxidation Treatment, and the ozone in the organic waste water after process is removed, again through ionizing rays radiotreatment, selective destruction and/or the removal of Pre-Ozonation on Organic Matter matter or intermediate product can be realized, avoid containing ozone wastewater loss of equipment etc. under halved tie in radiation chamber.Organic waste water is after the selectivity process of ozone, again through the ionizing rays process of non-selectivity, " synergistic effect " is there is in the removal effect of organic pollutants, make the radiation dose needed for ionizing rays process relatively little, reduce radiation energy consumption, be applicable to being applied to ionizing rays Industrial Wastewater Treatment.
Accompanying drawing explanation
Fig. 1 is the process schematic of a kind of ozone oxidation and ionizing rays process organic waste water in the present invention.
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.
Main element nomenclature
| Organic wastewater synergetic treatment system | 100 |
| Electron beam irradiation device | 10 |
| Rumbatron | 12 |
| The lower power system of bundle | 14 |
| Radiation chamber | 16 |
| Aeration tank | 20 |
| Ozone-depleting pond | 30 |
| Ozone delivery device | 40 |
| Waste water e Foerderanlage | 50 |
Following embodiment will further illustrate the present invention in conjunction 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 process organic waste water is described in further detail.
Refer to Fig. 1, the invention provides the Synergistic method of a kind of ozone oxidation and ionizing rays process organic waste water, it comprises the following steps:
S1, carries out ozonation aerated by organic waste water in aeration tank;
S2, removes the ozone in the organic waste water after ozonation aerated, obtains a pretreated water; And
S3, carries out ionizing rays process by this pretreated water.
The method is ozone oxidation-ionizing rays associated treatment organic waste water, namely by organic waste water first through ozone Oxidation Treatment, treat ozone depletion, then by ionizing rays process.This waste water is preferably pbz polymer polymkeric substance or has the waste water of organic hardly degraded organic substance of double bond and/or phenyl ring.
Particularly, in step sl, ozone can be passed into this organic waste water, ozone can be provided by ozonizer, when ionizing rays process in step S3 adopts rumbatron as irradiation source, the ozone in S1 also can be provided by the discarded ozone extracted out in the radiation chamber 16 of ionizing rays device.Aeration tank and aerating system all adopt the material of resistance to ozone oxidation to prepare, and airtight.The ozone amount passed into and aeration time all can determine according to the kind of organic waste water and concentration.
In step s 2, 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 little of 24 hours.This organic waste water can leave standstill in aeration tank, also can pass in special ozone-depleting pond and leave standstill, thus the ozone in organic waste water is removed.This ozone-depleting pond adopts the material of resistance to ozone oxidation to prepare, and is preferably closed structure.For raising the efficiency, also by bleeding or shortening the modes such as organic waste water hydraulic detention time (HRT), the ozone in organic waste water is removed.
In step s3, this pretreated water can pass into a radiation chamber, in this radiation chamber, accept ionizing rays, last water outlet.This ionizing rays can be gamma Rays, electron beam irradiation or X-radiation.Wherein, gamma-rays obtains by gamma Rays device, specifically by
60co or
137cs 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 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 Accelerating electron and extraction, form an electron beam irradiation district, the lower power system 14 of bundle is for being transferred through this electron beam irradiation district to accept electron beam irradiation by pretreated water, Controlling System is for controlling this rumbatron 12 and lower power system 14 collaborative work of bundle.
When adopting electron beam to carry out radiation, can be further comprising the steps: this pretreated water is carried out electron beam irradiation with continuous fluid form by the electron beam irradiation district of rumbatron 12.Pretreated water is by restrainting the electron beam irradiation district of lower power system 14 continuously through this rumbatron.Particularly, pretreated water passes through the electron beam irradiation district of this rumbatron 12 with the form of moisture film, basic this water film surface vertical of radiation direction of this electron beam.Preferably, the penetration range of electron beam in water is no more than by the water film thickness in electron beam irradiation district.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 air be there is, and electron beam irradiation also irradiates the oxygen in ambient air while irradiating pretreated water, thus form ozone.Therefore, further by an air extractor, the ozone produced at radiation chamber can be extracted out in radiation chamber 16.In addition, can further by ozone delivery device by extract out Ozone transfer to aeration tank, pass into organic waste water, reach the recycling of ozone.
The present invention further provides a kind of organic wastewater synergetic treatment 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 be all connected by waste water e Foerderanlage 50 between this ozone-depleting pond 30 with this ionizing rays device.This waste water e Foerderanlage 50 can comprise pipeline and water pump, makes organic waste water can 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 wastewater synergetic treatment system can comprise ozone delivery device 40 further, and the ozone extracted out in the radiation chamber 16 of ionizing rays device is delivered to this aeration tank 20 by this ozone delivery device 40.This ozone delivery device 40 can comprise air extractor (as vacuum fan) and gas pipe line.
Embodiment 1
Handling object in the present embodiment is the organic waste water containing polyvinyl alcohol (PVA) 300 mg/L, and belong to organic wastewater with difficult degradation thereby, total organic carbon (TOC) value is 185 mg/L.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 regulates 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 (99.999%) that the air inlet of ozonizer provides for oxygen canister, and charge flow rate is controlled by gas meter.Oxygen prepares ozone through ozonizer, and ozone passes into bottom the aeration tank of in-built quantitative PVA waste water through stainless steel gas circuit and carries out continuous print ozone oxidation, and aeration tank is prepared by glass material.The delivery rate of this covering device ozone is 0.26 mg/ (minmL), is demarcated by iodimetry,iodometry.Keep delivery rate constant in test.Preferably, in the present embodiment, the aeration time of ozone is 20 min.
After ozonation aerated, waste water is transferred to ozone-depleting pond, and sealing and standing more than 12 hours, make ozone-depleting thorough, obtain a pretreated water.Pretreated water is put into radiation-resistant Glass Containers; This radiation-proof is placed in 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(i.e. irradiated material unit mass accept, unit kGy=kJ/kg).After irradiation, waste water is carried out TOC detection.
Contrast experiment 1
For investigating PVA waste water first through ozone oxidation, whether the combined treatment mode of carrying out ionizing rays again exists " synergistic effect " on the organic matter removal of PVA waste water, same PVA waste water is carried out respectively: (1) independent ozone oxidation 20 min also leaves standstill and within more than 12 hours, treats that ozone-depleting is thorough, obtains water sample 1; (2) ionizing rays process 6 kGy obtains water sample 2 separately.The clearance of the clearance of the TOC of water sample 1 with the TOC of water sample 2 is added.
If the first ozone oxidation of embodiment 1, the clearance of array mode to PVA waste water TOC of ionizing rays is greater than ozone oxidation and the ionizing rays under similarity condition of contrast experiment 1 respectively to PVA waste water TOC clearance sum again, namely occurs " synergistic effect " of " 1+1 > 2 ".
As shown in Figure 2, at the PVA waste water of initial pH 3.0, pH 7.0 and pH 9.4 through first ozone oxidation, after ionizing rays combined treatment again, TOC clearance all more than two kinds of technical point other places reason gained TOC clearance sums 6%, 2%, 5%, and improves 67%, 350% and 160% respectively.Therefore, in initial pH 3.0 ~ 9.4 scope, first ozone oxidation, then in the removal of TOC, there is " synergistic effect " in the combined treatment PVA waste water of ionizing rays.
Embodiment 2
Handling 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.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 regulates 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 (99.999%) that the air inlet of ozonizer provides for oxygen canister, and charge flow rate is controlled by gas meter.Oxygen prepares ozone through ozonizer, and ozone passes into bottom the aeration tank of in-built quantitative PVA waste water through stainless steel gas circuit and carries out continuous print ozone oxidation, and aeration tank is prepared by glass material.The delivery rate of this covering device ozone is 0.26 mg/ (minmL), is demarcated by iodimetry,iodometry.Keep delivery rate constant in test.Preferably, in the present embodiment, the aeration time of ozone is 10 min.
After ozonation aerated, ozone-depleting pond is put in waste water transfer, and sealing and standing more than 12 hours, make ozone-depleting thorough, obtain a pretreated water.This pretreated water is put into radiation-resistant Glass Containers; This radiation-proof is placed in 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(i.e. irradiated material unit mass accept, unit kGy=kJ/kg).After irradiation, waste water is carried out TOC detection.
Contrast experiment 2
For investigating AY-GG waste water first through ozone oxidation, whether the combined treatment mode of carrying out ionizing rays again exists " synergistic effect " on the organic matter removal of AY-GG waste water, carry out (1) independent ozone oxidation 10 min respectively and left standstill within more than 12 hours, treating that ozone-depleting is thorough to same AY-GG waste water, obtain water sample 1; (2) ionizing rays process 6 kGy obtains water sample 2 separately.The clearance of the clearance of the TOC of water sample 1 with the TOC of water sample 2 is added.
If the first ozone oxidation of embodiment 2, the clearance of array mode to AY-GG waste water TOC of ionizing rays is greater than ozone oxidation and the ionizing rays under similarity condition of contrast experiment 2 respectively to AY-GG waste water TOC clearance sum again, namely occurs " synergistic effect " of " 1+1 > 2 ".
As shown in Figure 3, at the AY-GG waste water of initial pH 7.3 and pH 10.9 through first ozone oxidation, then after ionizing rays combined treatment, TOC clearance reaches 61% and 67% respectively, all more than two kinds of technical point other places reason gained TOC clearance sums 56% and 62%.Therefore, in initial pH 7.3 ~ 10.9 scope, first ozone oxidation, then in the removal of TOC, there is " synergistic effect " in the combined treatment AY-GG waste water of ionizing rays.
Contrast experiment 3
For investigating the sequencing of organic waste water ozone oxidation and ionizing rays process to the impact of organic matter removal, to the AY-GG waste water of same initial pH 7.3 and initial pH 10.9, be respectively first by ionizing rays process 6 kGy, then the organic waste water through ionizing rays process is carried out ozonation aerated 10 minutes in aeration tank, and leave standstill more than 12 hours, ozone in organic waste water after aeration is removed, the TOC clearance difference 53% and 57% of gained after process, is still 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 ionizing rays process, then carries out ozone Oxidation Treatment, does not occur " synergistic effect ".
First organic waste water is carried out ozone oxidation by the technical program, allows ozone selectively (first attack the functional group such as double bond, phenyl ring) and destroys/remove Organic substance in water, and allow ozone self be consumed.The pretreated waste water of ozone, then through the non-selectivity process of ionizing rays, " synergistic effect " both easily producing on organic matter removal." synergistic effect " in the technical program act on from ozone and ionizing rays in the past simultaneously under the mechanism of action of generation synergistic effect different." synergistic effect " during the two effect simultaneously mainly produces due to the collaborative increase of hydroxyl radical free radical yield.And " synergistic effect " that first ozone oxidation, again ionizing rays produce is due to the two working in coordination with the removal pathway of Organic substance in water.Further, owing to adopting ionizing rays process to combine with (discarding) ozone Oxidation Treatment, make the radiation dose needed for ionizing rays process relatively little, reduce radiation energy consumption, be more suitable for being applied to Industrial Wastewater Treatment.
In addition, those skilled in the art also can do other changes in spirit of the present invention, and certainly, these changes done according to the present invention's spirit, all should be included within the present invention's scope required for protection.
Claims (9)
1. a Synergistic method for ozone oxidation and ionizing rays process organic waste water, comprising:
Carry out ozonation aerated in aeration tank by organic waste water, this organic waste water is the waste water containing polyvinyl alcohol or azoic dyestuff sodium p-nitrobenzene-azo-salicylate-GG;
Ozone in organic waste water after ozonation aerated is removed, obtains a pretreated water; And
This pretreated water is carried out ionizing rays process.
2. the Synergistic method of ozone oxidation as claimed in claim 1 and ionizing rays process organic waste water, it is characterized in that, this ionizing rays is gamma Rays, electron beam irradiation or X-radiation.
3. the Synergistic method of ozone oxidation as claimed in claim 1 and ionizing rays process organic waste water, is characterized in that, the removal of this organic waste water is for removing by leaving standstill.
4. ozone oxidation as claimed in claim 3 and the Synergistic method of ionizing rays process organic waste water, is characterized in that, this standing time is 6 little of 24 hours.
5. the Synergistic method of ozone oxidation as claimed in claim 3 and ionizing rays process organic waste water, it is characterized in that, this organic waste water leaves standstill in ozone-depleting pond.
6. the Synergistic method of ozone oxidation as claimed in claim 1 and ionizing rays process organic waste water, is characterized in that, comprise and this pretreated water is passed into a radiation chamber, in this radiation chamber, accept ionizing rays, last water outlet.
7. the Synergistic method of ozone oxidation as claimed in claim 6 and ionizing rays process organic waste water, it is characterized in that, when this ionizing rays is electron beam irradiation, comprises further and the ozone produced at radiation chamber is extracted out, and by the Ozone transfer of extraction to aeration tank.
8. an organic wastewater synergetic treatment system, it is characterized in that, comprise ionizing rays device, aeration tank and ozone-depleting pond, the ozone in this organic waste water is removed in this ozone-depleting pond, and this organic waste water is the waste water containing polyvinyl alcohol or azoic dyestuff sodium p-nitrobenzene-azo-salicylate-GG.
9. organic wastewater synergetic treatment system as claimed in claim 8, it is characterized in that, comprise ozone delivery device further, the ozone extracted out in the radiation chamber from this ionizing rays device is delivered to this aeration tank by this ozone delivery device.
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| 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 |
| 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 |
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