CN101423283B - High efficiency detoxifcation method and device of organic wastewater - Google Patents
High efficiency detoxifcation method and device of organic wastewater Download PDFInfo
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- CN101423283B CN101423283B CN2008101621988A CN200810162198A CN101423283B CN 101423283 B CN101423283 B CN 101423283B CN 2008101621988 A CN2008101621988 A CN 2008101621988A CN 200810162198 A CN200810162198 A CN 200810162198A CN 101423283 B CN101423283 B CN 101423283B
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Abstract
The invention relates to a high-efficiency detoxification method of organic waste water, and a device thereof. The method mainly comprises the following steps of: mixing, catalytic reaction, oxidant reduction and the like. Organic waste water to be treated is led to a pipeline mixer for sufficient mixing with H2O2 and O3, then enters a catalytic reactor composed of a catalytic reaction unit, the catalytic reaction is carried out under the action of catalysts which uses active carbons as carriers and under the inducement of ultraviolet light, and enters an oxidant reduction unit again; reducers are filled into the organic waste water, and after reduction reaction is carried out to the organic waste water, waste water which is in accordance with requirements is lead out. The device is composed of a pipeline mixer used for sufficient mixing for organic waste water, H2O2 and O3, wherein, the rear part of the pipeline mixer is connected with a catalytic reactor composed of a catalytic reaction unit; and the rear part of the catalytic reactor is connected with an oxidant reduction unit. The invention has the characteristics of simple technical allocation, low processing cost, simple operation control, good detoxification treatment effect and the like.
Description
Technical field
What the present invention relates to is a kind of high efficiency detoxifcation method and device of organic waste water, and the high efficiency detoxifcation method and the device of the biochemical organic waste water of especially a kind of novel difficulty belong to wastewater processing technology.
Background technology
It is the very popular technology focus of environmental protection specialized engineering technician of being devoted to the waste water treatment field now that bio-refractory organic waste water is administered always, especially in some medicine, agricultural chemicals, dyestuff, household chemicals manufacturing, refuse landfill, ooze industries such as drop liquid processing, it is many that its factory effluent contains bio-refractory, as most of halogen contained compounds, ether compound, nitro-compound, azo compound, tertiary amines and quaternary ammonium compound, contain S organism and some heterocyclic organism etc., intractability is big.In the treatment of Organic Wastewater field, biochemical processing is acknowledged as most economical technology, containing above-mentioned substance and be main organic waste water then often can't use biochemical treatment merely and just can produce a desired effect or not reach the water outlet requirement, therefore it often takes pre-treatment to make the inorganic elements that contains form the inorganics of high valence state earlier, molecular structure wherein produces the small molecules that breaks to form different oxidation state, thereby improve wastewater biochemical, promptly be called such waste water is realized detoxifcation, reach the purpose that then to handle by biochemical process.
Mainly contain at present at the organic waste water detoxification that uses:
(1) wet type advanced oxidation processes,
This technology be utilize air High Temperature High Pressure (〉=120 ℃, 〉=10atm) sometimes in the presence of catalyzer in the oxidized waste water pollutent reach the purpose of processing.This processing method requires under high-temperature and high-pressure conditions, the operational condition harshness, treatment facility investment and processing costs are all very expensive, reach the biochemical that improves waste water fully or remove the purpose of polluting, 1 ton of its processing costs of waste water of every processing is up to hundred yuan of RMB even higher, and equipment belongs to pressurized vessel, has bigger safety problem.
(2) Feton reagent homogeneous catalysis oxidation style, this method is to utilize H
2O
2Under certain pH condition by Fe
2+The purpose that pollutent in a large amount of HO (hydroxyl radical free radical) oxidized waste waters reaches processing is decomposed in katalysis.Organism in the Feton reagent oxidation waste water requires very harsh to pH, often require pH about 2-3, and rate of oxidation is low, uses a large amount of ferrous salts simultaneously, and secondary pollution is that sludge quantity is big, many alkaline waste waters that are are then needed to consume a large amount of acid, need consume a large amount of alkali and will satisfy the requirement of handling back continuation biochemistry, artificially increase salinity, not only the expense height, and often the salt of the former water of this type of waste water own is all higher, so caused the restraining effect of inorganic salt again to biology.
(3) O
3Or O
3/ UV co-oxidation method.This this technology is to utilize O
3Under certain pH condition or by the combined action of UV, decompose the purpose that pollutent in a large amount of HO (hydroxyl radical free radical) oxidized waste waters reaches processing.O
3Or O
3/ UV co-oxidation process process is slow, and need to be under alkali condition, existing O of while
3The incurred cost costliness, the O of 1kg/h generating capacity
3Its installed capacity of generator needs more than the 40KVA, and the disposal cost height installs hugely, and oxidation time of contact can not be less than 30min in principle, and take air as O
2The O that the source takes place
3Be difficult to reach the concentration more than the 5mg/L in water, the centering high concentrated organic wastewater is processed, adaptability and weak effect.
(4) H
2O
2/ UV co-oxidation method
This technology is to utilize H
2O
2The purpose that a large amount of HO (hydroxyl radical free radical) oxidized waste water pollutants reaches processing is decomposed in synergy by UV under certain pH condition.H
2O
2/ UV co-oxidation technology is final or need to rely on Fe
2+Catalytic action, its shortcoming and Feton reagent oxidation technology type with.
(5) O
3/ H
2O
2The co-oxidation method, this method is to utilize O
3/ H
2O
2The purpose that a large amount of HO (hydroxyl radical free radical) oxidized waste water pollutants reaches processing is decomposed in synergy under certain pH condition.For same wastewater treatment depth requirements, O
3/ H
2O
2The O that co-oxidation technology need consume
3Amount can obviously reduce, but owing to the purpose that will reach economical rationality still need to be with H
2O
2Be oxidized to Main Means, process still must be carried out under low pH condition, shortcoming is similar to H
2O
2/ UV and Feton reagent oxidation technology.
(6) high ferro oxidation style
This technology is to utilize pollutent in the superpower oxidisability of ferrate (as potassium ferrate) and the hypotoxicity oxidized waste water of itself to reach the purpose of processing.The shortcoming of this technology is that ferrate often needs interim preparation, process control and complex equipment, disposal cost height.
(7) other mainly contains ultrasonic, the ancillary technique of microwave and the co-oxidation technology of strong oxidizer etc., and they are also under test at present, and its ultrasonic and generation equipment microwave of scale operation all is difficult to adapt to.
Summary of the invention
The objective of the invention is to overcome the deficiency of above-mentioned existence, and provide a kind of Process configuration to simplify, processing cost is low, and operation control is simple, high efficiency detoxifcation method and the device of the organic wastewater that the detoxifcation treatment effect is good.
The objective of the invention is to finish by following technical solution, the high efficiency detoxifcation method of described organic wastewater, this method comprises three steps such as mixing, catalytic reaction and oxidant reduction, pending organic wastewater is passed in the pipe-line mixer and H
2O
2And O
3Fully mix, enter then in the catalytic reactor by the catalytic reaction cell formation, under ultraviolet light UV induces, via carrying out catalytic reaction under the catalyst action take active carbon as carrier, enter again an oxidant reduction unit, after adding reducing agent and reaction, draw satisfactory waste water.
Described pending organic wastewater is collected in earlier in collecting-tank or the groove, and pH is controlled at 5-11, sends into then a pipe-line mixer; And H
2O
2And O
3By water inlet CODcr/H
2O
2/ O
3The ratio of=1～2/2～3/0.06～0.10kg/h adds, and sneaks at the front end of pipe-line mixer with described organic wastewater.
After fully mixed organic waste water enters at least in the catalyticreactor that is made of two catalyzed reaction unit in the described line mixer, the organic contact load of beds in the described catalyzed reaction unit or to add load be 10～15kgCODcr/m
3.d; And the beds aeration intensity is controlled to be 1.2～1.5m
3/ m
2.h, to ensure auxiliary contact effect.
Organic wastewater after the described catalytic reaction unit enters the oxidant reduction unit, adds NaHSO in this oxidant reduction unit
4Or ferrous salt reducing agent, and with the dosage of oxidation-reduction potential ORP control reducing agent.Also mixing contacts its stirring intensity 0.6～1.0m to reductive agent in the described oxygenant reduction unit by pneumatic blending with waste water
3/ m
2.h.
A kind of for the device of the high efficiency detoxifcation method of organic wastewater as mentioned above, it mainly includes: organic wastewater and H
2O
2And O
3The pipe-line mixer that fully mixes usefulness, this pipe-line mixer upper inlet end is connected organic waste water collecting-tank or groove by pipeline, and this pipe-line mixer upper inlet end also is communicated with respectively O
3Generator and H
2O
2Throwing device; Described pipe-line mixer back is connected to one group at least by the catalytic reactor of two catalytic reaction cell formations, ultraviolet light generator UV and the air diffuser that is communicated in a roots blower all are installed in each catalytic reaction unit, be connected to an oxidant reduction unit in described catalytic reactor back, be connected to a reducing agent throwing device at this oxidant reduction unit, and be provided with oxidation-reduction potential ORP control device, with the injected volume of control reducing agent, the waste water after drawing processing after the oxidant reduction processing.
Pipe-line mixer of the present invention, its front end are provided with one section venturi pipeline section at least, introduce H with the vacuum that forms
2O
2And O
3, and make H
2O
2And O
3Fully mix with organic wastewater.
The unitary centre of described catalyzed reaction is for loading by the catalyzer fill area that with the gac is the solid-phase catalyst of carrier, and its top is equipped with ultraviolet light generator UV, and is furnished with air diffuser in its underpart.
The present invention compared with prior art has following technique effect: 1, simplified whole Process configuration; 2, reduced processing cost, the detoxifcation processing cost is no more than 2 yuan of RMB by kgCODcr; 3,, can realize the processing unit complete set according to different process object; 4, technological process pH is applied widely; 5, excessive oxygenant elimination speed is fast; 6, operation control is simple; 7, finished the Application and Development of efficient normal temperature and pressure catalysis agent; 8, HO concentration height in the treating processes waste water is effective; 9, do not produce secondary pollutant substantially.
Description of drawings
Fig. 1 is a structural arrangement synoptic diagram of the present invention.
Embodiment
The present invention will be described in detail: the high efficiency detoxifcation method of organic wastewater of the present invention below in conjunction with specific embodiment and accompanying drawing, this method mainly comprises three steps such as mixing, catalytic reaction and oxidant reduction, and pending organic wastewater is passed in the pipe-line mixer and H
2O
2And O
3Fully mix, enter then in the catalytic reactor by the catalytic reaction cell formation, induce lower at ultraviolet light UV, via carrying out catalytic reaction under the catalyst action take active carbon as carrier, enter again an oxidant reduction unit, after adding reducing agent, carry out drawing satisfactory waste water after the oxidant reduction.
Pending organic wastewater of the present invention is to be collected in earlier in collecting-tank or the groove, and pH is controlled at 5-11, sends into then a pipe-line mixer; And H
2O
2And O
3By water inlet CODcr/H
2O
2/ O
3The ratio of=1～2/2～3/0.06～0.10kg/h adds, and sneaks at the front end of pipe-line mixer with described organic wastewater.
After fully mixed organic waste water enters in the catalyticreactor that is made of at least two catalyzed reaction unit in the described line mixer, the organic contact load of the beds in the catalyzed reaction unit or to add load be 10～15kgCODcr/m
3.d; And the beds aeration intensity is controlled to be 1.2～1.5m
3/ m
2.h, to ensure auxiliary contact effect.
Organic wastewater after the described catalytic reactor enters the oxidant reduction unit, and adds NaHSO in this oxidant reduction unit
4Or ferrous salt reducing agent, and with the dosage of oxidation-reduction potential ORP control reducing agent.Also mixing contacts its stirring intensity 0.6～1.0m to reductive agent in the described oxygenant reduction unit by pneumatic blending with waste water
3/ m
2.h.
A kind of for the device of the high efficiency detoxifcation method of organic wastewater as mentioned above, see that it mainly includes shown in the accompanying drawing 1: organic wastewater and H
2O
2And O
3The pipe-line mixer 1 that fully mixes usefulness, this pipe-line mixer 1 upper inlet end is connected organic waste water collecting-tank or groove by waste pipe, and this pipe-line mixer 1 upper inlet end also is communicated with respectively O
3Generator 2 and H
2O
2Throwing device 3; Described pipe-line mixer 1 back is connected to one group by the catalytic reactor 4 of three catalytic reaction cell formations, ultraviolet light generator UV and the air diffuser 6 that is communicated in a roots blower 5 all are installed in each catalytic reaction unit, be connected to an oxidant reduction unit 7 in described catalytic reactor back, be connected to a reducing agent throwing device 8 at this oxidant reduction unit 7, and be provided with oxidation-reduction potential ORP control device 9, with the injected volume of control reducing agent, the waste water after drawing processing after the oxidant reduction processing.
Pipe-line mixer 1 of the present invention, its front end are provided with one section venturi pipeline section at least, introduce H with the vacuum that forms
2O
2And O
3, and make H
2O
2And O
3Fully mix with organic wastewater.The unitary centre of described catalyzed reaction is for loading by the catalyzer fill area 10 that with the gac is the solid-phase catalyst of carrier, and its top is equipped with ultraviolet light generator UV, and is furnished with air diffuser 6 in its underpart.
The present invention is by configured in advance medicament, wherein H
2O
2By 30% buying of concentration grade, storage tank stores; Reducing agent NaHSO
4The aqueous solution is by 20% preparation.Pending waste water (pH is controlled to be 5-11) after coagulation air-float or clarification is collected in collecting-tank or the groove, opens through the metering elevator pump to start simultaneously O
3Generator and H
2O
2Measuring pump is by water inlet CODcr/H
2O
2/ O
3The ratio of=1～2/2～3/0.06～0.10 (kg/h) adds, wherein H
2O
2And O
3Add at the pipe-line mixer front end earlier, waste water is by the pipe-line mixer of unique design, and this blender combines the separately advantage of venturi mixing and thread mixing, and the vacuum that the water intake mode that designs by similar venturi forms is introduced H
2O
2And O
3, and the three is fully mixed, the follow-up assembly of additional mixing device has further increased the contact strength of material.Enter each catalyzed reaction unit according to this through fully contacting mixed mixture, under the air diffuser effect, catalyst specific surface is fully used, under the bringing out of UV, form a large amount of hydroxyl radical free radicals with extremely strong oxidisability (OH), the beds aeration intensity is controlled to be 1.2～1.5m
3/ m
2.h, ensured auxiliary contact effect, economy is more reasonable simultaneously; Another core content of present technique is for the gac being the solid-phase catalyst of making through special process of carrier, this catalyzer is owing to gathered abundant selectivity rare metal, have processed pollutent catalytic condition wide, gac itself has just possessed stronger catalytic effect, catalytic performance is increased dramatically behind enrichment selectivity rare metal, thereby to the oxidising process less-restrictive, when handling hardly degraded organic substance waste water, the part hardly degraded organic substance is under UV-irradiation, improved energy level, be in excited state, hydroxylating take place, generate and be easy to biodegradable novel substance with the OH base; The purpose of its metal catalytic of heterogeneous catalytic oxidation is to promote O
3And H
2O
2Decomposition, strengthen its oxygenizement.
Remaining oxidant is then with H
2O
2Be main, because the final purpose of present technique is in order to make hardly degraded organic substance develop into biodegradable material by said process, Wastewater Pollutant is removed still depended on most economical biochemical treatment process degraded removal, but excessive oxidant then can be to the microorganisms lethal effect, therefore must remove, for the ease of operation control and management and economic, present technique has increased the destruction unit of superfluous oxidant, by adding an amount of reducing agent such as NaHSO
4Or ferrous salt, with the dosage of ORP (oxidation-reduction potential) control reducing agent, mixing contacts stirring intensity 0.6～1.0m to reducing agent by air stirring with waste water in the technology
3/ m
2.h.To be organic contact load (adding load) of beds be 10～15kgCODcr/m to another core parameter in the technology
3.d.
The present invention has gathered O
3/ H
2O
2/ UV normal temperature and pressure associating advanced catalytic oxidation technology, more traditional O
3/ H
2O
2/ UV associating its oxidant of advanced oxidation processes and the design of waste water mixed cell are ingenious, it is fast that free radical forms speed, the oxidant consumption amount is few, condition is wide, be easy to complete industrialization, preprocessing means as difficult for biological degradation organic wastewater is significant, is desirable difficult biochemical organic wastewater high-efficiency detoxication technology.
The process pH scope of application of the present invention is 5～11; O wherein
3: H
2O
2≈ 0.03～0.07:1; Hydraulic detention time HRT:2～5hr; And oxidant adds in proper order: H
2O
2-O
3/ UV; The pipeline premixed cellular construction uniqueness of oxidant, incorporation time 0.2～1min; Superfluous oxidant is H
2O
2Catalyst time of contact (TR): 1.0～3hr; Processing unit available depth: 1.5～2.5m; The present invention is with NaHSO
4For reducing agent is monitored excessive oxidant by ORP (EV), the protection microbial safety.
Claims (6)
1. the high efficiency detoxifcation method of an organic wastewater, this method mainly contain mixing, catalytic reaction and three steps of oxidant reduction, and pending organic wastewater is passed in the pipe-line mixer and H
2O
2And O
3Fully mix, enter then in the catalytic reactor by the catalytic reaction cell formation, UV light-induced lower, via carrying out catalytic reaction under the catalyst action take active carbon as carrier, enter again an oxidant reduction unit, after adding reducing agent and carrying out reduction reaction, draw satisfactory waste water; Described pending organic wastewater is collected in earlier in collecting-tank or the groove, and pH is controlled at 5-11, sends into then a pipe-line mixer; And H
2O
2And O
3By water inlet CODcr/H
2O
2/ O
3The ratio of=1～2/2～3/0.06～0.10kg/h adds, and sneaks at the front end of pipe-line mixer with described organic wastewater; After fully mixed organic wastewater enters at least in the catalytic reactor by two catalytic reaction cell formations in the described pipe-line mixer, the organic contact load of beds in the described catalytic reaction unit or to add load be 10～15kgCODcr/m
3.d; And the beds aeration intensity is controlled to be 1.2～1.5m
3/ m
2H is to ensure auxiliary contact effect.
2. the high efficiency detoxifcation method of organic waste water according to claim 1 is characterized in that the organic waste water after the described catalyticreactor enters the oxygenant reduction unit, and add NaHSO in this oxygenant reduction unit
4Or ferrous salt reductive agent, and with the dosage of redox potential ORP control reductive agent.
3. the high efficiency detoxifcation method of organic waste water according to claim 2 is characterized in that reductive agent in the described oxygenant reduction unit also mixes by pneumatic blending with waste water to contact its stirring intensity 0.6～1.0m
3/ m
2.h.
4. the device for the high efficiency detoxifcation method of organic wastewater as described in claim 1 or 2 or 3 is characterized in that it mainly comprises: organic wastewater and H
2O
2And O
3The pipe-line mixer that fully mixes usefulness, the entrance point of this pipe-line mixer is connected organic wastewater collecting-tank or groove by pipeline, and the entrance point of this pipe-line mixer also is communicated with respectively O
3Generator and H
2O
2Throwing device; Described pipe-line mixer back is connected to one group at least by the catalytic reactor of two catalytic reaction cell formations, ultraviolet light generator UV and the air diffuser that is communicated in a roots blower are installed in each catalytic reaction unit respectively, be connected to an oxidant reduction unit in back, described catalytic reaction unit, be connected to a reducing agent throwing device at this oxidant reduction unit, and be provided with oxidation-reduction potential ORP control device, with the injected volume of control reducing agent, the waste water after drawing processing after the oxidant reduction processing.
5. according to the device of the described high efficiency detoxifcation method for organic wastewater of claim 4, it is characterized in that described pipe-line mixer front end is provided with one section venturi pipeline section at least, introduce H with the vacuum that forms
2O
2And O
3, and make H
2O
2And O
3Fully mix with organic wastewater.
6. according to the described high efficiency detoxifcation method that is used for organic waste water of claim 5, it is characterized in that the unitary centre of described catalyzed reaction is for loading by the catalyzer fill area that with the gac is the solid-phase catalyst of carrier, its top is equipped with ultraviolet light generator UV, and is furnished with air diffuser in its underpart.
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|---|---|---|---|
| CN2008101621988A CN101423283B (en) | 2008-11-18 | 2008-11-18 | High efficiency detoxifcation method and device of organic wastewater |
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|---|---|---|---|
| CN2008101621988A CN101423283B (en) | 2008-11-18 | 2008-11-18 | High efficiency detoxifcation method and device of organic wastewater |
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| CN101423283A CN101423283A (en) | 2009-05-06 |
| CN101423283B true CN101423283B (en) | 2011-05-18 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219323B (en) * | 2011-03-31 | 2012-07-25 | 华中师范大学 | Method for simultaneously removing organic pollutants and ammonia in waste water and reactor |
| CN104071939B (en) * | 2014-07-16 | 2015-10-07 | 长春黄金研究院 | Nonferrous metal mine method of wastewater treatment |
| CN105461128B (en) * | 2015-12-18 | 2018-01-05 | 碳氢技术工程管理（武汉）有限公司 | A kind of device and processing method of combined treatment high COD sewage |
| CN107673460A (en) * | 2017-11-07 | 2018-02-09 | 苏州淡林环境科技有限公司 | A kind of advanced oxidation device for wastewater treatment |
| CN108585329A (en) * | 2018-07-05 | 2018-09-28 | 山东省城市供排水水质监测中心 | A kind of UV/O3/H2O2Advanced oxidation reactor and technique |
| CN109025868B (en) * | 2018-10-23 | 2023-08-18 | 中国科学院新疆生态与地理研究所 | Treatment method of drilling waste |
| CN110115993A (en) * | 2019-04-24 | 2019-08-13 | 广西博世科环保科技股份有限公司 | A kind of method of high-level oxidation technology processing adsorption saturation powdered activated carbon |
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| CN1194626A (en) * | 1995-08-29 | 1998-09-30 | 韩国科学技术研究院 | Waste water treatment by catalytic oxidation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1194626A (en) * | 1995-08-29 | 1998-09-30 | 韩国科学技术研究院 | Waste water treatment by catalytic oxidation |
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| 钟理.高级氧化技术在废水处理中的应用研究进展.上海环境科学.2000,(1000-3975),569页3.2节,570页4.2节. * |
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Owner name: ZHEJIANG DONGTIANHONG ENVIRONMENTAL PROTECTION ENG Free format text: FORMER OWNER: XIANG XIANFU Effective date: 20110728 |
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Effective date of registration: 20110728 Address after: 310012, 10F-2 building, A building, Paradise Software Park, 3 West Road, Hangzhou, Xihu District, Zhejiang, China Patentee after: Zhejiang Dongtianhong Environmental Protection Engineering Co., Ltd. Address before: 310012, 10F-2 building, A building, Paradise Software Park, 3 West Road, Hangzhou, Xihu District, Zhejiang, China Patentee before: Xiang Xianfu |