CN102503017A - Method for treating non-degradable organic wastewater by multielement multiphase membrane technology - Google Patents
Method for treating non-degradable organic wastewater by multielement multiphase membrane technology Download PDFInfo
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- 238000002360 preparation method Methods 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
The invention discloses a method for treating non-degradable organic wastewater by a multielement multiphase membrane technology. According to the method, Fe ions are loaded on montmorillonoid used as a carrier by an ion exchange method to catalyze Fenton reaction so as to treat non-degradable organic wastewater at high concentration; catalytic efficiency of photocatalysis is enhanced by using an ultrasonic cavitation effect, a radical effect and a mechanical effect, so organic matter in water is subjected to synergistic degradation by ultrasound and photocatalysis; and therefore, the degradation efficiency of organic pollutant can be improved, and filtering is performed by a membrane separation technology. The method is stable and reliable in treatment effect, and the removal rate of chemical oxygen demand (COD) can reach over 90 percent.
Description
Technical field
The present invention relates to technical field of waste water processing, particularly relate to the method that a kind of polynary heterogeneous membrane technique is handled organic wastewater with difficult degradation thereby.
Background technology
According to measuring and calculating, 50% of the human wealth in the world today derives from chemical, yet also can produce a large amount of organic pollutants in process of production when chemical brings glad tidings to the mankind.China has become big producing countries such as dyestuff, agricultural chemicals and medicine in the world at present; The factory effluent of these enterprises contains the organic pollutant of a large amount of poisonous and harmfuls and bio-refractory; These pollutents are complex structure, high, the long half time of toxicity mostly; And can persistently be present in the environment,, human beings'health and environment caused disadvantageous effect through the food web accumulation.
High-level oxidation technology is the radical that utilizes oxidisability extremely strong; Especially hydroxyl radical free radical (oxidizing potential 2.80V; Be only second to fluorine 2.87V) organic pollutant in the oxygenolysis water; Organic pollutant to poisonous and harmful in the water and difficult degradation is particularly effective, and it is fast, simple to operate and be easy to advantage such as equipment management to have speed of response, becomes the focus of water technology research gradually.
At present, existing many achievements in research have confirmed the practicality of high-level oxidation technology in water treatment, and have shown application prospects.According to the difference of free-radical generating mode, high-level oxidation technology mainly is divided into Fenton method, O
3Oxidation style, catalytic wet oxidation technology, supercritical water oxidation, photocatalytic oxidation, electrochemical catalysis method and ultrasonic degradation method etc.
Produce the shortcoming of a large amount of iron containing sludges and the loss of avoiding catalyzer in order to overcome traditional F enton catalytic oxidation reaction finishing back; A kind of method commonly used is that the iron ion that catalytic performance is the strongest loads on the different carriers; When keeping its catalytic activity, obtain the solid-liquid separating power, avoid secondary pollution.Therefore, people begin big quantity research loaded catalyst.And the appropriate catalyst carrier not only can increase the contact area of heterogeneous catalyst reaction, strengthens the hydrophobicity and the chemicalstability of catalyzer, and can prolong the work-ing life of catalyzer.
The mechanism of action of ultrasonic-photochemical catalytic oxidation recombining process is based on the influence to photocatalytic process of ultransonic cavitation effect, radical effect and mechanical effect.The HTHP that the ultrasonic cavitation effect produces is that ultrasonic-photocatalytic oxidation degradation has been created an extreme physicochemical environment.Simultaneously, the free radical reaction that HTHP causes has increased the concentration of radical in the solution, has promoted the destruction degraded of organic pollutant.Introduce ultrasonic after, it produces the intensive microjet at the photocatalyst microparticle surfaces, can depolymerization and dispersed light catalyzer, photocatalyst activity surface and catalytic site are come out more, the functionally active of raising photocatalyst.In addition, microjet can also improve reactant in the water to photocatalyst surface and the reaction product rate of mass transfer to water, thereby reaches the purpose that improves degradation efficiency.Therefore; In ultrasonic-photochemical catalysis recombining process; Ultrasonic not only can the oxidation organic pollutant, and photochemical catalytic oxidation had obvious facilitation, promptly ultrasonic-photochemical catalytic oxidation has realized synergy but not both simple mathematical stacks of ultrasonic and photocatalytic degradation.
Membrane separation technique is a kind of promotion by outside energy or chemical potential, is separating medium with the selective permeation film, and two components or multicomponent gas or liquid are carried out isolating technology.Compare with traditional separation method (evaporation, extraction or IX etc.), it can be operated at normal temperatures, does not have phase transformation.Be with a wide range of applications at aspects such as chemical industry, light industry, electronics, medicine, weaving, biotechnology, environmental improvement, metallurgy.
But up to now, Shang Weijian has and utilizes supported catalyst, ultrasonic-ultraviolet catalytic oxidation Synergistic method to combine with membrane separation technique to handle the relevant report of waste water.
Summary of the invention
Technical problem to be solved by this invention provides a kind of supported catalyst, ultrasonic-method of wastewater treatment that the ultraviolet catalytic oxidation Synergistic method combines with membrane separation technique that utilizes; Can effectively handle multiple high concentrated organic wastewater, make the waste water COD clearance after the processing high.
The present invention solves the problems of the technologies described above with following technical scheme:
The polynary heterogeneous membrane technique of the present invention is handled the method for organic wastewater with difficult degradation thereby; Its operation steps is; Waste water is handled through supported catalyst reaction zone, ultrasonic-ultraviolet catalytic reaction zone and membrane sepn filtering unit successively, and the concrete processing condition of each treatment zone are following:
1) supported catalyst reaction zone: this district adopts heterogeneous catalysis Fenton reaction, and active ingredient Fe ion is fixed on carrier polynite top layer again and H
2O
2Carry out the Fenton reaction, wherein catalyzer and H
2O
2The consumption mass ratio be 1: 2-3, the amount ranges of its reagent is 12-16ml/L, this reaction zone is adapted to the pH value and is the wastewater treatment of 2-10;
2) ultrasonic-ultraviolet catalytic reaction zone: this district is equipped with ultrasonic-ultraviolet catalytic reactor drum; It is made up of ultrasonic reactor, fixed photocatalyst and ultraviolet source; The fixed photocatalyst constitutes fixed bed or flow-through cell in ultrasonic reactor; Wherein, the ultrasonic reactor operating frequency is: 20-110KHz, ultraviolet dosage are 1000mJ/cm
2More than, the consumption of fixed photocatalyst is 0.05-0.3g/m
3
3) membrane sepn filtering unit: this unit filter membrane adopts submerged ultrafiltration, and material is PVDF, aperture 0.01 μ m.
Described supported catalyst reaction zone preferably is adapted to handle the waste water of pH value for 4.5-7.5.
Said at ultrasonic-ultraviolet catalytic reaction zone, the fixed photocatalyst of employing is a solid nano titanium oxide, and its carrier is sand, sheet glass or ring pipe inwall.
The inventive method compared with prior art has the following advantages:
The inventive method has combined technology such as load heterogeneous catalysis Fenton reaction, ultrasonic cavitation processing, photochemistry synergistic oxidation reduction reaction and membrane separation technique; Traditional technology of utilizing Fenton reagent to handle waste water has been done improvement significantly; Effectively reduce the consumption of Fenton reagent; Greatly reduced simultaneously the generation of chemical sludge, can efficiently handle the high concentrated organic wastewater of difficult degradation, the waste water COD clearance after the processing reaches more than 90%.
Description of drawings
Fig. 1 is the process flow diagram of the inventive method.
Fig. 2 is the structural representation of the device that the supported catalyst reaction zone adopts among Fig. 1.
Fig. 3 is the structural representation of the device of ultrasonic among Fig. 1-ultraviolet catalytic reaction zone employing.
Fig. 4 is the schematic top plan view of Fig. 3.
Fig. 5 is the structural representation of membrane sepn filtering unit among Fig. 1.
Wherein, 1. water inlet, 2.H
2O
2Pond, 3. peristaltic pump, 4. aerating apparatus, 5. water outlet, 6. submerged membrane assembly; 7.Fe ion/MMT catalyzer, 8.UV light source, 9. silica tube, 10. water outlet, 11. fixed catalysts; 12. water inlet, 13. ultrasonic reactors, 14. water inlets, 15. peristaltic pumps, 16. aerating apparatuss; 17. concentrated solution outlet, the outlet of 18. scavenging solutions, 19. membrane modules, 20. back flushing pipelines, 21. flush boxs.
Embodiment
Below in conjunction with accompanying drawing the present invention is done further description.
As shown in Figure 1; The polynary heterogeneous membrane technique of the present invention is handled the method for organic wastewater with difficult degradation thereby; Mainly be to utilize supported catalyst, ultrasonic-ultraviolet cooperating degradation technique and membrane separation technique to combine to handle organic wastewater with difficult degradation thereby; Waste water is handled through supported catalyst reaction zone, ultrasonic-ultraviolet catalytic reaction zone and membrane sepn filtering unit successively, and the concrete processing condition of each treatment zone are following:
1) supported catalyst reaction zone: this district adopts heterogeneous catalysis Fenton reaction, and active ingredient Fe ion is fixed on carrier polynite top layer again and H
2O
2Carry out the Fenton reaction.Wherein, the preparation of catalyzer utilization traditional technology, the mass ratio of its Fe ion and polynite is 1: 8.Catalyzer and H
2O
2The consumption mass ratio be 1: 2-3, the amount ranges of its reagent is 12-16ml/L, this reaction zone is adapted to the pH value and is the wastewater treatment of 2-10, but more excellent scope then is 4.5-7.5.Organic initial degradation rate obviously improves along with the increase of catalyst levels, and the transformation efficiency of eventual degradation thing also slightly improves.But degradation effect worsened on the contrary to some extent when catalyst levels was excessive, so, in the Fenton reaction, all there is optimum catalyst levels usually.Usually along with H
2O
2The increase of concentration, organic degradation rate improve synchronously and at a certain H
2O
2Concentration reaches optimum value.Impel Fe through controlling above condition
3+/ Fe
2+Circulation and H
2O
2Thereby be converted into hydroxyl radical free radical and improve the Fenton oxidizing reaction.
This district can adopt device as shown in Figure 2, and Fe ion/MMT catalyzer 7 is housed in this device, and the bottom is provided with aerating apparatus 4, and the outside, bottom connects H through peristaltic pump 3
2O
2Pond 2, the device internal upper part has submerged membrane assembly 6 and water inlet 1, and submerged membrane assembly 6 connects water outlet 5 through peristaltic pump.Its working process is: pending waste water is fed through water inlet 1 be equipped with in the device of Fe ion/MMT catalyzer 7, feed H through peristaltic pump 3
2O
2After, open aerating apparatus 4 reactions 30 minutes, last, the waste water after handling is got into next reaction zone through the submerged membrane assembly with the peristaltic pump extraction.
2) ultrasonic-ultraviolet catalytic reaction zone: this district is equipped with fixed-bed type ultrasonic-ultraviolet catalytic reactor drum, it is made up of ultrasonic reactor, fixed photocatalyst and ultraviolet source.The common carrier of fixed catalyzer is sand, sheet glass or ring pipe inwall.Catalyzer constitutes fixed bed or flow-through cell in ultrasonic reactor, through the excitation of light source, the organic pollutant of the fixed bed of flowing through is by photocatalyst and supersonic synergic degraded.This type of reactor drum has been avoided aftertreatment problems such as separation and the recovery of photocatalyst, and can carry out successive reaction.Wherein, ultrasonic generator operating frequency: 20-110KHz is through the effect of ultrasonic generator, and making the organic macromolecule compound decomposition is small molecules, and ultraviolet dosage is 1000mJ/cm
2More than, the fixed photocatalyst can adopt the solid nano titanium deoxide catalyst, and its consumption is 0.05-0.3g/m
3
This district can adopt like Fig. 3 and device shown in Figure 4; This device inner core is equipped with the UV light source 8 with silica tube 9 protections, and the device inwall is equipped with ultrasonic reactor 13, and fixed photocatalyst 11 is housed between inner core and the inwall; Water inlet 12 is arranged at the bottom in the device simultaneously, and water outlet 10 is arranged at top.Its working process is: the waste water after will handling from a last reaction zone feeds this device through water inlet 12, gets into next reaction zone through water outlet in reaction under the synergy of ultraviolet catalytic and ultrasonic generator after 10-15 minute.
3) membrane sepn filtering unit: this unit filter membrane adopts ultra-filtration membrane, is to be impellent with pressure, is separated into purpose with macromole and small molecules, and the submerged ultrafiltration material that this unit adopts is PVDF, aperture 0.01 μ m.In ultra-filtration process, depth of water liquid is under force, and through stream film surface, solute and the solute group bigger than fenestra are trapped, and discharge with current, become liquid concentrator, and liquid concentrator and a small amount of waste residue are handled by solid waste; Solvent (water) and small molecules solute less than fenestra see through film, become scavenging solution (cleaner liquid).
This district can adopt device as shown in Figure 5, and this device is equipped with membrane module 19, and the bottom is provided with aerating apparatus 16.Membrane module left side down connects into the mouth of a river 14 through peristaltic pump 15, and the right side connects concentrated solution outlet 17; The membrane module upper left side connects flush box 21 through back flushing pipeline 20, and the right side connects scavenging solution outlet 18.Its working process is: at first, close concentrated solution outlet 17 and open scavenging solution outlet 18, the waste water after will handling from a last reaction zone gets into membrane module 19 through water inlet 14, through behind aerating apparatus 16 aerations treated water being discharged from scavenging solution outlet 18.When scavenging solution exports 18 water outlets and has some setbacks; Should carry out back flushing; Its operational process is: close scavenging solution outlet 18 and open concentrated solution outlet 17; From flush box 21, extract washing lotion out through back flushing pipeline 20 rinsing membrane modules 19 with peristaltic pump, discharge by concentrated solution outlet at last and accomplish backwash process.
Embodiment one
The bagasse that method of the present invention is applied to after early stage materialization, the biochemical treatment is stacked waste water (COD
CrBe 2635mg/L), its pH value is 7.5.Waste water is injected the supported catalyst reaction zone.Open peristaltic pump, inject H
2O
2And input Fe ion/MMT catalyzer, wherein catalyzer and H
2O
2The consumption mass ratio be 1: 2, total consumption of its reagent is 12ml/L.Opening aerating apparatus subsequently makes catalyzer fully contact with waste water.Open the water outlet peristaltic pump again and water is evacuated to ultrasonic-ultraviolet catalytic reaction zone.After getting into ultrasonic-ultraviolet catalytic reaction zone, regulate throttling valve to proper flow quantitative response 10 minutes, open uv lamp and ultrasonic generator then, wherein ultraviolet dosage is 1200mJ/cm
2, the consumption of solid nano titanium deoxide catalyst is 0.05g/m
3, the ultrasonic reactor operating frequency is 80KHz.At last water is evacuated to membrane sepn filtering unit (pvdf membrane, aperture are 0.01 μ m).Take a sample after the water outlet, measure COD
CrBe 138.1mg/L, COD
CrClearance reach more than 90%, treatment effect is good.
Embodiment two
Be applied to the starch wastewater (COD of tapioca(flour) factory after early stage materialization, the biochemical treatment
CrBe 5250mg/L), its pH value is 4.5.Waste water is injected the supported catalyst reaction zone.Open peristaltic pump, inject H
2O
2And input Fe ion/MMT catalyzer, wherein catalyzer and H
2O
2The consumption mass ratio be 2: 5, total consumption of its reagent is 16ml/L.Opening aerating apparatus subsequently makes catalyzer fully contact with waste water.Open the water outlet peristaltic pump again and water is evacuated to ultrasonic-ultraviolet catalytic reaction zone.After getting into ultrasonic-ultraviolet catalytic reaction zone, regulate throttling valve to proper flow quantitative response 15 minutes, open uv lamp and ultrasonic generator then, wherein ultraviolet dosage is 1000mJ/cm
2, the consumption of solid nano titanium deoxide catalyst is 0.2g/m
3, the ultrasonic reactor operating frequency is 110KHz.At last water is evacuated to membrane sepn filtering unit (pvdf membrane, aperture are 0.01 μ m).Take a sample after the water outlet, measure COD
CrBe 261.2mg/L, COD
CrClearance can reach more than 90%.
Embodiment three
Be applied to the molasses containing waste water (COD of sugar refinery after early stage materialization, the biochemical treatment
CrBe 4815mg/L), its pH value is 7.3.Waste water is injected the supported catalyst reaction zone.Open peristaltic pump, inject H
2O
2And input Fe ion/MMT catalyzer, wherein catalyzer and H
2O
2The consumption mass ratio be 1: 3, total consumption of its reagent is 15ml/L.Opening aerating apparatus subsequently makes catalyzer fully contact with waste water.Open the water outlet peristaltic pump again and water is evacuated to ultrasonic-ultraviolet catalytic reaction zone.After getting into ultrasonic-ultraviolet catalytic reaction zone, regulate throttling valve to proper flow quantitative response 15 minutes, open uv lamp and ultrasonic generator then, wherein ultraviolet dosage is 1200mJ/cm
2, the consumption of solid nano titanium deoxide catalyst is 0.3g/m
3, the ultrasonic reactor operating frequency is 20KHz.At last water is evacuated to membrane sepn filtering unit (pvdf membrane, aperture are 0.01 μ m).Take a sample after the water outlet, measure COD
CrBe 337.1mg/L, COD
CrClearance can reach more than 90%.
Certainly; The embodiment of the above, application examples; It is preferred embodiments of the present invention; Be not to limit practical range of the present invention,, include in claim of the present invention so all equivalences of doing according to the described technology of claim of the present invention, treatment process and principle change or modify.
Claims (3)
1. a polynary heterogeneous membrane technique is handled the method for organic wastewater with difficult degradation thereby; It is characterized in that; Waste water is handled through supported catalyst reaction zone, ultrasonic-ultraviolet catalytic reaction zone and membrane sepn filtering unit successively, and the concrete processing condition of each treatment zone are following:
1) supported catalyst reaction zone: this district adopts heterogeneous catalysis Fenton reaction, and active ingredient Fe ion is fixed on carrier polynite top layer again and H
2O
2Carry out the Fenton reaction, wherein, the preparation of catalyzer utilization traditional technology, the mass ratio of its Fe ion and polynite is 1: 8; Catalyzer and H
2O
2The consumption mass ratio be 1: 2-3, the amount ranges of its reagent is 12-16ml/L, this reaction zone is adapted to the pH value and is the wastewater treatment of 2-10;
2) ultrasonic-ultraviolet catalytic reaction zone: this district is equipped with ultrasonic-ultraviolet catalytic reactor drum; It is made up of ultrasonic reactor, fixed photocatalyst and ultraviolet source; The fixed photocatalyst constitutes fixed bed or flow-through cell in ultrasonic reactor; Wherein, the ultrasonic reactor operating frequency is: 20-110KHz, ultraviolet dosage are 1000mJ/cm
2More than, the consumption of fixed photocatalyst is 0.05-0.3g/m
3
3) membrane sepn filtering unit: this unit filter membrane adopts submerged ultrafiltration, and material is PVDF, aperture 0.01 μ m.
2. handle the method for organic wastewater with difficult degradation thereby according to the said polynary heterogeneous membrane technique of claim 1, it is characterized in that described supported catalyst reaction zone preferably is adapted to handle the waste water of pH value for 4.5-7.5.
3. handle the method for organic wastewater with difficult degradation thereby according to the said polynary heterogeneous membrane technique of claim 1; It is characterized in that; Said at ultrasonic-ultraviolet catalytic reaction zone, the fixed photocatalyst of employing is a solid nano titanium oxide, and its carrier is sand, sheet glass or ring pipe inwall.
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| CN104193083A (en) * | 2014-07-25 | 2014-12-10 | 中国环境科学研究院 | Combined device for third-level sewage filtration and sewage treatment method |
| CN104211254A (en) * | 2014-08-26 | 2014-12-17 | 常州大学 | Biofilm-photocatalysis device of phosphorus-containing substances in micro-polluted water |
| CN104211256A (en) * | 2014-08-26 | 2014-12-17 | 常州大学 | COD biological film-photocatalytic device in slightly-polluted water body |
| CN104843901A (en) * | 2015-05-14 | 2015-08-19 | 苏州膜海分离技术有限公司 | Bleaching and dyeing wastewater treatment method with combination of advanced oxidation and ultrafiltration |
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| CN109502857A (en) * | 2017-09-15 | 2019-03-22 | 上海江柘环境工程技术有限公司 | A kind of processing equipment and its processing method of polyvinyl chloride centrifugation mother liquid waste water |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101406838A (en) * | 2008-11-20 | 2009-04-15 | 武汉大学 | Method for preparing active carbon supported ferriferous oxide catalyst and wastewater treatment system thereof |
| CN101786756A (en) * | 2010-02-09 | 2010-07-28 | 广西博世科环保科技有限公司 | Process method for treating hardly-biodegradable organic wastewater |
| CN101786689A (en) * | 2010-02-10 | 2010-07-28 | 厦门市威士邦膜科技有限公司 | Membrane separation concentrated water treatment method and integral coupling device |
-
2011
- 2011-11-09 CN CN 201110351925 patent/CN102503017B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101406838A (en) * | 2008-11-20 | 2009-04-15 | 武汉大学 | Method for preparing active carbon supported ferriferous oxide catalyst and wastewater treatment system thereof |
| CN101786756A (en) * | 2010-02-09 | 2010-07-28 | 广西博世科环保科技有限公司 | Process method for treating hardly-biodegradable organic wastewater |
| CN101786689A (en) * | 2010-02-10 | 2010-07-28 | 厦门市威士邦膜科技有限公司 | Membrane separation concentrated water treatment method and integral coupling device |
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