CN100371261C - Method for treating wastewater through catalysis of connected load type Ti02 of plasma in liquid phase - Google Patents
Method for treating wastewater through catalysis of connected load type Ti02 of plasma in liquid phase Download PDFInfo
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- CN100371261C CN100371261C CNB2006100520035A CN200610052003A CN100371261C CN 100371261 C CN100371261 C CN 100371261C CN B2006100520035 A CNB2006100520035 A CN B2006100520035A CN 200610052003 A CN200610052003 A CN 200610052003A CN 100371261 C CN100371261 C CN 100371261C
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- Prior art keywords
- titanium dioxide
- wastewater
- liquid phase
- present
- catalysis
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000002351 wastewater Substances 0.000 title claims abstract description 27
- 239000007791 liquid phase Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 9
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000005495 cold plasma Effects 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims abstract description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003344 environmental pollutant Substances 0.000 claims description 5
- 231100000719 pollutant Toxicity 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 239000000356 contaminant Substances 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 244000005700 microbiome Species 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 241000700605 Viruses Species 0.000 abstract 1
- 238000006065 biodegradation reaction Methods 0.000 abstract 1
- 239000010842 industrial wastewater Substances 0.000 abstract 1
- 230000001473 noxious effect Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000013543 active substance Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 230000009931 harmful effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 230000007096 poisonous effect Effects 0.000 description 3
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000002925 chemical effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229940090668 parachlorophenol Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000003612 virological effect Effects 0.000 description 1
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- Water Treatment By Electricity Or Magnetism (AREA)
- Physical Water Treatments (AREA)
Abstract
The present invention discloses a method for treating wastewater through the catalysis of liquid phase plasma combined with load type Ti02, which utilizes the cold plasma generated by the electric discharge of high voltage impulse liquid phase to remove contaminants in the wastewater, activated carbon loading and containing anatase crystal type titanium dioxide is added in the treated wastewater, the mass loading content of the titanium oxide is from 0.2 to 20.0%, and the concentration of the activated carbon loading the titanium dioxide in the wastewater is from 0.1 g/L to 2.0 g/L. The method of the present invention has simple and convenient operation; the present invention can absorb ultraviolet light and excite the separation of electrons in the conduction band and holes in the valence band through the titanium dioxide of solid oxide having good photocatalysis property, and the wave length of the ultraviolet light is less than 320 NM; the present invention utilizes the high oxidation of the holes to generate OH free radicals or to directly oxidize the contaminants, the combined activated carbon simultaneously has higher adsorption for the contaminants, and the removing benefit of the organic contaminants is enhanced. The present invention has the advantage of low operation cost, and can be used for treating toxic and noxious hard biodegradation industrial wastewater and removing and decontaminating viruses and microorganisms.
Description
Technical field
The present invention relates to a kind of method of handling waste water, especially liquid phase plasma combined loading type TiO
2The method for the treatment of wastewater through catalysis of connected.
Background technology
At a large amount of trade effluents that discharged in the present industrial production, it is of a great variety, complicated component, and chemical oxygen demand (COD) (COD) concentration height, biodegradability is poor, and characteristics such as poisonous and harmful adopt conventional materialization or biochemical processing to be difficult to control effectively and to have administered.Therefore, high-level oxidation technology becomes the new technology and the novel method of current processing difficult for biological degradation and poisonous and harmful trade effluent.
High-level oxidation technology utilizes the larger molecular organics (or microorganism) in the various living radicals attack trade effluents, destroys its molecular structure (or cell), thereby organic waste water is purified.But,, cause it further having certain limitation and subject range in the popularization because there are shortcomings such as severe reaction conditions, poor selectivity, cost height in high-level oxidation technology.The disclosed pulse liquid phase plasma power supply unit of CN1673103, utilize liquid phase electricimpulse technology, employing high-voltage pulse power source generation voltage rise time weak point (＜100ns), pulse width is narrow, and (＜200ns) forceful electric power is pressed, the operating parameter of high-voltage pulse is: voltage peak 10-40KV, leading edge of impulse 100ns, pulse-repetition 50-200Hz, thereby can be under the situation that does not make the acceleration of ions in the electric field, electronics is quickened, thereby produce the high energy unbound electron, form cold plasma, excite the generation active substance in water body, pollutants in waste water is removed in degraded.Have physical influence and chemical effect in this excitation process simultaneously, physical influence can form UV-light and shockwave, and its intensity depends on the energy of discharge; Chemical effect is mainly impelled the formation of active substance, as: OH, O, H
2O
2, O
3Etc. various living radicals, thereby high pressure pulse discharge is handled UV-light, shockwave and living radical that waste water can utilize discharge to form, form multifactorial Synergistic degradation effects such as high-energy electron, ultraviolet ray, ozone, the enhancement process effect is that light harvesting, electricity, chemical oxidation are in the novel water technology of one.
But, in the conventional liquid electro-plasma system degradation of contaminant time longer, energy consumption is bigger, and power supply and electrode are all had great loss.Simultaneously, liquid electricity produces light moment launches, and fully do not absorbed by water body, so that photochemical effect is not fully utilized to the degraded of pollutent, and the photochemical energy utilization ratio is extremely low in this system.
Summary of the invention
The purpose of this invention is to provide and a kind ofly can make full use of the luminous energy that produces in the liquid electricity system, improve pollutants removal rate, reduce the liquid phase plasma combined loading type TiO of power supply energy consumption
2The method for the treatment of wastewater through catalysis of connected.
Liquid phase plasma combined loading type TiO of the present invention
2The method for the treatment of wastewater through catalysis of connected, be that the cold plasma that utilizes the high-voltage pulse discharge in water to produce is removed pollutants in waste water, adding the mass loading per-cent of gac titanium dioxide that load contains the titanium dioxide of anatase crystal in processed waste water is 0.2-20.0%, and the concentration of the gac of carried titanium dioxide in waste water is 0.1-2.0g/L.
Among the present invention, the mass loading per-cent of titanium dioxide is 1.7%.The preferred concentration of the gac of carried titanium dioxide in waste water is 0.5g/L.
The inventive method is simple, and is easy and simple to handle, utilizes soild oxide titanium dioxide to have fabulous photocatalysis characteristic, can absorb UV-light less than the 320nm wavelength, excite the electronics of conduction band and separating of valence band hole, utilize the strong oxidation in hole to produce the OH free radical, or the direct oxidation pollutent.The electronics of conduction band has reductibility simultaneously.When handling waste water, on liquid electro-plasma reactor, apply high-voltage pulse, produce the liquid phase cold plasma,, thereby produce more active substances in conjunction with the photocatalysis performance of titanium dioxide.Simultaneously, utilize gac that pollutent is had stronger adsorption, unite the photocatalysis of its surperficial titanium dioxide, improve the removal benefit of organic pollutant, the conserver power source energy consumption.All improve the active substance productive rate in liquid phase and liquid phase gas phase mixed system, improved processing efficiency to a greater extent, running cost is low, and can reuse the gac of carried titanium dioxide.The present invention can apply under single liquid phase, gas phase volatile pollutants and the gas-liquid two-phase mixed solution electrical environment, has improved degradation capability, thereby has improved the generation efficient of the active substance in the water body greatly, strengthens the water treatment effect.The present invention can be used for handling difficult for biological degradation and poisonous and harmful trade effluent and viral micro-organisms and removes purification.
Embodiment
Example 1
Contain the waste water that para-chlorophenol is a pollutent with the inventive method processing, the starting point concentration of pollutent is 100mg/L in the waste water, initial pH:6.5-7.0, specific conductivity: 3.0-6.0.Used high-voltage pulse power source is a 4-37 type high-voltage pulse power source, operating parameter: voltage peak (14.0KV), leading edge of impulse (about 100ns), pulse-repetition: (150Hz).Needle electrode and board-like interelectrode distance are 2mm under the liquid, and amount of oxygen exposes to the sun: 100L/h.Treatment time is 42min.With this understanding, add the gac (AC-TiO that load contains the titanium dioxide of anatase crystal
2), its concentration in waste water is 0.2g/L.Load TiO
2The diameter of activated carbon granule be 55-110 μ m, the mass loading per-cent of titanium dioxide is 1.7%.
Table 1 has provided example 1 and has added the gac of carried titanium dioxide, do not add the gac of carried titanium dioxide and only add the comparison of the liquid electricity system of gac to water treatment effect and efficiency.
Table 1
| Pollutent | Catalyst for titanium dioxide loaded | Add concentration (g/L) | Reaction rate constant, K 4-CP，(×10 -3S -1) | Remove efficiency (g/kWh) |
| Para-chlorophenol | AC-TiO 2 | 0 | 1.56 | 0.92 |
| AC | 2.0 | 1.86 | 1.10 | |
| AC-TiO 2 | 2.0 | 3.23 | 1.90 |
By table 1 as seen, add load TiO
2The system of AC in reaction digit rate constant (plan first _ order kinetics equation) all improved 107.1% than the liquid electricity system that does not add the gac of carried titanium dioxide and only add gac.Add load TiO
2The system of AC in removal efficiency (promptly removing 50% o'clock energy expenditure (g/kWh) of starting point concentration) all improved 107.1% than the system that does not add the gac of carried titanium dioxide and do not add gac, and add load TiO
2The system of AC in reaction digit rate constant and remove the system that Energy Efficiency Ratio adds AC and all improved 73.7%.
Claims (3)
1. liquid phase plasma combined loading type TiO
2The method for the treatment of wastewater through catalysis of connected, the cold plasma that utilizes the high-voltage pulse discharge in water to produce is removed pollutants in waste water, the operating parameter of high-voltage pulse is: voltage peak 10-40KV, leading edge of impulse 100ns, pulse-repetition 50-200Hz, it is characterized in that in processed waste water, adding the gac that load contains the titanium dioxide of anatase crystal, load TiO
2The diameter of activated carbon grain be 55-110 μ m, the mass loading per-cent of titanium dioxide is 0.2-20.0%, the concentration of the gac of carried titanium dioxide in waste water is 0.1-2.0g/L.
2. liquid phase plasma combined loading type TiO according to claim 1
2The method for the treatment of wastewater through catalysis of connected, the mass loading per-cent that it is characterized in that titanium dioxide is 1.7%.
3. liquid phase plasma combined loading type TiO according to claim 1
2The method for the treatment of wastewater through catalysis of connected is characterized in that the concentration of gac in waste water of carried titanium dioxide is 0.5g/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100520035A CN100371261C (en) | 2006-06-16 | 2006-06-16 | Method for treating wastewater through catalysis of connected load type Ti02 of plasma in liquid phase |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100520035A CN100371261C (en) | 2006-06-16 | 2006-06-16 | Method for treating wastewater through catalysis of connected load type Ti02 of plasma in liquid phase |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1872716A CN1872716A (en) | 2006-12-06 |
| CN100371261C true CN100371261C (en) | 2008-02-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100520035A Expired - Fee Related CN100371261C (en) | 2006-06-16 | 2006-06-16 | Method for treating wastewater through catalysis of connected load type Ti02 of plasma in liquid phase |
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| Country | Link |
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| CN (1) | CN100371261C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008113128A1 (en) * | 2007-03-19 | 2008-09-25 | Viva Blu Pty Ltd | Method and apparatus for effecting a predetermined transformation |
| CN104860381A (en) * | 2015-03-31 | 2015-08-26 | 南京大学 | Method and apparatus for treating atrazine waste water by using combination of multi-needle corona discharge and titanium dioxide catalyst |
| CN106277545A (en) * | 2016-09-30 | 2017-01-04 | 成都信息工程大学 | A kind of method of circulated sprinkling photocatalyst Cement Composite Treated by Plasma painting wastewater |
| CN106277177A (en) * | 2016-10-25 | 2017-01-04 | 浙江富春江环保热电股份有限公司 | The device and method of plasma body cooperative photocatalysis treatment percolate |
| CN110776110A (en) * | 2019-10-18 | 2020-02-11 | 黑龙江大学 | Method for treating phenolic wastewater by integrated photocatalysis-microorganism-adsorption process |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005138076A (en) * | 2003-11-10 | 2005-06-02 | Yamaha Corp | Ethylene oxide decomposition processing apparatus |
| CN1673103A (en) * | 2005-03-24 | 2005-09-28 | 浙江大学 | Pulse liquid phase plasma power supply unit for waste water treatment |
| CN1695796A (en) * | 2005-03-11 | 2005-11-16 | 哈尔滨工业大学 | Preparation for catalyst of Nano titanium dioxide, and method for treating ozonized water of catalysis |
| CN1695797A (en) * | 2005-03-15 | 2005-11-16 | 浙江大学 | Method for preparing photocatalyst of titanium dioxide carried by active carbon |
| EP1640343A1 (en) * | 2003-06-13 | 2006-03-29 | Reiken, Inc. | Photocatalyst water treating apparatus |
| CN2780745Y (en) * | 2005-03-24 | 2006-05-17 | 浙江大学 | Pulsed plasma gas liquid discharge device for waste water treatment |
-
2006
- 2006-06-16 CN CNB2006100520035A patent/CN100371261C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1640343A1 (en) * | 2003-06-13 | 2006-03-29 | Reiken, Inc. | Photocatalyst water treating apparatus |
| JP2005138076A (en) * | 2003-11-10 | 2005-06-02 | Yamaha Corp | Ethylene oxide decomposition processing apparatus |
| CN1695796A (en) * | 2005-03-11 | 2005-11-16 | 哈尔滨工业大学 | Preparation for catalyst of Nano titanium dioxide, and method for treating ozonized water of catalysis |
| CN1695797A (en) * | 2005-03-15 | 2005-11-16 | 浙江大学 | Method for preparing photocatalyst of titanium dioxide carried by active carbon |
| CN1673103A (en) * | 2005-03-24 | 2005-09-28 | 浙江大学 | Pulse liquid phase plasma power supply unit for waste water treatment |
| CN2780745Y (en) * | 2005-03-24 | 2006-05-17 | 浙江大学 | Pulsed plasma gas liquid discharge device for waste water treatment |
Non-Patent Citations (1)
| Title |
|---|
| 活性炭－纳米二氧化钛电催化氧化处理染料废水. 刘占孟等.水资源保护，第22卷第3期. 2006 * |
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| CN1872716A (en) | 2006-12-06 |
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Granted publication date: 20080227 Termination date: 20130616 |