CN102942241B - Method for organic wastewater electro-fenton treatment adopting bentonite - Google Patents
Method for organic wastewater electro-fenton treatment adopting bentonite Download PDFInfo
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- CN102942241B CN102942241B CN201210329716.7A CN201210329716A CN102942241B CN 102942241 B CN102942241 B CN 102942241B CN 201210329716 A CN201210329716 A CN 201210329716A CN 102942241 B CN102942241 B CN 102942241B
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- waste water
- wilkinite
- electrolytic cell
- organic wastewater
- bentonite
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- 239000002351 wastewater Substances 0.000 title claims abstract description 65
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 30
- 229910000278 bentonite Inorganic materials 0.000 title abstract description 7
- 239000000440 bentonite Substances 0.000 title abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010439 graphite Substances 0.000 claims abstract description 9
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 9
- 239000002244 precipitate Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- 239000010815 organic waste Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 71
- 229910052742 iron Inorganic materials 0.000 abstract description 33
- -1 iron ions Chemical class 0.000 abstract description 7
- 238000005868 electrolysis reaction Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005341 cation exchange Methods 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 239000003344 environmental pollutant Substances 0.000 description 12
- 231100000719 pollutant Toxicity 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 6
- 239000000975 dye Substances 0.000 description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- SXQCTESRRZBPHJ-UHFFFAOYSA-M lissamine rhodamine Chemical compound [Na+].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=C(S([O-])(=O)=O)C=C1S([O-])(=O)=O SXQCTESRRZBPHJ-UHFFFAOYSA-M 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003933 environmental pollution control Methods 0.000 description 1
- 235000021321 essential mineral Nutrition 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 210000000697 sensory organ Anatomy 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical group [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012799 strong cation exchange Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention provides a method for organic wastewater electro-fenton treatment adopting bentonite. The method comprises the following steps of 1, adding organic wastewater in an electrolytic cell, 2, adding dried bentonite into the electrolytic cell, 3, adding 0.1 to 0.2mL of a H2O2 solution into each liter of the organic wastewater, and 4, electrifying in the electrolytic cell at an electrolytic cell current of 5 to 40mA with continuous stirring for 3 to 6 hours so that organics in the organic wastewater are degraded by oxidation and is precipitated and separated, wherein an anode of the electrolytic cell is an iron sheet electrode; a cathode is a graphite electrode; after being carried out for 15 to 20min, an electrifying process is stopped for 30 to 40min and the electrifying cycle is repeated; and a stirring rate is in a range of 50 to 150r/min. Organic wastewater treated by the method satisfies discharge standards. Through cation exchange performances of bentonite, iron ions produced by electrolysis are transferred to bentonite layers so that the concentration of iron ions residual in wastewater is reduced and iron ion-modified bentonite having catalytic activity is obtained.
Description
Technical field
The present invention relates to environmental pollution control technique field, the electric Fenton that relates in particular to a kind of wilkinite participation is processed the method for organic waste water.
Background technology
Within 1894, by Fenton, found ferrous ion (Fe
2+) be hydrogen peroxide (H
2o
2) catalyzer, produce a kind of free radical of high oxidative capacity, (hydroxyl free radical, OH), is finally oxidized to carbonic acid gas and water with decontamination by the organism in waste water.The Fe that utilizes electrochemical process to produce
2+and H
2o
2as continuing source, we are referred to as electrolysis Fenton process.During electrolyzer energising, iron anode loses two electronics and is oxidized to Fe
2+, Fe
2+with the H adding
2o
2there is Fenton's reaction and generate OH.
In this system, cause the factor of organic matter degradation except OH, also have Fe
2+, Fe
3+although, part Fe
2+, Fe
3+hydrolyzable becomes Fe (OH)
2, Fe (OH)
3can precipitate, but still have a large amount of Fe
2+, Fe
3+still be present in waste water, the iron contamination that this brings water on the one hand, on the other hand due to the existence of yellow iron, can affect the sense organ of water.
Wilkinite is the tonstein take montmorillonite (Montmorillonite) as essential mineral.Montmorillonite is a kind of moisture layer aluminosilicate mineral, by aluminium of two silicon-oxy tetrahedron therebetween (magnesium) oxygen (hydrogen-oxygen) are octahedra, forms, and belongs to the three-layer clay mineral of 2:1 type.Lattice spacing is from being 0.96 ~ 2.14nm, and these nanoscale twins are reunited together, forms the clay particle that hundreds of nanometer arrives several microns.Due to the extremely strong wetting ability of wilkinite surface silicon oxide structure and the hydrolysis of interlayer cation, the non-constant of performance of the wilkinite adsorption treatment organic pollutant of non-modified.But wilkinite has very strong cation exchange capacity (CEC), under certain physical-chemical condition, not only Ca
2+, Mg
2+, Na
+, K
+deng can mutually exchange, and can and organic cation (as cats product) exchange crystal layer between positively charged ion.
Iron is exchanged between bentonite bed, can prepare the iron catalyst (research of montmorillonite-iron (III) catalyzer of alta-mud load, University Of Hebei's journal (natural science edition), 2001, the 1st phase, 65 pages), there is good catalytic effect, but this process complexity, needs the series of steps such as stirring, washing, oven dry, activation.
Summary of the invention
The technical problem to be solved in the present invention is: the iron ion difficulty that overcomes electric Fenton generation in prior art is removed, contaminant removal efficiency is low, the deficiency of alta-mud load iron catalyst process complexity, provides a kind of electric Fenton of wilkinite participation to process the method for organic waste water.
For solving the problems of the technologies described above the technical solution used in the present invention, be: the electric Fenton that a kind of wilkinite participates in is processed the method for organic waste water, and step is as follows:
In electrolyzer, add organic waste water, then add wilkinite, anode electrolytic cell electrode is the ferroelectric utmost point, and cathode electrode is Graphite Electrodes, connects electrolytic cell currents, in whole process, continue to stir, and after reaction finishes, precipitate and separate, waste water gets final product qualified discharge.
Described wilkinite was for pulverizing the dry wilkinite of 50 ~ 100 mesh sieves.
The solid-liquid mass ratio of described wilkinite and waste water is 1:100 ~ 500.
Described H
2o
2solution usage is in every liter of waste water, to add 0.1 ~ 0.2mL H
2o
2solution, the H that the present invention is used
2o
2solution is the H that common commercially available massfraction is 30%
2o
2solution.
Described electrolytic cell currents is 5 ~ 40mA, after every connection 15 ~ 20min, disconnects 30 ~ 40min, cyclical operation, reaction total time 3 ~ 6h.
Described mixing speed is 50 ~ 150r/min.
The invention has the beneficial effects as follows:
(1) in electrolysis, the ferroelectric utmost point is progressively oxidized the H that enters solution and add
2o
2reaction produces strong oxidizer OH, promotes pollutent to decompose.Intermittently power-on can be saved many electric energy.
(2) utilize the adsorptive power of wilkinite itself, the pollutent in waste water is adsorbed onto to solid surface, be conducive to electrolysis.
(3) utilize bentonitic cation exchange property, the iron ion that electrolysis is produced exchanges between bentonite bed, can reduce iron concentration remaining in waste water on the one hand, can obtain on the other hand having the iron ion modified alta-mud of catalytic activity.
Embodiment
3 embodiment of the present invention are below further provided:
Embodiment 1
In electrolyzer, adding concentration is the dyestuff orange II waste water of 30mg/L, then adds the dry wilkinite of pulverizing 100 mesh sieves, and the solid-liquid mass ratio of wilkinite and waste water is 1:500, in every liter of waste water, adds 0.2mLH
2o
2(30%, massfraction), anode electrolytic cell electrode is iron plate electrode, negative electrode is Graphite Electrodes, connects electrolytic cell currents 40mA, after every connection 20min, disconnect 40min, cyclical operation, continues in whole process to stir, mixing speed is 150r/min, through total time 3h, and the oxidized degraded of organism in waste water, precipitate and separate, analyze Pollutants in Wastewater concentration, clearance reaches 98.7%, and iron concentration remaining in waste water is 1.4mg/L.
The wilkinite that obtains of precipitation, after 105 ℃ of oven dry, continues for processing waste water as catalyzer, adds wilkinite 1g that this precipitation obtains and the H of 0.1mL in 1L concentration in the dyestuff that is 25mg/L orange II waste water
2o
2(30%, massfraction), stirs 50min, and precipitate and separate is analyzed Pollutants in Wastewater concentration, and clearance reaches 98.5%.
For same waste water, under same electric Fenton condition, but do not add wilkinite, in the identical treatment time, pollutants removal rate is 75.1%, iron concentration is 3.2g/L; Turn-off current, in waste water after treatment, continue to add wilkinite, the solid-liquid mass ratio of wilkinite and waste water is 1:500, in whole process, continue to stir, mixing rotating speed is 150r/min, through total time 3h, and precipitate and separate, final that the total clearance of pollutent is 78.3%, iron concentration is 11.7mg/L.
Be same waste water, under the same conditions, only add the wilkinite of same amount, but disconnect electric current, in the identical treatment time, pollutants removal rate is 2.1%; Precipitate and separate, removes wilkinite in above-mentioned waste water, waste water is put into every liter of waste water of electrolyzer and add 0.2mL H
2o
2(30%, massfraction), anode electrolytic cell electrode is iron plate electrode, negative electrode is Graphite Electrodes, connect electrolytic cell currents 40mA, after every connection 20min, disconnect 40min, cyclical operation, in whole process, continue to stir, mixing speed is 150r/min, through total time 3h, final that the total clearance of pollutent is 73.5%, iron concentration is 3.4g/L.
Embodiment 2
In electrolyzer, adding concentration is the dyestuff Xylene Red waste water of 25mg/L, then adds the dry wilkinite of pulverizing 50 mesh sieves, and the solid-liquid mass ratio of wilkinite and waste water is 1:100, in every liter of waste water, adds 0.1mLH
2o
2(30%, massfraction), anode electrolytic cell electrode is iron plate electrode, cathode electrode is Graphite Electrodes, connects electrolytic cell currents 5mA, after every connection 15min, disconnect 30min, cyclical operation, continues in whole process to stir, mixing speed is 50r/min, through total time 6h, and the oxidized degraded of organism in waste water, precipitate and separate, analyze Pollutants in Wastewater concentration, clearance reaches 99.1%, and iron concentration remaining in waste water is 2.1mg/L.
The wilkinite that obtains of precipitation, after 105 ℃ of oven dry, continues for processing waste water as catalyzer, adds wilkinite 1g that this precipitation obtains and the H of 0.1mL in 1L concentration in the dyestuff Xylene Red waste water that is 25mg/L
2o
2(30%, massfraction), stirs 50min, and precipitate and separate is analyzed Pollutants in Wastewater concentration, and clearance reaches 98.8%.
For same waste water, under same electric Fenton condition, but do not add wilkinite, in the identical treatment time, pollutants removal rate is 71.2%, iron concentration is 2.7g/L; Turn-off current, in waste water after treatment, continue to add wilkinite, the solid-liquid mass ratio of wilkinite and waste water is 1:500, in whole process, continue to stir, mixing rotating speed is 150r/min, through total time 3h, and precipitate and separate, final that the total clearance of pollutent is 73.3%, iron concentration is 13.4mg/L.
Be same waste water, under the same conditions, only add the wilkinite of same amount, but disconnect electric current, in the identical treatment time, pollutants removal rate is 1.7%; Precipitate and separate, removes wilkinite in above-mentioned waste water, waste water is put into every liter of waste water of electrolyzer and add 0.1mL H
2o
2(30%, massfraction), anode electrolytic cell electrode is iron plate electrode, cathode electrode is Graphite Electrodes, connect electrolytic cell currents 5mA, after every connection 15min, disconnect 30min, cyclical operation, in whole process, continue to stir, mixing speed is 50r/min, through total time 6h, final that the total clearance of pollutent is 72.7%, iron concentration is 3.7g/L.
Embodiment 3
In electrolyzer, adding concentration is the phenolic waste water of 15mg/L, then adds the dry wilkinite of pulverizing 100 mesh sieves, and the solid-liquid mass ratio of wilkinite and waste water is 1:500, adds 0.1mL H in every liter of waste water
2o
2(30%, massfraction), anode electrolytic cell electrode is iron plate electrode, cathode electrode is Graphite Electrodes, connects electrolytic cell currents 40mA, after every connection 20min, disconnect 40min, cyclical operation, continues in whole process to stir, mixing speed is 100r/min, through total time 5h, and the oxidized degraded of organism in waste water, precipitate and separate, analyze Pollutants in Wastewater concentration, clearance reaches 96.7%, and iron concentration remaining in waste water is 1.7mg/L.
The wilkinite that obtains of precipitation, after 105 ℃ of oven dry, continues for processing waste water as catalyzer, adds wilkinite 1g that this precipitation obtains and the H of 0.1mL in 1L concentration in the phenolic waste water that is 15mg/L
2o
2(30%, massfraction), stirs 50min, and precipitate and separate is analyzed Pollutants in Wastewater concentration, and clearance reaches 97.2%.
For same waste water, under same electric Fenton condition, but do not add wilkinite, in the identical treatment time, pollutants removal rate is 65.2%, iron concentration is 4.7g/L; Turn-off current, in waste water after treatment, continue to add wilkinite, the solid-liquid mass ratio of wilkinite and waste water is 1:500, in whole process, continue to stir, mixing rotating speed is 150r/min, through total time 3h, and precipitate and separate, final that the total clearance of pollutent is 70.5%, iron concentration is 10.3mg/L.
Be same waste water, under the same conditions, only add the wilkinite of same amount, but disconnect electric current, in the identical treatment time, pollutants removal rate is 1.3%; Precipitate and separate, removes wilkinite in above-mentioned waste water, waste water is put into every liter of waste water of electrolyzer and add 0.1mL H
2o
2(30%, massfraction), anode electrolytic cell electrode is iron plate electrode, cathode electrode is Graphite Electrodes, connect electrolytic cell currents 40mA, after every connection 20min, disconnect 40min, cyclical operation, in whole process, continue to stir, mixing speed is 100r/min, through total time 5h, final that the total clearance of pollutent is 73.5%, iron concentration is 4.5g/L.
Claims (4)
1. the electric Fenton that wilkinite participates in is processed a method for organic waste water, it is characterized in that: step is as follows:
In electrolyzer, add organic waste water, then add wilkinite, anode electrolytic cell electrode is the ferroelectric utmost point, and cathode electrode is Graphite Electrodes, connects electrolytic cell currents, in whole process, continue to stir, and after reaction finishes, precipitate and separate, waste water gets final product qualified discharge;
H
2o
2solution usage is in every liter of waste water, to add 0.1～0.2mL H
2o
2solution;
Described electrolytic cell currents is 5～40mA, after every connection 15～20min, disconnects 30～40min, cyclical operation, reaction total time 3～6h.
2. the electric Fenton that wilkinite according to claim 1 participates in is processed the method for organic waste water, it is characterized in that: described wilkinite is the dry wilkinite of pulverizing 50～100 mesh sieves.
3. the electric Fenton that wilkinite according to claim 1 participates in is processed the method for organic waste water, it is characterized in that: the solid-liquid mass ratio of described wilkinite and waste water is 1:100～500.
4. the electric Fenton that wilkinite according to claim 1 participates in is processed the method for organic waste water, it is characterized in that: described mixing speed is 50～150r/min.
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| CN107585834B (en) * | 2017-09-20 | 2020-05-15 | 中国地质大学（武汉） | electro-Fenton water treatment method based on iron-containing clay mineral supported palladium catalyst |
| CN108751382A (en) * | 2018-07-11 | 2018-11-06 | 常州大学 | A kind of preparation method of electricity Fenton packing material |
Citations (3)
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|---|---|---|---|---|
| CN101955280A (en) * | 2010-08-13 | 2011-01-26 | 南京赛佳环保实业有限公司 | Technology for processing high-concentration organic wastewater in composite electrochemical method |
| CN102070230A (en) * | 2010-12-10 | 2011-05-25 | 华中师范大学 | Method for removing organic matters in water by utilizing three-dimensional electrode electro-fenton and device thereof |
| CN102139979A (en) * | 2011-05-05 | 2011-08-03 | 中国科学院生态环境研究中心 | Method for treating coking waste water by electro-Fenton-coagulation combination process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955280A (en) * | 2010-08-13 | 2011-01-26 | 南京赛佳环保实业有限公司 | Technology for processing high-concentration organic wastewater in composite electrochemical method |
| CN102070230A (en) * | 2010-12-10 | 2011-05-25 | 华中师范大学 | Method for removing organic matters in water by utilizing three-dimensional electrode electro-fenton and device thereof |
| CN102139979A (en) * | 2011-05-05 | 2011-08-03 | 中国科学院生态环境研究中心 | Method for treating coking waste water by electro-Fenton-coagulation combination process |
Non-Patent Citations (2)
| Title |
|---|
| 铁交联膨润土- H2O2 联合氧化预处理苯胺基乙腈生产废水的研究;龙腾锐等;《给水排水》;20091231;第35卷;325-329 * |
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