CN102491483B - Method for reducing and degrading chlorinated organic waste water by using two-metal powder - Google Patents
Method for reducing and degrading chlorinated organic waste water by using two-metal powder Download PDFInfo
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- CN102491483B CN102491483B CN 201110417669 CN201110417669A CN102491483B CN 102491483 B CN102491483 B CN 102491483B CN 201110417669 CN201110417669 CN 201110417669 CN 201110417669 A CN201110417669 A CN 201110417669A CN 102491483 B CN102491483 B CN 102491483B
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Abstract
The invention discloses a method for reducing and degrading chlorinated organic waste water by using two-metal powder, which comprises the following steps: regulating the pH value of the chlorinated organic waste water from which solid impurities are removed to 6 to 9; adding Fe-Al two-metal powder into the chlorinated organic waste water under a constant pressure, and fully stirring to obtain mixed liquid; and reducing and degrading the chlorinated organic waste water by the Fe-Al two-metal powder assisted by a bidirectional pulse current. The method has the advantages of great reduction in cost and high degrading effect, and thus, is more suitable to be used in industry.
Description
Technical field
The present invention relates to come chloro-organic waste water is carried out with thermometal-powder the method for harmless treatment.
Background technology
Chlorinatedorganic comprises chlorinated aliphatic hydrocarbon, chlorination aromatic hydrocarbon and organochlorine pesticide etc.Along with the widespread use of these chlorinatedorganics in every field, inevitable just have a large amount of organic chloro-organic waste waters of chloro that contains to be discharged in the environment.Because chlorinatedorganic is a class difficult degradation, the great organic compound of hazardness, so, must carry out harmless treatment to chloro-organic waste water, for this reason, people have done a large amount of research and many effective meanss have been arranged, and chemical reduction method is one of them.Chemical reduction method comprises Zero-valent Iron reduction method and thermometal-powder reduction method etc.Just, Zero-valent Iron reduction method deoxidization, degradation efficient is too low, though and the thermometal-powder reduction method can remedy the shortcoming of Zero-valent Iron reduction method, but general thermometal-powder catalyst preparation process is complicated, form thermometal-powder catalyzer coating at carrier and need special process, and the reducing metal that catalytic activity is high (such as palladium etc.) expensive, also need during degrading chloro-organic waste water under comparatively high temps and pressure, carry out, so that the total expenses that chloro-organic waste water is processed is higher.For overcoming the deficiency of above-mentioned thermometal-powder reduction method, publication number is that CN101575150A, name are called the patent application of " with the method for microwave reinforced thermometal-powder degrading chloro-organic waste water ", and the powder that has proposed direct use bimetal (Fe-Zn, Fe-Al, Fe-Mn) comes the method for degrading chloro-organic waste water.The prior art has added tensio-active agent (mixture of polyethers 2020 and propyl carbinol) simultaneously in chloro-organic waste water to be degraded, and adds microwave reinforced subsidiary conditions.The method has been saved complicated thermometal-powder catalyst preparation process; When degrading chloro-organic waste water, can carry out under the state of relatively low at normal pressure and temperature (25～40 ℃).Really obtained also that the waste water treatment cost is low, efficient is high, reduction effect good, effect simple to operate.Yet, because the thermometal-powder consumption of the prior art is too many, processes one liter of chloro-organic waste water and just need thermometal-powder 50g, and so that the reduction of its waste water treatment cost is still more limited.
Summary of the invention
The objective of the invention is, provide a kind of degradation effect poor unlike prior art, but the cost that chloro-organic waste water is administered can be got the method for more using thermometal-powder deoxidization, degradation chloro-organic waste water.
For the technical scheme that realizes described purpose is a kind of like this method with thermometal-powder deoxidization, degradation chloro-organic waste water, aspect same as the prior art is that the step of the method is as follows:
(1) chloro-organic waste water of collecting is filtered, to remove solid impurity;
(2) the pH value of the chloro-organic waste water of solid impurity has been removed in adjusting, to pH=6～9;
(3) under atmospheric pressure state, thermometal-powder added in the chloro-organic waste water regulated after the pH value fully stir, with the one-tenth mixed solution, then under subsidiary conditions, carry out deoxidization, degradation;
(4) in step (3) afterwards, filter out the thermometal-powder in the mixed solution, obtain the aqueous solution of deoxidization, degradation;
Its improvements are: the described thermometal-powder of step (3) is the Fe-Al thermometal-powder, and its granularity all is not more than 0.5mm, and the ratio of both molar weights is Fe: Al=1: 1～2: 1; Fe-Al thermometal-powder: chloro-organic waste water=3g/L～6g/L;
Described subsidiary conditions are electrode insertions and access Bipolar pulse current in mixed solution; Wherein, the direct impulse current density is 0.75A/cm
2～1.25A/cm
2, the forward conduction time is 5ms, and the turn-off time is 1ms, and the working hour is 60ms; The rp pulse current density is 0.125A/cm
2～0.25 A/cm
2, the reverse-conducting time is 5ms, and the turn-off time is 1ms, and the working hour is 12ms;
The temperature of the described deoxidization, degradation of step (3) is normal temperature, and the time finishes in can not proceeding down at deoxidization, degradation.
Can find out that from scheme the present invention processes the Fe-Al thermometal-powder consumption of one liter of chloro-organic waste water, and 3g～6g is only arranged, 50g compares with the prior art consumption, obviously provides cost savings.In addition, need add simultaneously tensio-active agent in the chloro-organic waste water because the present invention has also saved prior art, and only under the normal temperature state, degrade, therefore, further provide cost savings again.Greatly saving in the cost situation, but its degradation effect reason poor unlike prior art is, pulsed electrical field is that the sense of current and break-make are made the direct current that the gap changes, the peak point current of the direct current of this variation when conducting is equivalent to several times even tens times of conventional DC electricity, this instantaneous high current density can make the various ions in the chloro-organic waste water under high overpotential transfer transport occur just, and owing to the different asymmetry pulse electric fields that form of forward and reverse working hour, can produce discontinuous current, when current lead-through, electrochemical polarization increases, and metal ion fully is deposited near the cathodic area; When electric current turn-offed, discharge ion returned to again starting point concentration near the cathodic area, has eliminated concentration polarization.The asymmetry pulse electric field is accompanied by periodic reverse can produce the back diffusion layer at the solid-liquid interface place of negative electrode and chloro-organic waste water formation.Like this, can accelerate the rate of catalysis reaction of Fe-Al thermometal-powder as catalyzer on the one hand, the Fe-Al thermometal-powder can also carry out sufficient deoxidization, degradation to chlorinatedorganic at back diffusion layer place in addition, thereby become possibility so that only process chloro-organic waste water with a small amount of Fe-Al thermometal-powder, and obtain the good result poor unlike prior art (seeing the checking example for details).In brief, compared with prior art, the present invention is more suitable in industrial applications.
The invention will be further described below in conjunction with embodiment.
Embodiment
A kind of method with thermometal-powder deoxidization, degradation chloro-organic waste water, the step of the method is as follows:
(1) chloro-organic waste water of collecting is filtered, to remove solid impurity;
(2) the pH value of the chloro-organic waste water of solid impurity has been removed in adjusting, to pH=6～9;
(3) under atmospheric pressure state, thermometal-powder added in the chloro-organic waste water regulated after the pH value fully stir, with the one-tenth mixed solution, then under subsidiary conditions, carry out deoxidization, degradation;
(4) in step (3) afterwards, filter out the thermometal-powder in the mixed solution, obtain the aqueous solution of deoxidization, degradation;
In the present invention, the described thermometal-powder of step (3) is Fe-Al thermometal-powder (iron-Al bimetal powder), and its granularity all is not more than 0.5mm(namely, crosses 32 order Tyler standard sieves), the ratio of both molar weights is Fe: Al=1: 1～2: 1; Fe-Al thermometal-powder: chloro-organic waste water=3g/L～6g/L;
Described subsidiary conditions are electrode insertions and access Bipolar pulse current in mixed solution; Wherein, the direct impulse current density is 0.75A/cm
2～1.25A/cm
2, the forward conduction time is 5ms, and the turn-off time is 1ms, and the working hour is 60ms; The rp pulse current density is 0.125A/cm
2～0.25 A/cm
2, the reverse-conducting time is 5ms, and the turn-off time is 1ms, and the working hour is 12ms;
The temperature of the described deoxidization, degradation of step (3) is normal temperature, and the time finishes in can not proceeding down at deoxidization, degradation.
Further, for obtaining better effect, in this embodiment, the anode of the described electrode of its step (3) is Graphite Electrodes, and negative electrode is Pb-Ag-Ca-S
rThe quad alloy electrode.
The present invention has passed through verification experimental verification, and testing sequence is described identical with this embodiment.Wherein, in the Fe-Al thermometal-powder, its component is commercially available reduced iron powder and aluminium powder.Pulsed electrical field is provided by the SMD Double-pulse Plating Power Source, and the anode of electrode used therein is Graphite Electrodes, and negative electrode is Pb-Ag-Ca-S
rThe quad alloy electrode.The chloro-organic waste water that produces in the chloroprene rubber production is taken out in test with waste water; Measure the COD value of these wastewater treatment front and back during checking with dichromate titration (GB11914-89), and be calculated as follows out the COD clearance of reaction treatment effect.
COD clearance=(the initial COD value of chloro-organic waste water-process the COD value of the rear solution)/initial COD value of chloro-organic waste water * 100%
The result see the following form (test is 100mL with the amount of chloro-organic waste water).
Can find out that from proof list the present invention is former thereby cause cost significantly reduces except the consumption because of the Fe-Al thermometal-powder greatly reduces etc., the COD clearance is also quite high.
Claims (2)
1. method with thermometal-powder deoxidization, degradation chloro-organic waste water, the step of the method is as follows:
(1) chloro-organic waste water of collecting is filtered, to remove solid impurity;
(2) the pH value of the chloro-organic waste water of solid impurity has been removed in adjusting, to pH=6～9;
(3) under atmospheric pressure state, thermometal-powder added in the chloro-organic waste water regulated after the pH value fully stir, with the one-tenth mixed solution, then under subsidiary conditions, carry out deoxidization, degradation;
(4) in step (3) afterwards, filter out the thermometal-powder in the mixed solution, obtain the aqueous solution of deoxidization, degradation;
It is characterized in that: the described thermometal-powder of step (3) is the Fe-Al thermometal-powder, and its granularity all is not more than 0.5mm, and the ratio of both molar weights is Fe: Al=1: 1～2: 1; Fe-Al thermometal-powder: chloro-organic waste water=3g/L～6g/L;
Described subsidiary conditions are electrode insertions and access Bipolar pulse current in described mixed solution; Wherein, the direct impulse current density is 0.75A/cm
2～1.25A/cm
2, the forward conduction time is 5ms, and the turn-off time is 1ms, and the working hour is 60ms; The reverse impulse current density is 0.125A/cm
2～0.25 A/cm
2, the reverse-conducting time is 5ms, and the turn-off time is 1ms, and the working hour is 12ms;
The temperature of the described deoxidization, degradation of step (3) is normal temperature, and the time finishes in can not proceeding down at deoxidization, degradation.
2. described method with thermometal-powder deoxidization, degradation chloro-organic waste water according to claim 1 is characterized in that the anode of the described electrode of step (3) is Graphite Electrodes, and negative electrode is Pb-Ag-Ca-Sr quad alloy electrode.
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| CN 201110417669 CN102491483B (en) | 2011-12-14 | 2011-12-14 | Method for reducing and degrading chlorinated organic waste water by using two-metal powder |
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| CN 201110417669 CN102491483B (en) | 2011-12-14 | 2011-12-14 | Method for reducing and degrading chlorinated organic waste water by using two-metal powder |
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| CN102491483A CN102491483A (en) | 2012-06-13 |
| CN102491483B true CN102491483B (en) | 2013-03-27 |
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| CN107758809A (en) * | 2017-11-16 | 2018-03-06 | 贵州省新材料研究开发基地 | A kind of method that bimetallic assists electric treatment organic wastewater |
| CN107673448A (en) * | 2017-11-16 | 2018-02-09 | 贵州省新材料研究开发基地 | A kind of electrode material of organic wastewater treatment by electrochemical electrolytic engineering |
| CN109879374A (en) * | 2019-02-24 | 2019-06-14 | 贵州省过程工业技术研究中心 | A kind for the treatment of of Organic Wastewater electrode material and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575150A (en) * | 2009-06-10 | 2009-11-11 | 重庆大学 | Method for degrading chloro-organic waste water by using double-metals reinforced by microwaves |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575150A (en) * | 2009-06-10 | 2009-11-11 | 重庆大学 | Method for degrading chloro-organic waste water by using double-metals reinforced by microwaves |
Non-Patent Citations (2)
| Title |
|---|
| 电解对氯苯酚稀水溶液中脱氯降解机理研究;郑璐等;《环境科学研究》;20041231;第17卷(第6期);54-58,69 * |
| 郑璐等.电解对氯苯酚稀水溶液中脱氯降解机理研究.《环境科学研究》.2004,第17卷(第6期),54-58,69. |
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