CN1850643A - Method for degrading aminobenzene or/and nitrobenzene in waste water by electrolytic process - Google Patents
Method for degrading aminobenzene or/and nitrobenzene in waste water by electrolytic process Download PDFInfo
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- CN1850643A CN1850643A CN200610040664.6A CN200610040664A CN1850643A CN 1850643 A CN1850643 A CN 1850643A CN 200610040664 A CN200610040664 A CN 200610040664A CN 1850643 A CN1850643 A CN 1850643A
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- nitrobenzene
- aniline
- anode
- wastewater
- cathode
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- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 title claims abstract description 82
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000002351 wastewater Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000000593 degrading effect Effects 0.000 title claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000012528 membrane Substances 0.000 claims abstract description 15
- 238000005341 cation exchange Methods 0.000 claims abstract description 13
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 12
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000005684 electric field Effects 0.000 claims abstract description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 7
- 239000010935 stainless steel Substances 0.000 claims abstract description 7
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 6
- 239000010439 graphite Substances 0.000 claims abstract description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 5
- 150000001768 cations Chemical class 0.000 claims abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- 229910052719 titanium Inorganic materials 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 238000005070 sampling Methods 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 238000010525 oxidative degradation reaction Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 3
- 238000011033 desalting Methods 0.000 claims 1
- 238000007599 discharging Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 239000002585 base Substances 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000010405 anode material Substances 0.000 abstract description 3
- 239000010406 cathode material Substances 0.000 abstract description 3
- 150000004679 hydroxides Chemical class 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- -1 etc. Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 244000208060 Lawsonia inermis Species 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Abstract
The invention is a method for degrading aniline or/and nitrobenzene in waste water by electrolysis process, adopting an electrobath with a dividing cation exchange membrane in the middle, adding the waste water containing aniline or/and nitrobenzene and salts into an anode chamber, adding thin NaOH solution into an cathode chamber, circulating by circulating pump, separately, where the anode material is Ti-base coated ruthenium or Ti-base coated lead dioxide, and the cathode material is stainless steel or graphite, electrolyzing by DC, and oxidizing and degrading and removing aniline or/and nitrobenzene, and besides, cations dissociated from the salts in the waste water pass through the cation exchange membrane into the cathode chamber under the action of the DC electric field and combine with OH groups to produce hydroxides, thus able to recover alkali solution and desalt the waste water so as to benefit follow-up biochemical processing units. And after the solutions in the anode and cathode chambers are circulated for a period of time, it samples them, and as the concentrations of the aniline or/and nitrobenzene in the solution in the anode chamber decrease to the required values, it stops operating and discharges the solutions.
Description
Technical Field
The invention relates to a wastewater treatment method, in particular to a method for treating aniline or nitrobenzene wastewater.
Background
In the production processes of fine chemical engineering, light industry and the like, various aniline and nitrobenzene waste water is often generated and is difficult to biodegrade. At present, the methods for treating the wastewater mainly adopt physical methods such as adsorption, extraction, steam stripping, chemical oxidation, micro-electrolysis, biological treatment and the like, and have the defects that the cost is high, the removal rate is not high, or the stable standard reaching is difficult to ensure.
Disclosure of Invention
The invention aims to provide an electrochemical treatment method of aniline or nitrobenzene wastewater, which degrades aniline and nitrobenzene through electrode reaction and catalytic oxidation of an anode chamber.
The technical scheme of the invention is as follows.
A method for degrading aniline or/and nitrobenzene in waste water by electrolysis is characterized in that waste water containing aniline or/and nitrobenzene (shown in figure 1) is placed in an electrolysis bath provided with a stirrer, and selected anode materials are titanium-based metal oxide coating electrodes such as: titanium base coating ruthenium, titanium base coating iridium or titanium base coating lead dioxide, etc., the cathode material is stainless steel or graphite, direct current electrolysis is conducted, aniline or/and nitrobenzene are removed by oxidative degradation, sampling is conducted after certain time of electrolysis, when the concentration of aniline or/and nitrobenzene in the feed liquid is reduced to a required value, the operation is stopped, and the feed liquid is discharged.
The method for degrading aniline or/and nitrobenzene in wastewater by electrolysis can adopt an electrolytic cell separated by a cation exchange membrane (an ionic membrane electrolytic cell is shown in figure 2) when the wastewater contains salts. Adding wastewater containing aniline or/and nitrobenzene and salt into an anode chamber, adding a dilute NaOH solution (with the mass percentage concentration of 0.5-4%) into a cathode chamber as an auxiliary electrolyte, and using a titanium-based metal oxide coating electrode as an anode material: titanium-based coating ruthenium, titanium-based coating iridium or titanium-based coating lead dioxide, etc., wherein the cathode material is stainless steel or graphite, the ionic membrane is heterogeneous and homogeneous cation exchange membrane, direct current electrolysis is performed, aniline or/and nitrobenzene are removed by oxidative degradation, and meanwhile, salt-dissociated cations such as Na in the wastewater+And the like, under the action of a direct current electric field, penetrates through the cation exchange membrane to enter the cathode chamber, and reacts with OH-The hydroxide is generated by combination, so that the alkali liquor can be recovered, the original wastewater can be desalted, and the subsequent biochemical treatment unit is facilitated. Yang (Yang)After the electrode chamber and cathode chamber feed liquid is electrolyzed for a certain time, sampling is carried out, when the concentration of aniline or/and nitrobenzene in the anode chamber feed liquid is reduced to a required value, the operation is stopped, and the feed liquid is discharged.
In the method for degrading aniline or/and nitrobenzene in wastewater by using the electrolyticmethod, the electrolytes in the anode chamber and the cathode chamber can be respectively circulated by using the circulating pumps so as to enhance mass transfer and reduce the volume of the electrolytic cell.
The principle of the invention is as follows:
the following reactions take place in the electrolytic cell:
cathode:
anode:
under the action of electric field H2Dissociation of O into H+And OH-，H+Obtaining electrons at the cathode to form H2，OH-Discharge at the cathode to generate nascent states [ O]and H+. Catalytic oxidation and nascent oxygen [ O]at the anode]Under the combined action of the two components, aniline or/and nitrobenzene are oxidized and degraded.
In the method for degrading the aniline or/and the nitrobenzene in the wastewater by the electrolytic method, the temperature of the solution in the electrolytic cell is controlled by the electric heater so as to achieve the best treatment effect.
The method can simply, conveniently and effectively oxidize and degrade the aniline or/and nitrobenzene, can effectively desalt and recycle alkali when the waste water contains salt, and can effectively treat the waste liquid containing the aniline or/and nitrobenzene by matching with the subsequent biochemical treatment.
Drawings
FIG. 1 is a schematic view of an electrolytic cell in which: 1 is an anode; 2 is a stirrer; 3 is a cathode; 4 is an electrolytic bath.
FIG. 2 is an electrolytic cell divided by a cation exchange membrane in the middle, wherein: 1 is an anode: 3 is a cathode; 5 is an anode chamber; 6 is a cathode chamber; 7 is a treated water outlet; 8 is a circulating pump; 9 is a cation exchange membrane; and 10 is a heater.
Detailed Description
The present invention is described in further detail below with reference to examples.
Example 1
M-type dye wastewater, aniline concentration 210mg/l, nitrobenzene concentration 240mg/l, salt content 15g/l, chroma 3500And (4) doubling. 500ml of wastewater is taken and placed in the anode chamber 4 of the electrolytic cell as shown in figure 2. 500ml of 0.5% NaOH solution is placed in a cathode chamber 5 of an electrolytic cell and is respectively circulated by a circulating pump 7, a cation exchange membrane 2 is a polyethylene heterogeneous cation exchange membrane (3361 BW type produced by Shanghai chemical water treatment materials Co., Ltd.), an anode 1 is made of titanium-based coated ruthenium (produced by future water chemistry Co., Ltd., Xinxiang city, Henan), a cathode 3 is made of stainless steel and has the specification of 0.2 x 0.4m, the circulating liquid flow of the anode chamber 4 and the cathode chamber 5 is both 20L/h, the temperature of wastewater in the anode chamber 4 is controlled by an electric heater 6 at 60 ℃, the pH is 4, the circulating time is 3h under the voltage of a direct current electric field, and the wastewater is sampled and analyzed after the machine is shut down. After treatment, the aniline removal rate in the wastewater is 97.5%, the nitrobenzene removal rate is 75%,and the TOC removal rate is 84.3% (indicating that the degraded aniline and nitrobenzene in the wastewater are almost completely oxidized into CO2And H2O), the inorganic salt removal rate is 38%, and the chroma removal rate is 98%.
Example 2
The K type dye wastewater has aniline concentration of 175mg/l, nitrobenzene concentration of 199mg/l, salt content of 10g/l and chroma of 4000 times. 500ml of wastewater is taken and placed in the anode chamber 4 of the electrolytic cell as shown in figure 2. Placing 500ml of 4% NaOH solution in cathode chamber 5 of electrolytic cell without pump circulation, wherein cation exchange membrane 2 is polyethylene heterogeneous cation exchange membrane (Shanghai Kazai Water treatment materials Co., Ltd.)Model 3362BW produced), the anode 1 was made of titanium-based coated iridium (produced by future water chemistry ltd, new and rural areas, henna), the cathode 3 was made of stainless steel with a specification of 0.2 × 0.4m, the temperature of wastewater in the anode chamber 4 was controlled to 40 ℃ with a heater, pH 6, and the cycle time was 3 hours under a dc electric field voltage of 4V. After the machine is stopped, sampling and analysis are carried out, and after treatment, the removal rate of aniline in the wastewater is 95.3 percent, the removal rate of nitrobenzene is 53.4 percent, and the removal rate of TOC is 69.4 percent (indicating that the degraded aniline and nitrobenzene in the wastewater are almost completely oxidized into CO2And H2O), the inorganic salt removal rate is 20%, and the chroma removal rate is 94%.
Example 3
The nitrobenzene production wastewater has aniline concentration of 340mg/l and nitrobenzene concentration of 284 mg/l. 500ml of wastewater is taken and put into an electrolytic tank 4 with a stirrer 2, as shown in figure 1, the anode 1 is made of titanium-based coated lead dioxide (future water chemistry Co., Ltd. in Xinxiang city of Henan province), the cathode 3 is made of graphite (Nantong carbon plant), a heater is used for controlling the temperature of the wastewater in the electrolytic tank to be normal temperature (25 ℃), the voltage of a direct current electric field is 10V, and the electrolysis time is 3 h. After the machine is stopped, sampling and analysis are carried out, and the removal rate of aniline, nitrobenzene, TOC and chroma in the treated wastewater is 95.4%, 83.2%, 85.2% and 75% respectively.
Claims (5)
1. A method for degrading aniline or/and nitrobenzene in wastewater by an electrolytic method is characterized by comprising the following steps: placing wastewater containing aniline or/and nitrobenzene in an electrolytic tank (4) provided with a stirrer (2), wherein the anode (1) is a titanium-based metal oxide coating electrode, the cathode (3) is made of stainless steel or graphite, electrifying direct current for electrolysis, removing the aniline or/and nitrobenzene by oxidative degradation, sampling after electrolyzing for a certain time, and stopping operation when the concentration of the aniline or/and nitrobenzene in feed liquid is reduced to a required value to discharge the feed liquid.
2. A method for degrading aniline or/and nitrobenzene in wastewater by an electrolytic method is characterized by comprising the following steps: it is an electrolytic tank with a cation exchange membrane (2) in the middle for separation, the anode chamber (4) is added with waste water containing aniline or/and nitrobenzene and salt, the cathode chamber(5) Adding a dilute NaOH solution (with the concentration range of 0.5-4%) as an auxiliary electrolyte, selecting a titanium-based metal oxide coating electrode as an anode (1) material, adopting stainless steel or graphite as a cathode (3) material, electrifying direct current electrolysis, removing aniline or/and nitrobenzene by oxidative degradation, and simultaneously, leading cations dissociated from salt in the wastewater to pass through a cation exchange membrane under the action of a direct current electric field to enter a cathode chamber (5) and react with OH to form an OH-containing solution-Combining to generate hydroxide, desalting the original wastewater, circulating the feed liquid in the anode chamber (4) and the cathode chamber (5) for a certain time, sampling, and stopping operation when the concentration of aniline or/and nitrobenzene in the feed liquid in the anode chamber (4) is reduced to a required value, and discharging the feed liquid.
3. The method for degrading aniline or/and nitrobenzene in wastewater by electrolysis according to claim 2, characterized in that: the electrolytes in the anode chamber and the cathode chamber are circulated by a circulation pump (7) respectively.
4. A method according to claim 1 or 2, characterized by: the metal oxide coating electrode selected as the anode (1) material is a titanium-based ruthenium-coated electrode, a titanium-based iridium-coated electrode or a titanium-based lead dioxide-coated electrode.
5. A method according to claim 1 or 2, characterized by: the solution in the anode chamber (4) is controlled by an electric heater (6).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100406646A CN100389076C (en) | 2006-05-26 | 2006-05-26 | Method for degrading aminobenzene or/and nitrobenzene in waste water by electrolytic process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100406646A CN100389076C (en) | 2006-05-26 | 2006-05-26 | Method for degrading aminobenzene or/and nitrobenzene in waste water by electrolytic process |
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| CN1850643A true CN1850643A (en) | 2006-10-25 |
| CN100389076C CN100389076C (en) | 2008-05-21 |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102211829A (en) * | 2010-04-01 | 2011-10-12 | 上海晶园环保科技有限公司 | Advanced oxidation device and method for treating high-concentration organic substance wastewater |
| CN101514070B (en) * | 2009-04-07 | 2011-11-09 | 达斯玛环境科技（北京）有限公司 | Disposal technique of nitrobenzene-containing sewage |
| WO2011144594A1 (en) | 2010-05-21 | 2011-11-24 | Basf Se | Method and device for removing nitroaromatics from waste water |
| CN102328972A (en) * | 2011-10-27 | 2012-01-25 | 大连理工大学 | Device and method for treating waste water and preparing hydrogen simultaneously |
| CN102417264A (en) * | 2010-09-28 | 2012-04-18 | 中国石油化工股份有限公司 | Method for treating nitrochlorobenzene production wastewater |
| CN102417265A (en) * | 2010-09-28 | 2012-04-18 | 中国石油化工股份有限公司 | Method for effectively removing organic matters in wastewater from nitrochlorobenzene production |
| CN103466852A (en) * | 2013-09-26 | 2013-12-25 | 南京大学 | Sludge-reduction electrocatalytic reduction-oxidation pretreatment method for nitrotoluene production waste water |
| CN103708584A (en) * | 2013-12-24 | 2014-04-09 | 常州和方环保科技有限公司 | Aniline wastewater treatment process and application of product thereof |
| CN104891626A (en) * | 2015-06-25 | 2015-09-09 | 金双蕾 | Water treatment chemical for removing aniline compounds in water |
| CN105253958A (en) * | 2015-10-20 | 2016-01-20 | 河北丰源环保科技股份有限公司 | Electrochemical cathode and anode combined wastewater treatment method and device |
| CN108147505A (en) * | 2017-12-19 | 2018-06-12 | 北京科技大学 | A kind of device and method of Driven by Solar Energy wastewater treatment coupling production hydrogen |
| CN108164056A (en) * | 2017-12-28 | 2018-06-15 | 山西猗顿生态环保股份有限公司 | Aniline alkaline waste water treatment method |
| CN110054262A (en) * | 2019-05-27 | 2019-07-26 | 安徽工业大学 | A kind of ternary modified titanium-matrix electrode, preparation method and application |
| CN113044931A (en) * | 2021-03-23 | 2021-06-29 | 南京环保产业创新中心有限公司 | Treatment device for nitroaromatic wastewater, and cathode preparation method and application thereof |
-
2006
- 2006-05-26 CN CNB2006100406646A patent/CN100389076C/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101514070B (en) * | 2009-04-07 | 2011-11-09 | 达斯玛环境科技（北京）有限公司 | Disposal technique of nitrobenzene-containing sewage |
| CN102211829A (en) * | 2010-04-01 | 2011-10-12 | 上海晶园环保科技有限公司 | Advanced oxidation device and method for treating high-concentration organic substance wastewater |
| WO2011144594A1 (en) | 2010-05-21 | 2011-11-24 | Basf Se | Method and device for removing nitroaromatics from waste water |
| CN102417264A (en) * | 2010-09-28 | 2012-04-18 | 中国石油化工股份有限公司 | Method for treating nitrochlorobenzene production wastewater |
| CN102417265A (en) * | 2010-09-28 | 2012-04-18 | 中国石油化工股份有限公司 | Method for effectively removing organic matters in wastewater from nitrochlorobenzene production |
| CN102328972A (en) * | 2011-10-27 | 2012-01-25 | 大连理工大学 | Device and method for treating waste water and preparing hydrogen simultaneously |
| CN102328972B (en) * | 2011-10-27 | 2012-11-07 | 大连理工大学 | Device and method for treating waste water and preparing hydrogen simultaneously |
| WO2015043449A1 (en) * | 2013-09-26 | 2015-04-02 | 南京大学 | Method for sludge-reduced electrocatalytic reduction-oxidation pretreatment of nitrotoluene production wastewater |
| CN103466852A (en) * | 2013-09-26 | 2013-12-25 | 南京大学 | Sludge-reduction electrocatalytic reduction-oxidation pretreatment method for nitrotoluene production waste water |
| CN103466852B (en) * | 2013-09-26 | 2015-04-01 | 南京大学 | Sludge-reduction electrocatalytic reduction-oxidation pretreatment method for nitrotoluene production waste water |
| CN103708584A (en) * | 2013-12-24 | 2014-04-09 | 常州和方环保科技有限公司 | Aniline wastewater treatment process and application of product thereof |
| CN104891626A (en) * | 2015-06-25 | 2015-09-09 | 金双蕾 | Water treatment chemical for removing aniline compounds in water |
| CN105253958A (en) * | 2015-10-20 | 2016-01-20 | 河北丰源环保科技股份有限公司 | Electrochemical cathode and anode combined wastewater treatment method and device |
| CN108147505A (en) * | 2017-12-19 | 2018-06-12 | 北京科技大学 | A kind of device and method of Driven by Solar Energy wastewater treatment coupling production hydrogen |
| CN108164056A (en) * | 2017-12-28 | 2018-06-15 | 山西猗顿生态环保股份有限公司 | Aniline alkaline waste water treatment method |
| CN110054262A (en) * | 2019-05-27 | 2019-07-26 | 安徽工业大学 | A kind of ternary modified titanium-matrix electrode, preparation method and application |
| CN113044931A (en) * | 2021-03-23 | 2021-06-29 | 南京环保产业创新中心有限公司 | Treatment device for nitroaromatic wastewater, and cathode preparation method and application thereof |
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| CN100389076C (en) | 2008-05-21 |
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