CN102416336B - Preparation method of FeCl2/C-Cu catalyst used in post-processing of aniline and nitrobenzene biochemical wastewater - Google Patents
Preparation method of FeCl2/C-Cu catalyst used in post-processing of aniline and nitrobenzene biochemical wastewater Download PDFInfo
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- CN102416336B CN102416336B CN 201110316615 CN201110316615A CN102416336B CN 102416336 B CN102416336 B CN 102416336B CN 201110316615 CN201110316615 CN 201110316615 CN 201110316615 A CN201110316615 A CN 201110316615A CN 102416336 B CN102416336 B CN 102416336B
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Abstract
The invention belongs to the technical field of environmental water processing, and relates to a preparation method of a FeCl2/C-Cu catalyst used in the post-processing of aniline and nitrobenzene biochemical wastewater. According to the invention, the FeCl2/C-Cu chemical hydrolysis catalyst is used in the post-processing of the aniline and nitrobenzene biochemical wastewater. The preparation method of the catalyst comprises steps that: FeCl2 powder is stirred, and is dissolved in a water bath; when the FeCl2 powder is completely dissolved, extruded active carbon bars and NaCO3 powder are added to the solution; the mixture is stirred, vacuum-filtered, and washed; a washing terminal is determined by using AgNO3; when no white precipitate is produced, the mixture is baked, and cured with an increased temperature; Cu chips are added to the obtained material, and the mixture is well mixed. The catalyst is filled in a catalytic hydrolysis reaction tank which is connected to a biochemical tank, such that the post-processing of aniline and nitrobenzene biochemical wastewater can be carried out. Both the COD and the chromaticity of the aniline and nitrobenzene biochemical wastewater processed with the method reach a discharging standard. The FeCl2/C-Cu catalyst provided by the invention is advantaged in long service life and simple operation. The catalyst can be recovered and reused. The catalyst causes no secondary pollution. With the catalyst, the processing effect is substantially better than that with a common processing method.
Description
Technical field
The invention belongs to the ambient water processing technology field, relate to a kind of FeCl of passing through
2/ C-Cu electrochemical catalysis hydrolysis makes colourity and COD aniline not up to standard, nitrobenzene biochemical waste water reach the method for treating water of discharging standards.
Background technology
The method of processing at present aniline, nitrobenzene industrial wastewater mainly contains Physical, chemical oxidization method, biochemical process.Contain aniline, nitrobenzene waste water and usually can run into the problems such as secondary pollution or processing cost height with physics, chemical method processing.Also have in addition gamma-irradiation facture, ultrasonic wave facture, supercritical water oxidation method etc., for the processing of waste water provides larger space, but also use on a large scale in actual treatment.
The processing research of such waste water begins to low energy consumption, can not cause to environment the future development of processing method or the technique of secondary pollution.Certain company adopts the HSB bacterial classification of the Taiwan patent that Taiwan long Rong Huanbao limited company provides to carry out biochemical treatment, to adopt HSB(High Soution Bacteria) a kind of of technical development process effective method to aniline and nitrobenzene, but exist discharge water colourity after biochemical treatment, COD higher than discharging standards, and hard degradation.FeCl
2/ C-Cu electrochemical catalysis Hydrolyze method is processed for discharge water again, has effectively solved discharge water problem not up to standard.
Post processing report about this type of waste water is less.Tongji University, Zhenjiang Water Company's patent, the number of applying for a patent CN200910197532.8 introduces: a kind of for the catalytic internal electrolysis of iron of indegradable industrial effluent processing and the method for suspended filler biofilm integrated treatment industrial wastewater, comprise the following steps: the first step, preparation catalytic internal electrolysis of iron filtrate; Second step arranges conventional biological reaction pool, adds floating stuffing in biological reaction pool; The 3rd goes on foot, and the catalytic internal electrolysis of iron filtrate is positioned over the appropriate location of the top of aerating system in biological reaction pool, and the catalytic internal electrolysis of iron filtering device is placed in the current vertical direction; In the 4th step, sewage enters above-mentioned interior processing of biological reaction pool of having placed catalytic internal electrolysis of iron filtrate and floating stuffing; In the 5th step, the mixed liquor that will come from biological reaction pool enters second pond to carry out mud-water separation and discharges respectively.The present invention can process the difficult for biological degradation industrial wastewater with catalytic internal electrolysis of iron technology and bioanalysis organic coupling, can reduce toxic pollutant to the toxic action of microorganism, the biodegradability that improves waste water, enhancing Biochemical Treatment.
Peking University's patent, the number of applying for a patent CN200810113140.4 introduces: the present invention mainly processes by immobilized microorganism-anaerobic biofilter (I-AF) and immobilized microorganism-BAF (I-BAF); Wherein: after waste water process regulating reservoir homogeneous, add polymerization iron or polymeric aluminum coagulating, enter sedimentation basin and remove suspension (SS) in waste water; After this water outlet enters three grades of I-AF reactors and the further processing of level Four I-BAF reactor, qualified discharge.The method detailed step is seen specification.Advantage of the present invention is that immobilized microorganism technique has been adopted in biological treatment, has improved the mithridatism of microorganism, has realized the high-performance bio of the poisonous and harmful substances such as high nitrobenzene, aniline is removed, and has reduced processing cost, has realized discharged wastewater met the national standard.
Above-mentioned two patent p-nitrophenyls, aniline waste waters have certain treatment effect.But as pre-treatment, general for the treatment effect of high concentration entry, can not effectively alleviate the pressure of biological treatment, especially can not guarantee the up to standard of discharge water colourity, COD, and the present invention is biochemical water post processing, can effectively solve the drawback that foregoing invention exists.
Summary of the invention
The present invention is directed to that aniline, nitrobenzene waste water biochemical treatment drawback provide a kind of economy, are effective to aniline, the novel FeCl of nitrobenzene biochemical waste water post processing
2/ C-Cu electrochemistry hydrolysis method for preparing catalyst.
Technical solution of the present invention is: the FeCl that is used for aniline, the post processing of nitrobenzene biochemical waste water
2/ C-Cu method for preparing catalyst is: with the FeCl of 100-500g
2Powder is treated FeCl through stirring the water-bath dissolving
2After powder dissolves fully, add the NaCO of 200-800g extrusion active carbon and 20-200g
3Powder stirred after 3-8 hour, and filtering and washing is with AgNO
3Solution is judged the washing terminal point, when not producing white precipitate, cures under 50-200 ℃, and after drying fully, rising 100-400 ℃ solidifies 2-6, adds at last the broken wood shavings of 50-300gCu, mixes, and namely makes catalyst.
Usually, the preferred technical solution of the present invention is: with 350 gram FeCl
2Powder is placed in 3L distilled water, stirs the water-bath dissolving, treats FeCl
2After powder dissolves fully, add 500g extrusion active carbon, then add 100gNaCO
3Powder stirred 6 hours, with the material filtering and washing, with AgNO
3Solution is judged the washing terminal point, when not producing white precipitate, takes out material and cures under 105 ℃ 10 hours, and after drying fully, rising temperature to 270 ℃ curing 4 hours adds the broken wood shavings of 200gCu at last, mixes stand-by.
Adopt the FeCl of the inventive method preparation
2/ C-Cu electrochemistry hydrolysis catalyst carries out post processing to aniline, nitrobenzene biochemical waste water, is about to the FeCl of above-mentioned preparation
2/ C-Cu electrochemistry hydrolysis catalyst filling is in 10L catalytic hydrolysis reaction pond, and amount of filling is 1kg, and is connected to biochemistry pool, can carry out the post processing of aniline, nitrobenzene biochemical waste water.
Aniline, nitrobenzene biochemical waste water after the catalyst treatment of the inventive method preparation, COD, colourity all reach discharge standard.FeCl of the present invention
2/ C-Cu catalyst, its long service life, simple to operate, recyclable recycling, and do not bring the advantage such as secondary pollution into, treatment effect obviously is better than processing method commonly used, is worthy to be popularized.
The specific embodiment
Below by specific embodiment, the inventive method is described in detail.
FeCl used in following embodiment
2/ C-Cu electrochemistry hydrolysis catalyst adopts following method preparation: take 350 gram FeCl
2Powder is placed in the 3L beaker, adds distilled water to stir the water-bath dissolving, treats FeCl
2After powder dissolves fully, take 500g extrusion active carbon and add beaker, then add 100gNaCO
3Powder stirred 6 hours, poured sample into the funnel filtering and washing, with AgNO
3Solution judgement washing terminal point when not producing white precipitate, takes out sample to clean beaker and cured under 105 ℃ 10 hours, and after drying fully, rising temperature to 270 ℃ curing 4 hours is taken out sample and added the broken wood shavings of 200gCu, mixes stand-by.
With above-mentioned FeCl
2/ C-Cu electrochemistry hydrolysis catalyst filling is in 10L catalytic hydrolysis reaction pond, and amount of filling is 1kg, and is connected to biochemistry pool, opens valve and injects aniline and nitrobenzene biochemical treatment waste water, and water inlet speed is that every 10L stopped 20 hours.
Embodiment one:
First biochemical waste discharge of certain factory of taking a sample and the inventive method are processed waste water again and are carried out COD, determination of colority.
1, experiment device therefor
722N type visible spectrophotometer Shanghai rib light
YH type environmental protection Special electric hot jacket Shandong Yongxing instrument plant
Secondary quartz pure water distiller
The buret volumetric flask
2, experiment reagent
Mercuric sulfate is analyzed pure
Silver sulfate is analyzed pure
The concentrated sulfuric acid is analyzed pure
The ferron indicator
0.1mol/L sulfate of ammoniac standard liquid
Secondary distillation water (self-control)
3, sample treatment determination step
COD measures: biochemical water and process water sample 20mL again and be placed in cucurbit after getting 100 times of dilutions respectively, add 1g mercuric sulfate powder to mix, access constant temperature reflux, add silver sulfate powder 1g, add again the 30mL concentrated sulfuric acid, with the distilled water flushing tube wall that refluxes, add hot reflux 2h, add 80mL distilled water after cooling in sample, add three ferron indicator to shake up, with the titration of 0.1mol/L sulfate of ammoniac standard liquid, terminal point becomes the brownish red reading result, biochemical water 18.31ml, then to process water sample be 19.90ml.
Determination of colority: open spectrophotometer preheating half an hour, get distilled water and make zero stand-byly, get respectively 100 times of biochemical water of dilution and process again water sample 100mL and be placed in volumetric flask, add in cuvette respectively and measure, reading result, biochemical water light absorption value 1.38, then process water sample light absorption value 0.107.
4, result is calculated
COD formula: COD
Cr(O
2, mg/L)=(V
0-V
1) * C*8*1000/V
In formula: V
0The NH that consumes when-titration is blank
4(SO4) volume of standard liquid (mL);
V
1The NH that consumes during-Titration Water Sample
4(SO4) volume of standard liquid (mL);
V-volume of water sample (mL);
C-NH
4(SO4) concentration of standard solution (mol/L);
The molal weight (g/mol) of 8-oxygen (1/2O).
By calculating: biochemical water sample COD is 150mg/L, then to process waste water COD be 77.84mg/L.
Colourity computing formula: colourity=standard specimen chromatic value/standard specimen light absorption value * test sample light absorption value * extension rate
By calculating: biochemical water sample colourity is 283 times, then to process chroma in waste water be 21.83 times.
Embodiment two:
The take a sample biochemical waste discharge of certain factory and the inventive method of second batch processed waste water again and carried out COD, determination of colority.
1, sample treatment determination step
COD measures: biochemical water and process water sample 20mL again and be placed in cucurbit after getting 100 times of dilutions respectively, add 1g mercuric sulfate powder to mix, access constant temperature reflux, add silver sulfate powder 1g, add again the 30mL concentrated sulfuric acid, with the distilled water flushing tube wall that refluxes, add hot reflux 2h, add 80mL distilled water after cooling in sample, add three ferron indicator to shake up, with the titration of 0.1mol/L sulfate of ammoniac standard liquid, terminal point becomes the brownish red reading result, biochemical water 20.38ml, then to process water sample be 21.4ml.
Determination of colority: open spectrophotometer preheating half an hour, get distilled water and make zero stand-byly, get respectively 100 times of biochemical water of dilution and process again water sample 100mL and be placed in volumetric flask, add in cuvette respectively and measure, reading result, biochemical water light absorption value 2.33, then process water sample light absorption value 0.289.
2, result is calculated
COD formula: COD
Cr(O
2, mg/L)=(V
0-V
1) * C*8*1000/V
In formula: V
0The NH that consumes when-titration is blank
4(SO4) volume of standard liquid (mL);
V
1The NH that consumes during-Titration Water Sample
4(SO4) volume of standard liquid (mL);
V-volume of water sample (mL);
C-NH
4(SO4) concentration of standard solution (mol/L);
The molal weight (g/mol) of 8-oxygen (1/2O).
By calculating: biochemical water sample COD is 79.32mg/L, then to process waste water COD be 33.87mg/L.
Colourity computing formula: colourity=standard specimen chromatic value/standard specimen light absorption value * test sample light absorption value * extension rate
By calculating: biochemical water sample colourity is 378 times, then to process chroma in waste water be 48.54 times.
Embodiment three:
The 3rd batch of biochemical waste discharge of certain factory of sampling and the inventive method are processed waste water again and are carried out COD, determination of colority.
1, sample treatment determination step
COD measures: biochemical water and process water sample 20mL again and be placed in cucurbit after getting 100 times of dilutions respectively, add 1g mercuric sulfate powder to mix, access constant temperature reflux, add silver sulfate powder 1g, add again the 30mL concentrated sulfuric acid, with the distilled water flushing tube wall that refluxes, add hot reflux 2h, add 80mL distilled water after cooling in sample, add three ferron indicator to shake up, with the titration of 0.1mol/L sulfate of ammoniac standard liquid, terminal point becomes the brownish red reading result, biochemical water is 19.92ml, then to process water sample be 25.82ml.
Determination of colority: open spectrophotometer preheating half an hour, getting distilled water makes zero stand-by, get respectively 100 times of biochemical water of dilution and process again water sample 100mL and be placed in volumetric flask, add in cuvette respectively and measure, reading result, biochemical water light absorption value is 2.89, then to process the water sample light absorption value be 0.248.
2, result is calculated
COD formula: COD
Cr(O
2, mg/L)=(V
0-V
1) * C*8*1000/V
In formula: V
0The NH that consumes when-titration is blank
4(SO4) volume of standard liquid (mL);
V
1The NH that consumes during-Titration Water Sample
4(SO4) volume of standard liquid (mL);
V-volume of water sample (mL);
C-NH
4(SO4) concentration of standard solution (mol/L);
The molal weight (g/mol) of 8-oxygen (1/2O).
By calculating: biochemical water sample COD is 245mg/L, then to process waste water COD be 26.02mg/L.
Colourity computing formula: colourity=standard specimen chromatic value/standard specimen light absorption value * test sample light absorption value * extension rate
By calculating: biochemical water sample colourity is 590 times, then to process chroma in waste water be 50.9 times.
Claims (3)
1. FeCl who is used for aniline, the post processing of nitrobenzene biochemical waste water
2/ C-Cu method for preparing catalyst is characterized in that the preparation method is: with the FeCl of 100-500g
2Powder is treated FeCl through stirring the water-bath dissolving
2After powder dissolves fully, add the NaCO of 200-800g extrusion active carbon and 20-200g
3Powder stirred after 3-8 hour, and filtering and washing is with AgNO
3Solution is judged the washing terminal point, when not producing white precipitate, cures under 50-200 ℃, and after drying fully, rising 100-400 ℃,
Solidified 2-6 hour, and added at last the broken wood shavings of 50-300gCu, mix, namely make catalyst.
2. the preparation method of catalyst as claimed in claim 1, is characterized in that: with 350 gram FeCl
2Powder is placed in 3L distilled water, stirs the water-bath dissolving, treats FeCl
2After powder dissolves fully, add 500g extrusion active carbon, then add 100gNaCO
3Powder stirred 6 hours, with the material filtering and washing, with AgNO
3Solution is judged the washing terminal point, when not producing white precipitate, takes out material and cures under 105 ℃ 10 hours, and after drying fully, rising temperature to 270 ℃ curing 4 hours adds the broken wood shavings of 200gCu at last, mixes, and namely gets catalyst.
3. the preparation method of catalyst as claimed in claim 1 or 2, it is characterized in that prepared catalyst filling in 10L catalytic hydrolysis reaction pond hydrolytic tank, amount of filling is 1kg, and be connected to biochemistry pool, carry out the post processing of aniline, nitrobenzene biochemical waste water, the water inlet speed of aniline, nitrobenzene biochemical treatment waste water is that every 10L stopped 20 hours.
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| CN103464174A (en) * | 2012-06-08 | 2013-12-25 | 中国石油化工股份有限公司 | Preparation method for FeSO4 catalyst used for postprocessing of biochemical waste water of aniline and nitrobenzene |
| CN104276632A (en) * | 2013-07-12 | 2015-01-14 | 中国石油化工股份有限公司 | FeSO4 catalytic hydrolyzing method for post-treatment of aniline and nitrobenzene biochemical wastewater |
| CN106540720A (en) * | 2015-09-16 | 2017-03-29 | 中国石油化工股份有限公司 | For aniline nitrobenzene waste water post processing FeCl2The preparation method of-Cu/ carbon cloth electrolytic catalysts |
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| CN1240409A (en) * | 1996-11-08 | 2000-01-05 | 索卡尔有限公司 | Water Treatment process |
| CN101664683A (en) * | 2009-09-17 | 2010-03-10 | 新奥科技发展有限公司 | Catalytic agent for treating industrial waste water at normal temperature and pressure and preparation method thereof |
| CN101734817A (en) * | 2009-12-31 | 2010-06-16 | 江苏苏净集团有限公司 | Method for treating organic chemical waste water |
| CN101780412A (en) * | 2010-02-12 | 2010-07-21 | 新奥科技发展有限公司 | Catalyst for treating industrial waste water under normal temperature and normal pressure and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1240409A (en) * | 1996-11-08 | 2000-01-05 | 索卡尔有限公司 | Water Treatment process |
| CN101664683A (en) * | 2009-09-17 | 2010-03-10 | 新奥科技发展有限公司 | Catalytic agent for treating industrial waste water at normal temperature and pressure and preparation method thereof |
| CN101734817A (en) * | 2009-12-31 | 2010-06-16 | 江苏苏净集团有限公司 | Method for treating organic chemical waste water |
| CN101780412A (en) * | 2010-02-12 | 2010-07-21 | 新奥科技发展有限公司 | Catalyst for treating industrial waste water under normal temperature and normal pressure and preparation method thereof |
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Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee after: CHINA PETROCHEMICAL Corp. Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee before: CHINA PETROCHEMICAL Corp. Patentee before: Nanhua Group Research Institute |