CN1911822A - Catalytic electrode for treating nitro aromatic compound and halogenated substance and device - Google Patents
Catalytic electrode for treating nitro aromatic compound and halogenated substance and device Download PDFInfo
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- CN1911822A CN1911822A CN 200510090094 CN200510090094A CN1911822A CN 1911822 A CN1911822 A CN 1911822A CN 200510090094 CN200510090094 CN 200510090094 CN 200510090094 A CN200510090094 A CN 200510090094A CN 1911822 A CN1911822 A CN 1911822A
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Abstract
The present invention relates to one kind of catalytic electrode and device for treating nitro aromatic compound and halogenated organic matter. The electrode is prepared with oxidized and activated graphite grain as the base electrode material and co-dispersant liquid comprising carboxylated carbon nanotube, double-chain surfactant and deionized water, and through vibration and dispersion. The electrode is filled into work electrode bed layer of cathode chamber to form fluidized fixed bed electrolysis reactor for treating nitro aromatic compound and halogenated organic matter. The catalytic electrode has high stability, high catalyzing efficiency, high current efficiency and bath voltage lower than 2.5 V. The filled fixed bed electrolysis reactor has great electrode work area, high mass transfer efficiency and fast electrolytic reaction speed, and may be used in treat different pollutants via regulating the work voltage.
Description
Technical field
The present invention relates to a kind of catalysis electrode and device that is used to handle nitroaromatic and halogenated organic matters.
Background technology
Nitroaromatic and halogenated organic matters are a kind of important chemical intermediates, are widely used among the industry such as national defence, weaving, printing and dyeing, explosive, process hides, agricultural chemicals and medicine.And, be present in widely in the various factory effluents along with the fast development of industry.Because nitroaromatic and halogenated organic matters are very big to the toxicity of biology, have stronger carcinogenic, teratogenesis and mutagenesis, classified as the pollutent of preferential control by various countries.Thereby these contain the waste water of nitroaromatic and halogenated organic matters as not treated discharging, can cause serious pollution to environment.
It is to adopt absorption method (as Chinese patent CN1266820), extraction process (as Chinese patent CN1132725) that prior art handles one to nitroaromatic and halogenated organic matters, perhaps handle the back by physicochemical method and destroy its nitryl group or dehalogenation, that improves nitroaromatic or halogenated organic matters can be biological.But, because the recovery value of most nitroaromatic and halogenated organic matters is very low, the cost of adsorbent reactivation and extraction agent is very high again, and the complicated component of waste water, make that absorption method and extraction process cost are higher, use extraction agent to introduce secondary pollution again simultaneously.
Prior art also can adopt high-level oxidation technology to the processing of nitroaromatic and halogenated organic matters, comprises electrochemical oxidation, wet oxidation (comprising supercritical oxidation) and Fenton reagent etc.As disclosing a kind of technology of wet oxidation treatment of Nitrobenzene class waste water in the U.S. Pat 5250193, need the high pressure of 220～345 crust, 325～370 ℃ high temperature and corrosion resistant apparatus, investment and running cost height.Chinese patent CN1587091 discloses a kind of method of using chlorophenol in the hydrogen peroxide chemical oxidation water, owing to use a large amount of hydrogen peroxide, also makes processing cost very high.These methods all can't be practical owing to processing cost is very high.
When using oxidative treatment nitroaromatic and halogenated organic matters, because the stability of this two compounds is strong, the Chang Zuowei lewis' acid exists, it is oxidized to be difficult for losing electronics, and when the oxidation nitroaromatic in addition can toxigenicity stronger pyridine carboxylic acid, handle this two compounds so use reduction method in recent years instead.Wherein, electrolytic reduction is exactly comparatively common a kind of in the iron carbon, and this method is with low cost, but activity is not high, and iron particle top layer easily forms oxyhydroxide or oxide passivation layer, and stops reaction further to be carried out, and produces a large amount of iron mud simultaneously and forms secondary pollution.Chinese patent CN1168865 discloses the method for wastewater treatment that a kind of oil of mirbane shortening prepares p-aminophenol.This method is with the waste water evaporation concentration, and energy consumption is very big, and handling waste water simultaneously still needs charcoal absorption to handle.Chinese patent CN 1569677 has reported the method for halogeno-benzene phenolic compounds pollution in a kind of catalytic reduction hydrodehalogenation elimination water, (hydrogen of 0.05MPa～1.0MPa) is as hydrogen source need to use certain pressure, and using precious metal as hydrogenation catalyst, cost is very high.
By contrast, electrochemical reducing is a kind of treatment technology of cleaning.As disclose a kind of use electrochemical treatment oil of mirbane, 2 in Chinese patent CN1559933, the method for wastewater treatment of 4-dinitrophenol, p-Nitrophenyl chloride, bath voltage are up to 20～60V, and electric current is up to 10～30A.This is owing to the concentration of nitroaromatic in the waste water and halogenated organic matters is very low, the reduction overpotential height on conventional electrodes, and liberation of hydrogen is serious, thus current efficiency is low, and cost is very high.
Summary of the invention
The objective of the invention is to overcome prior art uses electrochemical reduction to handle the reduction overpotential height in nitroaromatic and the halogenated organic matters, the shortcoming that liberation of hydrogen is serious and current efficiency is low, thereby a kind of catalysis electrode and device that can be used to handle nitroaromatic and halogenated organic matters economic, practical, efficiently is provided, solves handling problem for the organic waste water of nitroaromatic and this class difficult degradation of halogenated organic matters.
The objective of the invention is to realize by the following technical solutions:
The catalysis electrode that is used to handle nitroaromatic and halogenated organic matters provided by the invention, it is what obtain by following method:
1) will carry out activation treatment as the granular graphite of base electrode 400～600 ℃ of aerobic oxidations 2～4 hours in tube furnace;
Described granular graphite is pole shape or blocky-shaped particle, and the volume of each granular graphite is at 1～500mm
3, preferred 10～100mm
3
2) CNT (carbon nano-tube) is placed the concentrated nitric acid or the vitriol oil, carboxylated processing is 1～5 hour under 60～100 ℃; Then carboxylated carbon nanotube is added double linked list surface-active agent and deionized water, ultra-sonic dispersion 5～20 minutes makes common dispersion liquid;
Described carbon nanotube comprises single wall or multi-walled carbon nano-tubes, and external diameter is 1～40nm;
Described double linked list surface-active agent is didodecyldimethylammbromide bromide, double hexadecyl alkyl phosphate or two octadecyl dimethyl brometo de amonio;
The carbon nanotube that adds and the mass ratio of double linked list surface-active agent are 0.5～2: 1, and the total mass of carbon nanotube and double linked list surface-active agent and the ratio of water are (0.5～4.0) mg/1mL;
3) granular graphite of activatory with step 1) places step 2) common dispersion liquid, hunting speed is 80～150 rev/mins, vibration mixed 1～6 hour;
4) granular graphite is taken out from mixed solution, drying obtains the catalysis electrode that is used to handle nitroaromatic and halogenated organic matters of the present invention.
The invention provides a kind of above-mentioned device that is used to handle the catalysis electrode of nitroaromatic and halogenated organic matters that uses, it comprises: the fixed bed electrolysis reactor that flows, a direct current power supply, a waste water tank, an anolyte storage tank, 2 peristaltic pumps;
The outside of described mobile fixed bed electrolysis reactor is the square housing 1 that a synthetic glass is made, have inlet mouth 5, fluid inlet 6,7 and leakage fluid dram 8,9 on it, by a cationic exchange membrane 2 whole reactor is divided into cathode compartment 3 and anolyte compartment 4 in the middle of the housing; Described inlet mouth 5 and fluid inlet 6 lay respectively on the housing of cathode compartment 3 bottoms, and described fluid inlet 7 is positioned on the housing of 4 bottoms, anolyte compartment, and described leakage fluid dram 8,9 lays respectively on the housing at cathode compartment 3 and 4 tops, anolyte compartment;
The volume of described cathode compartment 3 is 30～100mL, and the volume of described anolyte compartment 4 is 20～60mL;
The bottom of described cathode compartment 3 has one by cellular-plastic panels 10, has filled the working electrode bed 11 that the above-mentioned catalysis electrode that is used to handle nitroaromatic and halogenated organic matters is formed on it;
Insert in the described working electrode bed 11 a collector graphite rod 12 as cathode current collector and a saturated calomel electrode 13 as reference electrode; Described collector graphite rod 12 is connected a voltmeter 14 and a reometer 15 respectively with saturated calomel electrode 13, and the positive pole of voltmeter 14 connects mercurous chloride electrode 13, and negative pole connects collector graphite rod 12 directions, is parallel-connected to the negative pole of direct supply 16 then;
The below of the cellular-plastic panels 10 of the bottom of described cathode compartment 3 also has the evenly gas distribution pipe 17 of (φ 1 * 10) of a cloth hole, and the high pure nitrogen that is fed by inlet mouth 5 enters cathode compartment 3 by gas distribution pipe 17, is used as the cathode compartment deoxygenation promoting the circulation of qi body of going forward side by side and stirs;
Insert a Graphite Electrodes 18 in the described anolyte compartment 4 as anode, it is connected to the positive pole of direct supply 16;
Described waste water tank 19 links to each other with the fluid inlet 6 of cathode compartment 3 by pipeline, also is connected with a peristaltic pump 20 on it;
Described anolyte storage tank 21 links to each other with the fluid inlet 7 of anolyte compartment 4 by pipeline, also is connected with a peristaltic pump 22 on it;
The exit end of described leakage fluid dram 9 is connected with a recycle control valve 23, and an outlet of recycle control valve 23 is connected to 19, one outlets of anolyte storage tank with liquid discharge by pipeline.
During use, controlling operating voltage by the output voltage of adjusting direct supply 16 is-800～-950mV (making the saturated calomel electrode electromotive force be higher than the working electrode electromotive force), the waste water that will contain nitroaromatic and halogenated compound from waste water tank 19 by peristaltic pump 20 with the flow pump of 0.5～2mL/min to cathode compartment 3, carry out electrochemical reduction in working electrode bed 11, the while carries out deoxygenation by gas distribution pipe 17 feeding high pure nitrogens and stirs; Treat effluent is discharged by leakage fluid dram 8.
With the 0.1M metabisulfite solutions in the anolyte storage tank 21 by peristaltic pump 22 with the flow pump of 1mL/min to the anolyte compartment 4, water outlet is discharged by leakage fluid dram 9 after the electrolysis, is partly refluxed to anolyte storage tank 19 and recycles, remaining discharging, reflux ratio is 2: 1, by recycle control valve 23 controls.
Compared with prior art, provided by the inventionly be used to handle the catalysis electrode of nitroaromatic and halogenated organic matters and the advantage of treatment unit is: under the electrocatalysis on the electrode of the present invention, nitroaromatic selective reduction before separating out the molecular hydrogen current potential is little, the biodegradable phenyl amines aromatic compound of toxicity, and halogenated compound can be reduced the dehalogenation detoxification.This catalysis electrode good stability, the catalytic efficiency height, the current efficiency that most of nitroaromatic is handled is greater than 80%, and the current efficiency that halogenated organic matters is handled is greater than 50%, and bath voltage is lower than 2.5V.It is big to fill fixed bed electrolysis reactor working electrode area, the mass-transfer efficiency height, and electrolytic reaction is fast.Handle different pollutents by regulating operating potential, satisfy the different treatment requirement.
Description of drawings
Fig. 1 is the schematic representation of apparatus that is used to handle the catalysis electrode of nitroaromatic and halogenated organic matters provided by the invention; Wherein:
1 mobile fixed bed electrolysis reactor housing, 2 cationic exchange membranes, 3 cathode compartments, 4 anolyte compartments, 5 nearly tracheaes, 6 cathode compartment fluid inlets, 7 anolyte compartment's fluid inlets, 8 cathode compartment leakage fluid drams, 9 anolyte compartment's leakage fluid drams, 10 cellular-plastic panels, 11 working electrode beds, 12 collector graphite rods, 13 saturated calomel electrode, 14 voltmeters, 15 reometers, the adjustable direct supply of 16 voltages, 17 gas distribution pipes, 18 Graphite Electrodess, 19 waste water tanks, 20 peristaltic pumps, 21 anolyte storage tanks, 22 peristaltic pumps, 23 recycle control valves.
Embodiment
Embodiment 1, preparation catalysis electrode I
φ 20mm graphite rod is cut into the right cylinder of many 10mm * 10mm * 5mm, placed 500 ℃ of aerobic oxidations of tube furnace 4 hours, carry out activation treatment; On abrasive paper for metallograph, polish smooth, as base electrode.The multi-walled carbon nano-tubes of caliber 30～40nm is placed concentrated nitric acid, and carboxylated processing is 5 hours under 60 ℃; Then that 50mg is carboxylated carbon nanotube adds 50mg didodecyldimethylammbromide bromide and 50mL deionized water, and ultra-sonic dispersion 10 minutes makes common dispersion liquid.The granular graphite of activatory that polishes smooth is placed this common dispersion liquid, and hunting speed is 120 rev/mins, and vibration mixed 3 hours.Granular graphite is taken out from mixed solution, and drying obtains the catalysis electrode I that is used to handle nitroaromatic and halogenated organic matters of the present invention.
Embodiment 2, preparation catalysis electrode II
φ 10mm graphite rod is cut into the right cylinder of many φ 8mm * 2mm, placed 600 ℃ of aerobic oxidations of tube furnace 2 hours, carry out activation treatment; On abrasive paper for metallograph, polish smooth, as base electrode.The multi-walled carbon nano-tubes of caliber 15～30nm is placed concentrated nitric acid, and carboxylated processing is 3 hours under 70 ℃; Then that 50mg is carboxylated carbon nanotube adds two octadecyl dimethyl brometo de amonios of 100mg and 50mL deionized water, and ultra-sonic dispersion 10 minutes makes common dispersion liquid.The granular graphite of activatory that polishes smooth is placed this common dispersion liquid, and hunting speed is 80 rev/mins, and vibration mixed 6 hours.Granular graphite is taken out from mixed solution, and drying obtains the catalysis electrode I that is used to handle nitroaromatic and halogenated organic matters of the present invention.
Embodiment 3, preparation catalysis electrode III
φ 20mm graphite rod is cut into the right cylinder of many φ 6mm * 2.5mm, placed 400 ℃ of aerobic oxidations of tube furnace 3 hours, carry out activation treatment; On abrasive paper for metallograph, polish smooth, as base electrode.The multi-walled carbon nano-tubes of caliber 5～15nm is placed the vitriol oil, and carboxylated processing is 5 hours under 90 ℃; Then that 50mg is carboxylated carbon nanotube adds 25mg double hexadecyl alkyl phosphate and 50mL deionized water, and ultra-sonic dispersion 10 minutes makes common dispersion liquid.The granular graphite of activatory that polishes smooth is placed this common dispersion liquid, and hunting speed is 150 rev/mins, and vibration mixed 1 hour.Granular graphite is taken out from mixed solution, and drying obtains the catalysis electrode III that is used to handle nitroaromatic and halogenated organic matters of the present invention.
Embodiment 4, preparation catalysis electrode IV
Graphite rod is cut into the particle of many 1mm * 1mm * 1mm, placed 450 ℃ of aerobic oxidations of tube furnace 4 hours, carry out activation treatment; On abrasive paper for metallograph, polish smooth, as base electrode.The Single Walled Carbon Nanotube of caliber 1～5nm is placed the vitriol oil, and carboxylated processing is 1 hour under 100 ℃; Then that 50mg is carboxylated carbon nanotube adds 50mg didodecyldimethylammbromide bromide and 200mL deionized water, and ultra-sonic dispersion 10 minutes makes common dispersion liquid.The granular graphite of activatory that polishes smooth is placed this common dispersion liquid, and hunting speed is 120 rev/mins, and vibration mixed 3 hours.Granular graphite is taken out from mixed solution, and drying obtains the catalysis electrode IV that is used to handle nitroaromatic and halogenated organic matters of the present invention.
Embodiment 5, preparation catalysis electrode V
Graphite rod is cut into the particle of 2mm * 2mm * 2.5mm, placed 550 ℃ of aerobic oxidations of tube furnace 2 hours, carry out activation treatment; On abrasive paper for metallograph, polish smooth, as base electrode.The multi-walled carbon nano-tubes of caliber 15～30nm is placed the vitriol oil, and carboxylated processing is 4 hours under 80 ℃; Then that 50mg is carboxylated carbon nanotube adds 50mg double hexadecyl alkyl phosphate and 25mL deionized water, and ultra-sonic dispersion 10 minutes makes common dispersion liquid.The granular graphite of activatory that polishes smooth is placed this common dispersion liquid, and hunting speed is 120 rev/mins, and vibration mixed 3 hours.Granular graphite is taken out from mixed solution, and drying obtains the catalysis electrode V that is used to handle nitroaromatic and halogenated organic matters of the present invention.
Embodiment 6, preparation catalysis electrode VI
φ 8mm graphite rod is cut into the right cylinder of many φ 8mm * 8mm, placed 550 ℃ of aerobic oxidations of tube furnace 3 hours, carry out activation treatment; On abrasive paper for metallograph, polish smooth, as base electrode.The multi-walled carbon nano-tubes of caliber 30～40nm is placed concentrated nitric acid, and carboxylated processing is 5 hours under 60 ℃; Then that 50mg is carboxylated carbon nanotube adds two octadecyl dimethyl brometo de amonios of 50mg and 100mL deionized water, and ultra-sonic dispersion 10 minutes makes common dispersion liquid.The granular graphite of activatory that polishes smooth is placed this common dispersion liquid, and hunting speed is 120 rev/mins, and vibration mixed 3 hours.Granular graphite is taken out from mixed solution, and drying obtains the catalysis electrode VI that is used to handle nitroaromatic and halogenated organic matters of the present invention.
The electrochemical treatment of embodiment 7, oil of mirbane and p-nitrophenyl
The device that is used to handle the catalysis electrode of nitroaromatic and halogenated organic matters provided by the invention, it comprises: the fixed bed electrolysis reactor that flows, a direct current power supply, a waste water tank, an anolyte storage tank, 2 peristaltic pumps;
The outside of described mobile fixed bed electrolysis reactor is the square housing 1 that a synthetic glass is made, have inlet mouth 5, fluid inlet 6,7 and leakage fluid dram 8,9 on it, by a cationic exchange membrane 2 whole reactor is divided into cathode compartment 3 and anolyte compartment 4 in the middle of the housing; Described inlet mouth 5 and fluid inlet 6 lay respectively on the housing of cathode compartment 3 bottoms, and described fluid inlet 7 is positioned on the housing of 4 bottoms, anolyte compartment, and described leakage fluid dram 8,9 lays respectively on the housing at cathode compartment 3 and 4 tops, anolyte compartment;
The volume of described cathode compartment 3 is 50mL, and the volume of described anolyte compartment 4 is 30mL;
The bottom of described cathode compartment 3 has one by cellular-plastic panels 10, and that has filled embodiment 1 preparation on it is used to handle the working electrode bed 11 that the catalysis electrode I of nitroaromatic and halogenated organic matters forms;
Insert in the described working electrode bed 11 a collector graphite rod 12 as cathode current collector and a saturated calomel electrode 13 as reference electrode; Described collector graphite rod 12 is connected a voltmeter 14 and a reometer 15 respectively with saturated calomel electrode 13, and the positive pole of voltmeter 14 connects mercurous chloride electrode 13, and negative pole connects collector graphite rod 12 directions, is parallel-connected to the negative pole of direct supply 16 then;
The below of the cellular-plastic panels 10 of the bottom of described cathode compartment 3 also has the evenly gas distribution pipe 17 of (φ 1 * 10) of a cloth hole, and the high pure nitrogen that is fed by inlet mouth 5 enters cathode compartment 3 by gas distribution pipe 17, is used as the cathode compartment deoxygenation promoting the circulation of qi body of going forward side by side and stirs;
Insert a Graphite Electrodes 18 in the described anolyte compartment 4 as anode, it is connected to the positive pole of direct supply 16;
Described waste water tank 19 links to each other with the fluid inlet 6 of cathode compartment 3 by pipeline, also is connected with a peristaltic pump 20 on it;
Described anolyte storage tank 21 links to each other with the fluid inlet 7 of anolyte compartment 4 by pipeline, also is connected with a peristaltic pump 22 on it.
The exit end of described leakage fluid dram 9 is connected with a recycle control valve 23, and an outlet of recycle control valve 23 is connected to 19, one outlets of anolyte storage tank with liquid discharge by pipeline.
Preparation oil of mirbane and para-nitrotoluene concentration are the simulated wastewater (supporting electrolyte is the phosphate buffered of pH=7.0) of 200mg/L, from waste water tank 19 by peristaltic pump 20 with the flow pump of 1mL/min to cathode compartment 3, carry out electrochemical reduction in working electrode bed 11, the output voltage of regulating voltage control voltmeter 16 is-800mV (making the saturated calomel electrode electromotive force be higher than the working electrode electromotive force).Feeding high pure nitrogen by gas distribution pipe 17 with 25mL/min simultaneously carries out deoxygenation and stirs the acceleration mass transfer.Oil of mirbane and para-nitrotoluene and product thereof use high performance liquid chromatography to analyze.The pumping capacity of anolyte compartment is 1mL/min, and the pump around circuit ratio is 5: 1.Oil of mirbane and para-nitrotoluene all can-0.800mV (with respect to saturated calomel electrode) catalytic reduction is an amino benzenes compounds, reaction current efficient is more than 80%.Cathode compartment oil of mirbane and para-nitrotoluene clearance are greater than 99%, and oil of mirbane near 100% and para-nitrotoluene all are converted into the amino benzenes compounds of easy degraded, and cathode compartment outlet oil of mirbane and the equal concentration of para-nitrotoluene are lower than 2mg/L.Handle the back water outlet and enter follow-up bio-contact oxidation, 5 hours residence time, amino benzenes compounds clearance 100%, COD clearance 70% detects less than oil of mirbane and para-nitrotoluene.Because the efficient catalytic of carbon nano tube modified electrode has reduced the reduction overpotential of oil of mirbane and para-nitrotoluene, the bath voltage between the whole positive and negative electrode that makes is very low, and whole process is less than 2.5V.
After catalysis electrode I used 20 times, catalytic current only descended 5%, illustrates that electrode stability provided by the invention is good, can repeatedly use.
The electrochemical treatment of embodiment 8, zellon
Use the device among the embodiment 7 that zellon is carried out electrochemical treatment, concrete steps are as follows:
The preparation tce concentration is the simulated wastewater (supporting electrolyte is the phosphate buffered of pH=7.0) of 100mg/L, peristaltic pump pumps into cathode compartment the reactor with the flow of 1mL/min from storage tank, and regulating voltage control voltmeter is-950mV (making the saturated calomel electrode electromotive force be higher than the working electrode electromotive force).The nitrogen that feeds 25mL/min carries out the deoxygenation promoting the circulation of qi body of going forward side by side and stirs and quicken mass transfer.The pumping capacity of anolyte compartment is 1mL/min, and the pump around circuit ratio is 5: 1.Zellon and product thereof use gas-chromatography to analyze.Zellon can be at-950mV (with respect to saturated calomel electrode) reduction dechlorination, and only the minute quantity molecular hydrogen is separated out, and reaction current efficient is more than 50%.Cathode compartment zellon clearance is greater than 95%, and the outlet tce concentration is lower than 5mg/L.Because the efficient catalytic of carbon nano tube modified electrode has reduced the reduction overpotential of zellon, the bath voltage between the whole positive and negative electrode that makes is very low, and whole process is less than 2.5V.
The electrochemical treatment of embodiment 9, zellon
Use the device among the embodiment 7 that zellon is carried out electrochemical treatment, just the working electrode bed is the catalysis electrode II of embodiment 2 preparations, and concrete steps are as follows:
The preparation tce concentration is the simulated wastewater (supporting electrolyte is the phosphate buffered of pH=7.0) of 100mg/L, peristaltic pump pumps into cathode compartment the reactor with the flow of 1mL/min from storage tank, and regulating voltage control voltmeter is-950mV (making the saturated calomel electrode electromotive force be higher than the working electrode electromotive force).The nitrogen that feeds 25mL/min carries out the deoxygenation promoting the circulation of qi body of going forward side by side and stirs and quicken mass transfer.The pumping capacity of anolyte compartment is 1mL/min, and the pump around circuit ratio is 5: 1.Zellon dechlorination current efficiency is more than 50%.Cathode compartment zellon clearance is greater than 93%, and the outlet tce concentration is lower than 5mg/L.Bath voltage between the positive and negative electrode is less than 2.5V.
After catalysis electrode II used 20 times, catalytic current only descended 5%, illustrates that electrode stability is good, can repeatedly use.
The electrochemical treatment of embodiment 10, trichoroacetic acid(TCA) and dibromoacetic acid
Use the device among the embodiment 7 that zellon is carried out electrochemical treatment, just the working electrode bed is the catalysis electrode III of embodiment 3 preparations, and concrete steps are as follows:
Preparation trichoroacetic acid(TCA) and dibromoacetic acid concentration are the simulated wastewater (supporting electrolyte is the phosphate buffered of pH=7.0) of 100mg/L, peristaltic pump pumps into cathode compartment the reactor with the flow of 1mL/min from storage tank, and regulating voltage control voltmeter is-850mV (making the saturated calomel electrode electromotive force be higher than the working electrode electromotive force).The nitrogen that feeds 25mL/min carries out the deoxygenation promoting the circulation of qi body of going forward side by side and stirs and quicken mass transfer.The pumping capacity of anolyte compartment is 1mL/min, and the pump around circuit ratio is 5: 1.Trichoroacetic acid(TCA) and dibromoacetic acid and product thereof use chromatography of ions to analyze.Trichoroacetic acid(TCA) and dibromoacetic acid can be at-0.850V (with respect to saturated calomel electrode) reductive dehalogenations, and reaction current efficient is more than 70%.The trichoroacetic acid(TCA) clearance is more than 95%, and the dibromoacetic acid clearance is more than 99%.Cathode compartment outlet trichoroacetic acid(TCA) concentration is lower than 5mg/L, and dibromoacetic acid concentration is lower than 1mg/L.Because the efficient catalytic of carbon nano tube modified electrode has reduced the reduction overpotential of trichoroacetic acid(TCA) and dibromoacetic acid, the bath voltage between the whole positive and negative electrode that makes is very low, and whole process is less than 2.5V.
After catalysis electrode III used 20 times, catalytic current only descended 5%, illustrates that electrode stability is good, can repeatedly use.
Claims (8)
1, a kind of catalysis electrode that is used to handle nitroaromatic and halogenated organic matters, it is what obtain by following method:
1) will carry out activation treatment as the granular graphite of base electrode 400～600 ℃ of aerobic oxidations 2～4 hours in tube furnace;
2) CNT (carbon nano-tube) is placed the concentrated nitric acid or the vitriol oil, carboxylated processing is 1～5 hour under 60～100 ℃; Then carboxylated carbon nanotube is added double linked list surface-active agent and deionized water, ultra-sonic dispersion 5～20 minutes makes common dispersion liquid;
The carbon nanotube that adds and the mass ratio of double linked list surface-active agent are 0.5～2: 1, and the total mass of carbon nanotube and double linked list surface-active agent and the ratio of water are: 0.5～4.0mg/1mL;
3) granular graphite of activatory with step 1) places step 2) common dispersion liquid, hunting speed is 80～150 rev/mins, vibration mixed 1～6 hour;
4) granular graphite is taken out from mixed solution, drying obtains the catalysis electrode that is used to handle nitroaromatic and halogenated organic matters of the present invention.
2, the catalysis electrode that is used to handle nitroaromatic and halogenated organic matters as claimed in claim 1 is characterized in that: described granular graphite is pole shape or blocky-shaped particle, and the volume of each granular graphite is 1～500mm
3
3, the catalysis electrode that is used to handle nitroaromatic and halogenated organic matters as claimed in claim 1 or 2 is characterized in that: the volume of described granular graphite is 10～100mm
3
4, the catalysis electrode that is used to handle nitroaromatic and halogenated organic matters as claimed in claim 1, it is characterized in that: described carbon nanotube comprises single wall or multi-walled carbon nano-tubes, external diameter is 1～40nm.
5, the catalysis electrode that is used to handle nitroaromatic and halogenated organic matters as claimed in claim 1 is characterized in that: described double linked list surface-active agent is didodecyldimethylammbromide bromide, double hexadecyl alkyl phosphate or two octadecyl dimethyl brometo de amonio.
6, a kind of described device that is used to handle the catalysis electrode of nitroaromatic and halogenated organic matters of claim 1 that uses, it comprises: the fixed bed electrolysis reactor that flows, a direct current power supply, a waste water tank, an anolyte storage tank, 2 peristaltic pumps;
The outside of described mobile fixed bed electrolysis reactor is the square housing (1) that a synthetic glass is made, have inlet mouth (5), fluid inlet (6), (7) and leakage fluid dram (8), (9) on it, by a cationic exchange membrane (2) whole reactor is divided into cathode compartment (3) and anolyte compartment (4) in the middle of the housing; Described inlet mouth (5) and fluid inlet (6) lay respectively on the housing of cathode compartment (3) bottom, described fluid inlet (7) is positioned on the housing of bottom, anolyte compartment (4), and described leakage fluid dram (8), (9) lay respectively on the housing at cathode compartment (3) and top, anolyte compartment (4);
The bottom of described cathode compartment (3) has one by cellular-plastic panels (10), has filled the working electrode bed (11) that the above-mentioned catalysis electrode that is used to handle nitroaromatic and halogenated organic matters is formed on it;
Insert in the described working electrode bed (11) a collector graphite rod (12) as cathode current collector and a saturated calomel electrode (13) as reference electrode; Described collector graphite rod (12) is connected a voltmeter (14) and a reometer (15) respectively with saturated calomel electrode (13), the positive pole of voltmeter (14) connects mercurous chloride electrode (13), negative pole connects collector graphite rod (12) direction, is parallel-connected to the negative pole of direct supply (16) then;
The below of the cellular-plastic panels (10) of the bottom of described cathode compartment (3) also has the uniform gas distribution pipe in a cloth hole (17), and the high pure nitrogen that is fed by inlet mouth (5) enters cathode compartment (3) by gas distribution pipe (17), is used as the cathode compartment deoxygenation promoting the circulation of qi body stirring of going forward side by side;
Insert a Graphite Electrodes (18) in the described anolyte compartment (4) as anode, it is connected to the positive pole of direct supply (16);
Described waste water tank (19) links to each other with the fluid inlet (6) of cathode compartment (3) by pipeline, also is connected with a peristaltic pump (20) on it;
Described anolyte storage tank (21) links to each other with the fluid inlet (7) of anolyte compartment (4) by pipeline, also is connected with a peristaltic pump (22) on it;
The exit end of described leakage fluid dram (9) is connected with a recycle control valve (23), and an outlet of recycle control valve (23) is connected to anolyte storage tank (19) by pipeline, and an outlet is with liquid discharge.
7, the device that is used to handle the catalysis electrode of nitroaromatic and halogenated organic matters as claimed in claim 6, it is characterized in that: the volume of described cathode compartment is 30～100mL, the volume of described anolyte compartment is 20～60mL.
8, the device that is used to handle the catalysis electrode of nitroaromatic and halogenated organic matters as claimed in claim 6, it is characterized in that: the aperture of described gas distribution pipe is diameter 1mm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100900947A CN100422091C (en) | 2005-08-12 | 2005-08-12 | Catalytic electrode for treating nitro aromatic compound and halogenated substance and device |
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| CNB2005100900947A CN100422091C (en) | 2005-08-12 | 2005-08-12 | Catalytic electrode for treating nitro aromatic compound and halogenated substance and device |
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| CN1911822A true CN1911822A (en) | 2007-02-14 |
| CN100422091C CN100422091C (en) | 2008-10-01 |
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| CNB2005100900947A Expired - Fee Related CN100422091C (en) | 2005-08-12 | 2005-08-12 | Catalytic electrode for treating nitro aromatic compound and halogenated substance and device |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103466852A (en) * | 2013-09-26 | 2013-12-25 | 南京大学 | Sludge-reduction electrocatalytic reduction-oxidation pretreatment method for nitrotoluene production waste water |
| CN105884098A (en) * | 2016-05-30 | 2016-08-24 | 中北大学 | Method and device for treating nitrobenzene wastewater through ultrasonic wave/iron-carbon micro-electrolysis-Fenton oxidation method |
| CN111087047A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Treatment method of bromine-containing organic wastewater |
| CN111792706A (en) * | 2020-08-27 | 2020-10-20 | 南京师范大学 | Electrochemical oxidation treatment reactor with cation exchange membrane and method for treating pyridine wastewater |
| CN112076884A (en) * | 2020-09-01 | 2020-12-15 | 江西理工大学 | Critical oxidation activation method for pyrite inhibited by lime |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999058452A2 (en) * | 1998-05-14 | 1999-11-18 | Upscale Water Technologies, Inc. | Electrodes for electrolytic removal of nitrates from water, methods of making same, and apparatus incorporating said electrodes |
| DE19844059A1 (en) * | 1998-09-25 | 2000-03-30 | Degussa | Electrolytic cell and its use |
| CN1544116A (en) * | 2003-11-13 | 2004-11-10 | 上海大学 | Making method for charcoal electrode of liquid flow type electroadsorption desalinization device |
| CN1300012C (en) * | 2004-02-26 | 2007-02-14 | 江苏省环境科学研究院 | Process for treating waste water of nitrobenzene, 2,4-dinitrophenol, p-nitro-chlorebenzene |
-
2005
- 2005-08-12 CN CNB2005100900947A patent/CN100422091C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105884098A (en) * | 2016-05-30 | 2016-08-24 | 中北大学 | Method and device for treating nitrobenzene wastewater through ultrasonic wave/iron-carbon micro-electrolysis-Fenton oxidation method |
| CN111087047A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Treatment method of bromine-containing organic wastewater |
| CN111792706A (en) * | 2020-08-27 | 2020-10-20 | 南京师范大学 | Electrochemical oxidation treatment reactor with cation exchange membrane and method for treating pyridine wastewater |
| CN112076884A (en) * | 2020-09-01 | 2020-12-15 | 江西理工大学 | Critical oxidation activation method for pyrite inhibited by lime |
| CN112076884B (en) * | 2020-09-01 | 2022-03-01 | 江西理工大学 | Critical oxidation activation method for pyrite inhibited by lime |
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| CN100422091C (en) | 2008-10-01 |
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Assignee: Beijing Saike Era Environmental Protection Technology Co.,Ltd. Assignor: Institute of Process Engineering, Chinese Academy of Sciences Contract record no.: 2010110000143 Denomination of invention: Catalytic electrode for treating nitro aromatic compound and halogenated substance and device Granted publication date: 20081001 License type: Exclusive License Open date: 20070214 Record date: 20100902 |
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