CN107697984A - Sn/Sb Mn GAC particles and its application in the Chlorophenol of three-dimensional electrochemical reaction treatment 4 - Google Patents
Sn/Sb Mn GAC particles and its application in the Chlorophenol of three-dimensional electrochemical reaction treatment 4 Download PDFInfo
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- CN107697984A CN107697984A CN201711132892.0A CN201711132892A CN107697984A CN 107697984 A CN107697984 A CN 107697984A CN 201711132892 A CN201711132892 A CN 201711132892A CN 107697984 A CN107697984 A CN 107697984A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
Abstract
The present invention discloses Sn/Sb Mn GAC particles, and the particle is the support type Sn/Sb Mn GAC particles that Sn, Sb, Mn metal ion are prepared using infusion process by loading modification granular activated carbon.Using support type Sn/Sb Mn GAC particles as granule electrode, using dimensional stable anode DSA electrodes as anode, using titanium plate as negative electrode, bipolar type three-dimensional electrochemical reactor is built, three-dimensional electrochemical reaction is carried out under electrochemical oxidation process, 4 chlorophenols are finally degraded to carbon dioxide and water.4 Chlorophenols are handled with Sn/Sb Mn GAC particles, the clearance of 4 chlorophenols can reach more than 99%.Meanwhile particle preparation technology is simple, particle may be reused, and greatly reduce the processing cost of 4 Chlorophenols, and improve 4 Chlorophenol treatment effeciencies.
Description
Technical field
The invention belongs to technical field of sewage, more particularly to Sn/Sb-Mn-GAC particles prepare and its in three-dimensional electrifications
Learn the application in reaction treatment 4- Chlorophenols.
Background technology
With the fast development of the industry such as petrochemical industry, plastics, synthetic fibers, caused phenol wastewater is discharged into certainly in production
Right boundary, while causing water pollution, also affect aquatile growth and breeding.Phenol wastewater is difficult degradation toxic organic compound,
It is the difficult point in environmental improvement, both at home and abroad to the discharge of strict control aldehydes matter.
Processing containing Phenol Industrial Wastewater also turns into one of hot research content.Current wastewater treatment containing aldehydes matter is general
Absorption method can be used, adsorbent is frequently with activated carbon, but the phase transfer of aldehydes matter is simply realized in absorption method processing, can not
Carry out poisonous and harmful substance depth and greenization processing.Electrochemistry oxygen is turned to high-level oxidation technology one kind, has oxidisability
By force, reaction rate is fast, and wide adaptability, non-secondary pollution, processing equipment is simple, the advantages that electrolytic condition easily operated control, into
One of study hotspot for the poisonous and harmful wastewater treatment of difficult degradation.Pang Jie etc. is using heterogeneous ion-exchange membrane electroosmose process processing benzene
Phenol waste water, the influence of different factor Pyrogentisinic Acid treatment effects is investigated.Test result indicates that the processing of this method Pyrogentisinic Acid's waste water
Effect is preferable, and the energy consumption for handling waste water is low, and operating process is also more convenient.ZUCHENGWU uses β-PbO2Anode have studied
The Oxidative Degradation Process of phenol, the shadow of initial pH value, current density and temperature Degradation of Phenol is investigated in research process
Ring, thus it is speculated that gone out the degradation pathway of phenol, and established the mathematical modeling of phenol and benzoquinones oxidative degradation.Wang Taibin etc. is used
A kind of homemade NEW TYPE OF COMPOSITE porous electrode-expanded graphite-based charcoal/charcoal combination electrode (EGC electrodes) Pyrogentisinic Acid has carried out electrochemistry
Oxidative degradation, and inquired into the degradation technique condition of phenol.Electricity-Fenton methods are mutually to tie electrochemical process with Fenton reagent method
The method of conjunction, the general principle of electricity-Fenton methods are in an acidic solution, to pass through the mode O of electrolysis2Given birth in cathodic reduction
Into H2O2, the H of generation2O2Rapidly and Fe2+React generation OH and Fe3+, OH is with its potential value of very high oxidizing potential
Up to 2.8V, the organic pollutant of difficult degradation can be degraded to using OH Strong oxdiative ability and be oxidized to having for small molecule
Machine thing, or thoroughly it is degraded to CO2And H2O；Fe simultaneously3+And can is reduced to Fe in negative electrode2+, carried out so as to form a circulation
Oxidation reaction.The essence of electricity-Fenton methods is exactly persistently to produce Fe by electrochemical process2+And H2O2, form a circulation.Electricity-
Fenton methods are widely used in processing containing phenols, organic acid, agricultural chemicals, You Jihe as a kind of new electrochemical process for treating
Into the experimental study of the used water difficult to degradate such as dyestuff, personal care product.Bai Wei etc. has been handled using electricity-Fenton methods and given up containing phenol
Water, the optimum reaction condition for drawing electricity-Fenton methods processing phenol synthetic water through experimental analysis are：PH value control is 2, electrolysis
Voltage 10V, reaction time 60min, Na2SO4Concentration is 30g/L, initial phenol concentration 150mg/L, condition Pyrogentisinic Acid's
Its clearance is handled up to 82%.Du Yan lifes et al. are handled dinitrodiazophenol wastewater using electricity-Fenton methods.It is real
Test result and show that the optimal treatment condition of dinitrodiazophenol wastewater is：Electrolysis time 3.5h, pH value 4, DC voltage 12V,
H2O2Dosage be 10mL/L, dinitrodiazophenol wastewater COD clearances up to 97.24%, go by colourity under this treatment conditions
Except rate is up to 93.75%.
Currently, industrial wastewater containing phenol is mainly handled using absorption method, and activated carbon has the internal pore structure of prosperity, surface area
Greatly, chemical stability is good, is resistant to strong acid and highly basic.Water logging, high temperature, high pressure are amenable to, is more conventional adsorbent.Activated carbon
There is powdered and granular active carbon (Granular Activated Carbon, GAC).Powdered Activated Carbon is easily prepared, price
Cheaply, adsorption capacity is strong, but regeneration is not easy, and reusability is poor.Compared to Powdered Activated Carbon, although granular activated carbon valency
Lattice are noble, but renewable reuse, are common used materials in water process.
The content of the invention
The present invention is big aiming at difficulty in the traditional treatment method of the industrial wastewater containing phenol in the prior art, is removed, and removes
The problems such as rate is limited, it is high to remove cost, complex operation, there is provided a kind of Sn/Sb-Mn-GAC particles prepare and its in three-dimensional electrochemical
Application in reaction treatment 4- Chlorophenols.
In order to realize the above-mentioned purpose of the present invention, technical scheme is as follows
Sn/Sb-Mn-GAC particles, the particle are that Sn, Sb, Mn metal ion are modified into particle by loading using infusion process
The support type Sn/Sb-Mn-GAC particles that activated carbon is prepared.
As the further improvement of technical scheme, above-described Sn/Sb-Mn-GAC particles, described support type Sn/
Sb-Mn-GAC particle preparation method specific steps include：First by SnCl4·5H2O、Mn(NO3)2、SbCl3It is molten to be dissolved in Organic Alcohol
Mixed solution is obtained in agent, then GAC is immersed in mixed solution, shaking table 150-200r/min shakes more than 2 hours, is born
Load type Sn/Sb-Mn-GAC particle crude products, then drying, 300-500 DEG C of roasting can obtain support type Sn/Sb-Mn-GAC grains
Son.
It is described in above-described Sn/Sb-Mn-GAC particles preparation method as the further improvement of technical scheme
Shaking table frequency is 150-200r/min, and described sintering temperature is 300-500 DEG C.
As the further improvement of technical scheme, above-described Sn/Sb-Mn-GAC particles, SnCl4·5H2O、Mn
(NO3)2、SbCl3Mass ratio with GAC is：8~16：1~5：0.4~2：60~80..
As the further improvement of technical scheme, above-described Sn/Sb-Mn-GAC particles, in addition to granular activated carbon
Pretreatment, the pretreatment of described granular activated carbon are that granular activated carbon is boiled to clean, drying with a large amount of deionized waters.
It is described in above-described Sn/Sb-Mn-GAC particles preparation method as the further improvement of technical scheme
Drying temperature is 100-110 DEG C.
Application of the Sn/Sb-Mn-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols described in any of the above,
Using support type Sn/Sb-Mn-GAC particles as granule electrode, using dimensional stable anode DSA electrodes as anode, using titanium plate as negative electrode, structure
Bipolar type three-dimensional electrochemical reactor, three-dimensional electrochemical reaction is carried out under electrochemical oxidation process, 4- chlorophenols are finally degraded
For carbon dioxide and water.
As the further improvement of technical scheme, above-described Sn/Sb-Mn-GAC particles are at three-dimensional electrochemical reaction
The application in 4- Chlorophenols is managed, the electrolyte that the reaction of described three-dimensional electrochemical uses is Na2SO4、NaCl、K2SO4, in KCl
One kind.
As the further improvement of technical scheme, above-described Sn/Sb-Mn-GAC particles are at three-dimensional electrochemical reaction
The application in 4- Chlorophenols is managed, in the reaction of described three-dimensional electrochemical, 4- Chlorophenols concentration is 100-500mg/L, simulation
Wastewater volume 200-300mL, electrolyte concentration 2-4g/L, the plate spacing between negative electrode and anode is 2-4cm, kinetic current is
1-2A, granule electrode dosage 10-20g.As the further improvement of technical scheme, above-described Sn/Sb-Mn-GAC particles
Application in three-dimensional electrochemical reaction treatment 4- Chlorophenols, the temperature of described three-dimensional electrochemical reaction is 40-60 DEG C.
As the further improvement of technical scheme, above-described Sn/Sb-Mn-GAC particles are at three-dimensional electrochemical reaction
The application in 4- Chlorophenols is managed, in the reaction of described three-dimensional electrochemical, 4- chlorophenols are first degraded in hydroxyl free radical
Between product, be finally degraded to carbon dioxide and water；The intermediate product benzoquinones of described hydroxyl free radical, 4- chlorine catechol,
Mixing more than one or both of hydroquinones, fumaric acid, oxalic acid.
As the further improvement of technical scheme, above-described Sn/Sb-Mn-GAC particles are at three-dimensional electrochemical reaction
The application in 4- Chlorophenols is managed, the clearance of 4- chlorophenols reaches more than 99% in described 4- Chlorophenols.
The invention has the advantages that：
The present invention is prepared for Sn/Sb-Mn-GAC particles using infusion process, and infusion process has behaviour compared with other preparation methods
Make the advantages of simple.Simultaneously because employing carrier of the granular activated carbon as granule electrode, make it than the particle of other carriers
Electrode has more preferable adsorption effect.The area that working electrode is considerably increased in three-dimensional electrochemical reactor is applied,
Current efficiency is improved, also has the more thorough non-secondary pollution of 4- chlorophenol degradations etc. excellent compared with other method degrades 4- chlorophenols
Point.Mn is adulterated in Sn-Sb simultaneously to be advantageous to change SnO2Oxygen vacancy concentration in lattice, improve the catalytic oxidative of granule electrode
Can, so as to substantially increase the degradation efficiency to 4- chlorophenols.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of Sn/Sb-Mn-GAC particles.
Fig. 2 schemes for Sn/Sb-Mn-GAC particle surface elementary analyses EDS.
Fig. 3 is Sn/Sb-Mn-GAC granule electrode XRDs
Fig. 4 is the analysis oxygen polarization curve of Sn/Sb-Mn-GAC granule electrodes
Fig. 5 is the cyclic voltammetry curve figure of Sn/Sb-Mn-GAC granule electrodes
Fig. 6 is the liquid chromatogram during 4- chlorophenol degradations
In Fig. 6：1. oxalic acid；2. fumaric acid；3. hydroquinones；4. 1,4-benzoquinone；5.4- chlorine catechols
Embodiment
Sn/Sb-Mn-GAC particles prepare embodiment 1
(1) granular activated carbon pre-processes：Granular activated carbon is boiled to clean, drying with a large amount of deionized waters, it is standby.
(2) it is in mass ratio：8：1：0.4：60 weigh SnCl successively4·5H2O、Mn(NO3)2、SbCl3And GAC.
(3) first by SnCl4·5H2O、Mn(NO3)2、SbCl3It is dissolved in organic alcohol solvent and obtains mixed solution, then by GAC
It is immersed in mixed solution, shaking table 150r/min shakes 2 hours, obtains support type Sn/Sb-Mn-GAC particle crude products, then dries
Dry, 300 DEG C of roastings can obtain support type Sn/Sb-Mn-GAC particles.
Sn/Sb-Mn-GAC particles prepare embodiment 2
(1) granular activated carbon pre-processes：Granular activated carbon is boiled to clean, drying with a large amount of deionized waters, it is standby.
(2) it is in mass ratio：10：2：1：65 weigh SnCl successively4·5H2O、Mn(NO3)2、SbCl3And GAC.
(3) first by SnCl4·5H2O、Mn(NO3)2、SbCl3It is dissolved in organic alcohol solvent and obtains mixed solution, then by GAC
It is immersed in mixed solution, shaking table 160r/min shakes 4 hours, obtains support type Sn/Sb-Mn-GAC particle crude products, then dries
Dry, 350 DEG C of roastings can obtain support type Sn/Sb-Mn-GAC particles.
Sn/Sb-Mn-GAC particles prepare embodiment 3
(1) granular activated carbon pre-processes：Granular activated carbon is boiled to clean, drying with a large amount of deionized waters, it is standby.
(2) it is in mass ratio：12：3：1.5：70 weigh SnCl successively4·5H2O、Mn(NO3)2、SbCl3And GAC.
(3) first by SnCl4·5H2O、Mn(NO3)2、SbCl3It is dissolved in organic alcohol solvent and obtains mixed solution, then by GAC
It is immersed in mixed solution, shaking table 170r/min shakes 3 hours, obtains support type Sn/Sb-Mn-GAC particle crude products, then dries
Dry, 400 DEG C of roastings can obtain support type Sn/Sb-Mn-GAC particles.
Sn/Sb-Mn-GAC particles prepare embodiment 4
(1) granular activated carbon pre-processes：Granular activated carbon is boiled to clean, drying with a large amount of deionized waters, it is standby.
(2) it is in mass ratio：14：4：42：75 weigh SnCl successively4·5H2O、Mn(NO3)2、SbCl3And GAC.
(3) first by SnCl4·5H2O、Mn(NO3)2、SbCl3It is dissolved in organic alcohol solvent and obtains mixed solution, then by GAC
It is immersed in mixed solution, shaking table 180r/min shakes 6 hours, obtains support type Sn/Sb-Mn-GAC particle crude products, then dries
Dry, 450 DEG C of roastings can obtain support type Sn/Sb-Mn-GAC particles.
Sn/Sb-Mn-GAC particles prepare embodiment 5
(1) granular activated carbon pre-processes：Granular activated carbon is boiled to clean, drying with a large amount of deionized waters, it is standby.
(2) it is in mass ratio：16：5：2：80 weigh SnCl successively4·5H2O、Mn(NO3)2、SbCl3And GAC.
(3) first by SnCl4·5H2O、Mn(NO3)2、SbCl3It is dissolved in organic alcohol solvent and obtains mixed solution, then by GAC
It is immersed in mixed solution, shaking table 200r/min shakes 5 hours, obtains support type Sn/Sb-Mn-GAC particle crude products, then dries
Dry, 500 DEG C of roastings can obtain support type Sn/Sb-Mn-GAC particles.
Sn/Sb-Mn-GAC particles prepare embodiment 1
(1) granular activated carbon pre-processes：Granular activated carbon is boiled to clean, drying with a large amount of deionized waters, it is standby.
(2) it is in mass ratio：8~16：1~5：0.4~2：60~80.SnCl is weighed successively4·5H2O、Mn(NO3)2、
SbCl3And GAC.
(3) first by SnCl4·5H2O、Mn(NO3)2、SbCl3It is dissolved in organic alcohol solvent and obtains mixed solution, then by GAC
It is immersed in mixed solution, shaking table 150-200r/min shakes more than 2 hours, and it is thick to obtain support type Sn/Sb-Mn-GAC particles
Product, then drying, 300-500 DEG C of roasting can obtain support type Sn/Sb-Mn-GAC particles.
The determination of the physicochemical property of support type Sn/Sb-Mn-GAC particles prepared by embodiment 1
Granule electrode surface topography and structural analysis：
(1) scanning electron microscope analysis
Using field emission scanning electron microscope (Sapphire of SUPRA 55, German Carl Zeiss Inc.) to activated carbon
Surface topography is analyzed, using the OXFORD X-MaxN51-XMX1004 energy disperse spectroscopies of ESEM configuration to modification activities
Element composition on charcoal is analyzed.
(2) X-ray diffraction analysis
Activated carbon is divided using X-ray diffractometer (X ' Pert PRO, Dutch PANalytical company PANalytical)
Analysis, test condition are：Copper target0.026 ° of step-length, 5 ° -80 ° of scanning range, often walks the residence time
20.4s, voltage 40V, electric current 40mA.
Granule electrode electrochemical property test：
Support type granule electrode electrochemical property test mainly provides theoretical foundation, electrochemistry for electro oxidation mechanism
Performance is typically tested from three-electrode system.This research is using occasion China CHI660E electrochemical workstations to granule electrode
Chemical property is tested, and using homemade carbon paste electrode as working electrode, saturated calomel electrode is as reference electrode, platinum electrode
Tested for auxiliary electrode.The preparation method of carbon paste electrode is：Appropriate granule electrode grind into powder is taken, with granule electrode：
Conductive black=8:1 amount adds a certain amount of conductive black, and liquid stone is added after granule electrode powder and conductive black are mixed
It is waxed into pasty state, inserted in carbon paste electrode.In the range of 1-1.5V, speed is swept respectively in 0.15mol/LNa with 20mV/s2SO4
And 0.15mol/LNa2SO4In+0.5g/L4- chlorophenol solution, its linear volt-ampere working curve and cyclic voltammetry curve is measured.
Through measuring：
The scanning electron microscope (SEM) photograph of Sn/Sb-Mn-GAC particles is as shown in figure 1, Fig. 1 shows the particle on Sn/Sb-Mn-GAC surfaces
Footpath is smaller, and the tiny size of activated carbon surface particle is homogeneous, and dispersiveness preferably, during as three-diemsnional electrode can be effectively increased granule electrode
Specific surface area, so as to add the contact area on granule electrode surface and organic pollution, to improve electro-oxidation reaction efficiency
Favorably.
Sn/Sb-Mn-GAC particle surface elementary analyses EDS schemes as shown in Fig. 2 Fig. 2 shows successfully to load on GAC
Corresponding Sn/Sb-Mn metal oxide.
Sn/Sb-Mn-GAC granule electrodes XRD as shown in figure 3, Fig. 3 show Sn/Sb-Mn-GAC only at 2 θ angles 26.7 ° go out
Show Sn elemental characteristic diffraction maximums, do not find Mn elements, Sb elemental characteristic diffraction maximums, but energy spectrum analysis detects manganese and antimony
The presence of element, show that he containing Mn oxide contains sb oxide into unformed armorphous fractions distribution in GAC surfaces.
The analysis oxygen polarization curve of Sn/Sb-Mn-GAC granule electrodes is as shown in figure 4, Fig. 4 shows Sn/Sb-Mn-GAC particles electricity
The electric current in Ji Xiyang areas is between 1.6V-1.8V.Oxygen evolution potential is the important of influence organic pollution electrochemical degradation efficiency
Factor, when electrode oxygen evolution potential is low, it is electrochemically reacted and analysis oxygen side reaction easily occurs, so as to cause organic pollutant removal
Efficiency reduces, so when carrying out activated carbon supported, it is desirable to obtain the high load type active carbon particle of oxygen evolution potential so that more
Electronics participates in organic pollutant removal, improves electrochemical reaction current efficiency.
The cyclic voltammetry curve figure of Sn/Sb-Mn-GAC granule electrodes is as shown in figure 5, Fig. 5 shows that Sn/Sb-Mn-GAC is being analysed
There is oxidation peak before oxygen current potential, illustrating 4- chlorophenols, there occurs Direct Catalytic Oxidation when these load type active carbons are granule electrode
Oxidation reaction.During direct oxidation, pollutant is attracted to electrode surface first, is then degraded and removed by electronics transfer
Go.
Further, the preparation-obtained support type Sn/Sb-Mn-GAC particles of embodiment 2-5 are chosen to carry out and embodiment 1
The support type Sn/Sb-Mn-GAC particles identical detection of preparation, the result that all embodiments detect to obtain are prepared with applying example 1
Support type Sn/Sb-Mn-GAC particles corresponding to every detection be identical, illustrate that prepared product reappearance is fabulous.
Application of the Sn/Sb-Mn-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols
Application Example 1 of the Sn/Sb-Mn-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols
Application of the Sn/Sb-Mn-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols：With Sn/Sb-Mn-GAC
It is granule electrode that particle, which prepares support type Sn/Sb-Mn-GAC particles prepared by embodiment 1, using dimensional stable anode DSA electrodes as sun
Pole, using titanium plate as negative electrode, with Na2SO4For electrolyte, bipolar type three-dimensional electrochemical reactor is built, described 4- Chlorophenols are dense
Spend for 100mg/L, simulated wastewater volume 200mL, electrolyte concentration 2g/L, the plate spacing between negative electrode and anode is 2cm, instead
Induced current is 1A, granule electrode dosage 10g.Three-dimensional electrochemical reaction, three-dimensional electrochemical are carried out under electrochemical oxidation process
The temperature of reaction is 40 degrees Celsius, and 4- chlorophenols are first degraded to the intermediate product of hydroxyl free radical, are finally degraded to titanium dioxide
Carbon and water.
Proceed to half then in electrochemical reaction, reaction solution is carried out to also want to chromatogram detection, obtains 4- chlorine described in Fig. 6
Liquid chromatogram in phenol degradation process, in Fig. 6：1. oxalic acid；2. fumaric acid；3. hydroquinones；4. 1,4-benzoquinone；5.4- chlorine
Catechol, Fig. 6 show mainly to generate during 4- chlorophenol degradations oxalic acid, fumaric acid, hydroquinones, to benzene
The intermediate products such as quinone, 4- chlorine catechols.
Electrochemical reaction terminates, and using the concentration of 4- chlorophenols in liquid chromatography analysis system, calculates 4- chlorophenol clearances,
Using 4- chlorophenols clearance, electric energy, current efficiency as index, investigate different loads granule electrode and the processing of 4- chlorophenols simulated wastewater is imitated
The influence of fruit.4- chlorophenol clearances are calculated as follows.
4- chlorophenol clearance y (%)：
In formula：C0For 4- chlorophenols initial concentration (mg/L), CtFor the concentration (mg/L) of t 4- chlorophenols.
After testing, the clearance of 4- chlorophenols reaches 99.5% in the present embodiment 4- Chlorophenols.
Application Example 2 of the Sn/Sb-Mn-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols
Application of the Sn/Sb-Mn-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols：With Sn/Sb-Mn-GAC
It is granule electrode that particle, which prepares support type Sn/Sb-Mn-GAC particles prepared by embodiment 2, using dimensional stable anode DSA electrodes as sun
Pole, using titanium plate as negative electrode, using NaCl as electrolyte, bipolar type three-dimensional electrochemical reactor is built, described 4- Chlorophenols are dense
Spend for 200mg/L, simulated wastewater volume 225mL, electrolyte concentration 2.5g/L, the plate spacing between negative electrode and anode is
2.5cm, kinetic current 1.25A, granule electrode dosage 12g.Three-dimensional electrochemical reaction is carried out under electrochemical oxidation process,
The temperature of three-dimensional electrochemical reaction is 45 degrees Celsius, and 4- chlorophenols are first degraded to the intermediate product of hydroxyl free radical, most final decline
Solve as carbon dioxide and water.
Proceed to half then in electrochemical reaction, reaction solution is carried out to also want to chromatogram detection, obtains 4- chlorine described in Fig. 6
Liquid chromatogram in phenol degradation process, in Fig. 6：1. oxalic acid；2. fumaric acid；3. hydroquinones；4. 1,4-benzoquinone；5.4- chlorine
Catechol, Fig. 6 show mainly to generate during 4- chlorophenol degradations oxalic acid, fumaric acid, hydroquinones, to benzene
The intermediate products such as quinone, 4- chlorine catechols.
Electrochemical reaction terminates, and using the concentration of 4- chlorophenols in liquid chromatography analysis system, calculates 4- chlorophenol clearances,
Using 4- chlorophenols clearance, electric energy, current efficiency as index, investigate different loads granule electrode and the processing of 4- chlorophenols simulated wastewater is imitated
The influence of fruit.4- chlorophenol clearances are calculated as follows.
4- chlorophenol clearance y (%)：
In formula：C0For 4- chlorophenols initial concentration (mg/L), CtFor the concentration (mg/L) of t 4- chlorophenols.
After testing, the clearance of 4- chlorophenols reaches more than 99.8% in the present embodiment 4- Chlorophenols.
Application Example 3 of the Sn/Sb-Mn-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols
Application of the Sn/Sb-Mn-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols：With Sn/Sb-Mn-GAC
It is granule electrode that particle, which prepares support type Sn/Sb-Mn-GAC particles prepared by embodiment 3, using dimensional stable anode DSA electrodes as sun
Pole, using titanium plate as negative electrode, with K2SO4For electrolyte, bipolar type three-dimensional electrochemical reactor is built, described 4- Chlorophenols are dense
Spend for 300mg/L, simulated wastewater volume 250mL, electrolyte concentration 3g/L, the plate spacing between negative electrode and anode is 3cm, instead
Induced current is 1.5A, granule electrode dosage 15g.Three-dimensional electrochemical reaction, three-dimensional electrification are carried out under electrochemical oxidation process
The temperature for learning reaction is 50 degrees Celsius, and 4- chlorophenols are first degraded to the intermediate product of hydroxyl free radical, are finally degraded to dioxy
Change carbon and water.
Proceed to half then in electrochemical reaction, reaction solution is carried out to also want to chromatogram detection, obtains 4- chlorine described in Fig. 6
Liquid chromatogram in phenol degradation process, in Fig. 6：1. oxalic acid；2. fumaric acid；3. hydroquinones；4. 1,4-benzoquinone；5.4- chlorine
Catechol, Fig. 6 show mainly to generate during 4- chlorophenol degradations oxalic acid, fumaric acid, hydroquinones, to benzene
The intermediate products such as quinone, 4- chlorine catechols.
Electrochemical reaction terminates, and using the concentration of 4- chlorophenols in liquid chromatography analysis system, calculates 4- chlorophenol clearances,
Using 4- chlorophenols clearance, electric energy, current efficiency as index, investigate different loads granule electrode and the processing of 4- chlorophenols simulated wastewater is imitated
The influence of fruit.4- chlorophenol clearances are calculated as follows.
4- chlorophenol clearance y (%)：
In formula：C0For 4- chlorophenols initial concentration (mg/L), CtFor the concentration (mg/L) of t 4- chlorophenols.
After testing, the clearance of 4- chlorophenols reaches 99.6% in the present embodiment 4- Chlorophenols.
Application Example 4 of the Sn/Sb-Mn-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols
Application of the Sn/Sb-Mn-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols：With Sn/Sb-Mn-GAC
It is granule electrode that particle, which prepares support type Sn/Sb-Mn-GAC particles prepared by embodiment 4, using dimensional stable anode DSA electrodes as sun
Pole, using titanium plate as negative electrode, using KCl as electrolyte, build bipolar type three-dimensional electrochemical reactor, described 4- Chlorophenol concentration
For 400mg/L, simulated wastewater volume 275mL, electrolyte concentration 3.5g/L, the plate spacing between negative electrode and anode is 3.5cm,
Kinetic current is 1.75A, granule electrode dosage 18g.Three-dimensional electrochemical reaction, three-dimensional electricity are carried out under electrochemical oxidation process
The temperature of chemical reaction is 55 degrees Celsius, and 4- chlorophenols are first degraded to the intermediate product of hydroxyl free radical, are finally degraded to two
Carbonoxide and water.
Proceed to half then in electrochemical reaction, reaction solution is carried out to also want to chromatogram detection, obtains 4- chlorine described in Fig. 6
Liquid chromatogram in phenol degradation process, in Fig. 6：1. oxalic acid；2. fumaric acid；3. hydroquinones；4. 1,4-benzoquinone；5.4- chlorine
Catechol, Fig. 6 show mainly to generate during 4- chlorophenol degradations oxalic acid, fumaric acid, hydroquinones, to benzene
The intermediate products such as quinone, 4- chlorine catechols.
Electrochemical reaction terminates, and using the concentration of 4- chlorophenols in liquid chromatography analysis system, calculates 4- chlorophenol clearances,
Using 4- chlorophenols clearance, electric energy, current efficiency as index, investigate different loads granule electrode and the processing of 4- chlorophenols simulated wastewater is imitated
The influence of fruit.4- chlorophenol clearances are calculated as follows.
4- chlorophenol clearance y (%)：
In formula：C0For 4- chlorophenols initial concentration (mg/L), CtFor the concentration (mg/L) of t 4- chlorophenols.
After testing, the clearance of 4- chlorophenols reaches 99.8% in the present embodiment 4- Chlorophenols.
Application Example 5 of the Sn/Sb-Mn-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols
Application of the Sn/Sb-Mn-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols：With Sn/Sb-Mn-GAC
It is granule electrode that particle, which prepares support type Sn/Sb-Mn-GAC particles prepared by embodiment 5, using dimensional stable anode DSA electrodes as sun
Pole, using titanium plate as negative electrode, with Na2SO is electrolyte, builds bipolar type three-dimensional electrochemical reactor, and described 4- Chlorophenols are dense
Spend for 500mg/L, simulated wastewater volume 300mL, electrolyte concentration 4g/L, the plate spacing between negative electrode and anode is 4cm, instead
Induced current is 2A, granule electrode dosage 20g.Three-dimensional electrochemical reaction, three-dimensional electrochemical are carried out under electrochemical oxidation process
The temperature of reaction is 60 degrees Celsius, and 4- chlorophenols are first degraded to the intermediate product of hydroxyl free radical, are finally degraded to titanium dioxide
Carbon and water.
Proceed to half then in electrochemical reaction, reaction solution is carried out to also want to chromatogram detection, obtains 4- chlorine described in Fig. 6
Liquid chromatogram in phenol degradation process, in Fig. 6：1. oxalic acid；2. fumaric acid；3. hydroquinones；4. 1,4-benzoquinone；5.4- chlorine
Catechol, Fig. 6 show mainly to generate during 4- chlorophenol degradations oxalic acid, fumaric acid, hydroquinones, to benzene
The intermediate products such as quinone, 4- chlorine catechols.
Electrochemical reaction terminates, and using the concentration of 4- chlorophenols in liquid chromatography analysis system, calculates 4- chlorophenol clearances,
Using 4- chlorophenols clearance, electric energy, current efficiency as index, investigate different loads granule electrode and the processing of 4- chlorophenols simulated wastewater is imitated
The influence of fruit.4- chlorophenol clearances are calculated as follows.
4- chlorophenol clearance y (%)：
In formula：C0For 4- chlorophenols initial concentration (mg/L), CtFor the concentration (mg/L) of t 4- chlorophenols.
After testing, the clearance of 4- chlorophenols reaches 99.6% in the present embodiment 4- Chlorophenols.
Claims (10)
1.Sn/Sb-Mn-GAC particles, it is characterised in that：Described Sn/Sb-Mn-GAC particles are by Sn, Sb, Mn metal ion
The support type Sn/Sb-Mn-GAC particles being prepared using infusion process by loading modification granular activated carbon.
2. Sn/Sb-Mn-GAC particles according to claim 1, it is characterised in that：Described support type Sn/Sb-Mn-GAC
Particle preparation method specific steps include：First by SnCl4·5H2O、Mn(NO3)2、SbCl3It is dissolved in organic alcohol solvent and is mixed
Solution is closed, then GAC is immersed in mixed solution, shaking table 150-200r/min shakes more than 2 hours, obtains support type Sn/Sb-
Mn-GAC particle crude products, then drying, 300-500 DEG C of roasting can obtain support type Sn/Sb-Mn-GAC particles.
3. Sn/Sb-Mn-GAC particles according to claim 1 or 2, it is characterised in that：SnCl4·5H2O、Mn(NO3)2、
SbCl3With GAC mass ratio：8~16：1~5：0.4~2：60~80.
4. Sn/Sb-Mn-GAC particles according to claim 1 or 2, it is characterised in that：Also locate in advance including granular activated carbon
Reason, the pretreatment of described granular activated carbon are that granular activated carbon is boiled to clean, drying with a large amount of deionized waters.
5. a kind of Sn/Sb-Mn-GAC particles as described in claim 1-4 is any give up in three-dimensional electrochemical reaction treatment 4- chlorophenols
Application in water, it is characterised in that：Using support type Sn/Sb-Mn-GAC particles as granule electrode, using dimensional stable anode DSA electrodes as
Anode, using titanium plate as negative electrode, bipolar type three-dimensional electrochemical reactor is built, three-dimensional electrochemical is carried out under electrochemical oxidation process
Reaction, carbon dioxide and water are finally degraded to by 4- chlorophenols.
6. Sn/Sb-Mn-GAC particles according to claim 5 answering in three-dimensional electrochemical reaction treatment 4- Chlorophenols
With, it is characterised in that：The electrolyte that described three-dimensional electrochemical reaction uses is Na2SO4、NaCl、K2SO4, one kind in KCl.
7. the Sn/Sb-Mn-GAC particles according to claim 5 or 6 are in three-dimensional electrochemical reaction treatment 4- Chlorophenols
Application, it is characterised in that：In described three-dimensional electrochemical reaction, described 4- Chlorophenols concentration is 100-500mg/L, mould
Intend wastewater volume 200-300mL, electrolyte concentration 2-4g/L, the plate spacing between negative electrode and anode is 2-4cm, kinetic current
For 1-2A, granule electrode dosage 10-20g.
8. Sn/Sb-Mn-GAC particles according to claim 7 answering in three-dimensional electrochemical reaction treatment 4- Chlorophenols
With, it is characterised in that：The temperature of described three-dimensional electrochemical reaction is 40-60 DEG C.
9. Sn/Sb-Mn-GAC particles according to claim 5 answering in three-dimensional electrochemical reaction treatment 4- Chlorophenols
With, it is characterised in that：In described three-dimensional electrochemical reaction, 4- chlorophenols are first degraded to the intermediate product of hydroxyl free radical,
Finally it is degraded to carbon dioxide and water；The intermediate product 1,4-benzoquinone of described hydroxyl free radical, 4- chlorine catechol, to benzene two
Mixing more than one or both of phenol, fumaric acid, oxalic acid.
10. Sn/Sb-Mn-GAC particles according to claim 5 are in three-dimensional electrochemical reaction treatment 4- Chlorophenols
Using, it is characterised in that：The clearance of 4- chlorophenols reaches more than 99% in described 4- Chlorophenols.
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