CN107902728A - Sn/Sb-GAC particles and its application in 4 Chlorophenol of three-dimensional electrochemical reaction treatment - Google Patents
Sn/Sb-GAC particles and its application in 4 Chlorophenol of three-dimensional electrochemical reaction treatment Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- 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
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Abstract
The present invention discloses Sn/Sb-GAC particles, which is the support type Sn/Sb-GAC particles that Sn, Sb metal ion are prepared using infusion process by loading modification granular activated carbon.Using support type Sn/Sb-GAC particles as granule electrode, using dimensional stable anode DSA electrodes as anode, using titanium plate as cathode, 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-GAC particles, the removal rate of 4 chlorophenols can reach more than 83%.Meanwhile particle preparation process 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-GAC particles prepare and its in three-dimensional electrochemicals
Application in reaction treatment 4- Chlorophenols.
Background technology
With the fast development of the industry such as petrochemical industry, plastics, synthetic fibers, the phenol wastewater produced in production is discharged into certainly
Right boundary, while causing water pollution, also affects 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 stringent control aldehydes matter.
Processing containing Phenol Industrial Wastewater also becomes 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, the advantages that reaction rate is fast, and wide adaptability, non-secondary pollution, processing equipment is simple, electrolytic condition easily operated control, into
One of research 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, has investigated the influence of different factor Pyrogentisinic Acid treatment effects.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.ZUCHENG WU use β-PbO2Anode have studied
The Oxidative Degradation Process of phenol, has investigated the shadow of initial pH value, current density and temperature Degradation of Phenol in the course of the research
Ring, thus it is speculated that gone out the degradation pathway of phenol, and established the mathematical model 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 basic 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 the Strong oxdiative ability of OH and be oxidized to having for small molecule
Machine thing, or thoroughly it is degraded to CO2And H2O；Fe at the same time3+Fe can be reduced in cathode again2+, 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, pesticide, 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 removal rate is handled up to 82%.Du Yan lifes et al. are handled dinitrodiazophenol wastewater using electricity-Fenton methods.It is real
Test the result shows 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 removal rates 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 common 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, removal is of high cost, complicated, there is provided a kind of Sn/Sb-GAC particles are prepared and its anti-in three-dimensional electrochemical
The application in 4- Chlorophenols should be handled.
In order to realize the above-mentioned purpose of the present invention, technical scheme is as follows
Sn/Sb-GAC particles, the particle are that Sn, Sb metal ion are modified granular activated carbon by loading using infusion process
Support type Sn/Sb-GAC the particles being prepared.
Further as technical solution is improved, above-described Sn/Sb-GAC particles, and the support type Sn/Sb-
GAC particle preparation method specific steps include：First by SnCl4·5H2O、SbCl3Be dissolved in organic alcohol solvent obtain mixing it is molten
Liquid, then GAC is immersed in mixed solution, when shaking table 150-200r/min concussions 2 are small more than, obtain support type Sn/Sb-GAC
Particle crude product, then drying, 300-500 DEG C of roasting can obtain support type Sn/Sb-GAC particles.
Further as technical solution is improved, in above-described Sn/Sb-GAC particle preparation methods, the shaking table
Frequency is 150-200r/min, and the calcination temperature is 300-500 DEG C.
Further as technical solution is improved, above-described Sn/Sb-GAC particles, SnCl4·5H2O、SbCl3With
The mass ratio of GAC is：8~16：0.4~2：60~80.
Further as technical solution is improved, and above-described Sn/Sb-GAC particles, further include granular activated carbon and locate in advance
Reason, granular activated carbon pretreatment are that granular activated carbon is boiled to clean, drying with a large amount of deionized waters.
Further as technical solution is improved, in above-described Sn/Sb-GAC particle preparation methods, the drying
Temperature is 100-110 DEG C.
Application of the Sn/Sb-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols described in any of the above, with
Support type Sn/Sb-GAC particles are granule electrode, using dimensional stable anode DSA electrodes as anode, using titanium plate as cathode, build bipolar type
Three-dimensional electrochemical reactor, three-dimensional electrochemical reaction is carried out under electrochemical oxidation process, 4- chlorophenols are finally degraded to dioxy
Change carbon and water.
Further as technical solution is improved, and above-described Sn/Sb-GAC particles are in three-dimensional electrochemical reaction treatment
Application in 4- Chlorophenols, the electrolyte that three-dimensional electrochemical reaction uses is Na2SO4、NaCl、K2SO4, in KCl
It is a kind of.
Further as technical solution is improved, and above-described Sn/Sb-GAC particles are in three-dimensional electrochemical reaction treatment
Application in 4- Chlorophenols, in three-dimensional electrochemical reaction, the 4- Chlorophenols concentration is 100-500mg/L,
Simulated wastewater volume 200-300mL, electrolyte concentration 2-4g/L, the plate spacing between cathode and anode is 2-4cm, reaction electricity
Flow for 1-2A, granule electrode dosage 10-20g.
Further as technical solution is improved, and above-described Sn/Sb-GAC particles are in three-dimensional electrochemical reaction treatment
Application in 4- Chlorophenols, the temperature of three-dimensional electrochemical reaction is 40-60 DEG C.
Further as technical solution is improved, and above-described Sn/Sb-GAC particles are in three-dimensional electrochemical reaction treatment
4- chlorophenols, in three-dimensional electrochemical reaction, are first degraded to the centre of hydroxyl free radical by the application in 4- Chlorophenols
Product, is finally degraded to carbon dioxide and water；The intermediate product 1,4-benzoquinone of the hydroxyl free radical, 4- chlorine catechol,
Mixing more than one or both of hydroquinone, fumaric acid, oxalic acid.
Further as technical solution is improved, and above-described Sn/Sb-GAC particles are in three-dimensional electrochemical reaction treatment
Application in 4- Chlorophenols, the removal rate of 4- chlorophenols reaches more than 83% in the 4- Chlorophenols.
The invention has the advantages that：
The present invention is prepared for Sn/Sb-GAC particles using infusion process, and infusion process has operation compared with other preparation methods
The advantages of simple.Simultaneously because employing carrier of the granular activated carbon as granule electrode, make it than the particle electricity of other carriers
Has more preferable adsorption effect.The area that working electrode is considerably increased in three-dimensional electrochemical reactor is applied, is carried
High current efficiency, it is excellent compared to also with the more thorough non-secondary pollution of 4- chlorophenol degradations etc. with other methods degraded 4- chlorophenols
Point.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of Sn/Sb-GAC particles.
Fig. 2 schemes for Sn/Sb-GAC particle surface elemental analyses EDS.
Fig. 3 is Sn/Sb-GAC granule electrode XRD diagram
Fig. 4 is the analysis oxygen polarization curve of Sn/Sb-GAC granule electrodes
Fig. 5 is the cyclic voltammetry curve figure of Sn/Sb-GAC granule electrodes
Fig. 6 is the liquid chromatogram during 4- chlorophenol degradations
In Fig. 6：1. oxalic acid；2. fumaric acid；3. hydroquinone；4. 1,4-benzoquinone；5.4- chlorine catechols
Embodiment
Sn/Sb-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 spare.
(2) it is in mass ratio：8：0.4：60 weigh SnCl successively4·5H2O、SbCl3And GAC.
(3) first by SnCl4·5H2O、SbCl3It is dissolved in organic alcohol solvent and obtains mixed solution, then GAC is immersed in mixed
Close in solution, when shaking table 150r/min concussions 2 are small, obtain support type Sn/Sb-GAC particle crude products, then drying, 300 DEG C of roastings
It can obtain support type Sn/Sb-GAC particles.
Sn/Sb-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 spare.
(2) it is in mass ratio：10：1：65 weigh SnCl successively4·5H2O、SbCl3And GAC.
(3) first by SnCl4·5H2O、SbCl3It is dissolved in organic alcohol solvent and obtains mixed solution, then GAC is immersed in mixed
Close in solution, when shaking table 160r/min concussions 3 are small, obtain support type Sn/Sb-GAC particle crude products, then drying, 350 DEG C of roastings
It can obtain support type Sn/Sb-GAC particles.
Sn/Sb-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 spare.
(2) it is in mass ratio：12：1.5：70 weigh SnCl successively4·5H2O、SbCl3And GAC.
(3) first by SnCl4·5H2O、SbCl3It is dissolved in organic alcohol solvent and obtains mixed solution, then GAC is immersed in mixed
Close in solution, when shaking table 170r/min concussions 4 are small, obtain support type Sn/Sb-GAC particle crude products, then drying, 400 DEG C of roastings
It can obtain support type Sn/Sb-GAC particles.
Sn/Sb-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 spare.
(2) it is in mass ratio：14：2：75 weigh SnCl successively4·5H2O、SbCl3And GAC.
(3) first by SnCl4·5H2O、SbCl3It is dissolved in organic alcohol solvent and obtains mixed solution, then GAC is immersed in mixed
Close in solution, when shaking table 180r/min concussions 6 are small, obtain support type Sn/Sb-GAC particle crude products, then drying, 450 DEG C of roastings
It can obtain support type Sn/Sb-GAC particles.
Sn/Sb-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 spare.
(2) it is in mass ratio：16：2：80 weigh SnCl successively4·5H2O、SbCl3And GAC.
(3) first by SnCl4·5H2O、SbCl3It is dissolved in organic alcohol solvent and obtains mixed solution, then GAC is immersed in mixed
Close in solution, when shaking table 200r/min concussions 3 are small, obtain support type Sn/Sb-GAC particle crude products, then drying, 500 DEG C of roastings
It can obtain support type Sn/Sb-GAC particles.
The physicochemical property of support type Sn/Sb-GAC particles prepared by embodiment 1 determines
Granule electrode surface topography and structural analysis：
(1) scanning electron microscope analysis
Using field emission scanning electron microscope (SUPRA 55Sapphire, German Carl Zeiss Inc.) to activated carbon table
Face pattern is analyzed, using the OXFORD X-MaxN51-XMX1004 energy disperse spectroscopies of scanning electron microscope configuration to modification activities charcoal
On element composition analyzed.
(2) X-ray diffraction analysis
Activated carbon is divided using X-ray diffractometer (X ' Pert PRO, Dutch Panaco 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 generally selects three-electrode system to be tested.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 production 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 paste, 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) photographs of Sn/Sb-GAC particles as shown in Figure 1, Fig. 1 show the grain diameter on Sn/Sb-GAC surfaces compared with
Small, the tiny size of activated carbon surface particle is homogeneous, and preferably, as three-diemsnional electrode when can be effectively increased the ratio of granule electrode to dispersiveness
Surface area, so that the contact area of granule electrode surface and organic pollution is added, it is favourable to improving electro-oxidation reaction efficiency.
Sn/Sb-GAC particle surface elemental analyses EDS is schemed as shown in Fig. 2, Fig. 2 shows successfully to have loaded phase on GAC
Answer the metal oxide of Sn/Sb.
Sn/Sb-GAC granule electrodes XRD diagram as shown in figure 3, Fig. 3 shows Sn/Sb-GAC in same diffraction maximum,
There are diffraction maximum at 26.7 °, 33.9 °, 51.9 °, which is SnO2Characteristic diffraction peak；Do not find that Sb element obvious characteristics are spread out
Peak is penetrated, but energy spectrum analysis detects the presence of antimony element, shows that load contains sb oxide into unformed armorphous form
It is distributed in GAC surfaces.
The analysis oxygen polarization curve of Sn/Sb-GAC granule electrodes is as shown in figure 4, Fig. 4 shows that Sn/Sb-GAC granule electrodes are being analysed
The electric current in oxygen area is between 1.4V-1.5V.An important factor for oxygen evolution potential is influence organic pollution electrochemical degradation efficiency, when
When electrode oxygen evolution potential is low, it is electrochemically reacted and analysis oxygen side reaction easily occurs, so as to causes organic pollutant removal efficiency to drop
It is low, 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 ginsengs
With organic pollutant removal, electrochemical reaction current efficiency is improved.
The cyclic voltammetry curve figure of Sn/Sb-GAC granule electrodes is as shown in figure 5, Fig. 5 shows Sn/Sb-GAC in oxygen evolution potential
Before there is oxidation peak, illustrating 4- chlorophenols, there occurs Direct Catalytic Oxidation oxidation is anti-when these load type active carbons are granule electrode
Should.During direct oxidation, pollutant is attracted to electrode surface first, then shifts the removing that is degraded by electronics.
Further, the preparation-obtained support type Sn/Sb-GAC particles of embodiment 2-5 are chosen make with embodiment 1
The identical detection of standby support type Sn/Sb-GAC particles, load of the result that all embodiments detect with applying the preparation of example 1
The corresponding every detection of type Sn/Sb-GAC particles is identical, and illustrates that prepared product reappearance is fabulous.
Application Example 1 of the Sn/Sb-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols
Application of the Sn/Sb-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols：With Sn/Sb-GAC particle systems
Support type Sn/Sb-GAC particles prepared by standby embodiment 1 are granule electrode, using dimensional stable anode DSA electrodes as anode, using titanium plate as
Cathode, with Na2SO4For electrolyte, bipolar type three-dimensional electrochemical reactor is built, the 4- Chlorophenols concentration is 100mg/
L, simulated wastewater volume 200mL, electrolyte concentration 2g/L, the plate spacing between cathode and anode is 2cm, kinetic current is
1A, granule electrode dosage 10g.Three-dimensional electrochemical reaction, the temperature of three-dimensional electrochemical reaction are carried out under electrochemical oxidation process
Spend for 40 degrees Celsius, 4- chlorophenols are first degraded to the intermediate product of hydroxyl free radical, are finally degraded to carbon dioxide and water.
Proceed to half then in electrochemical reaction, reaction solution is carried out to also want to chromatography detection, obtains 4- chlorine described in Fig. 6
Liquid chromatogram in phenol degradation process, in Fig. 6：1. oxalic acid；2. fumaric acid；3. hydroquinone；4. 1,4-benzoquinone；5.4- chlorine
Catechol, Fig. 6 show mainly to generate during 4- chlorophenol degradations oxalic acid, fumaric acid, hydroquinone, 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 removal rates,
Using 4- chlorophenols removal rate, 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 removal rates are calculated as follows.
4- chlorophenol removal rate y (%)：
In formula：C0For 4- chlorophenols initial concentration (mg/L), CtFor the concentration (mg/L) of t moment 4- chlorophenols.
After testing, the removal rate of 4- chlorophenols reaches 83.3% in the present embodiment 4- Chlorophenols.
Application Example 2 of the Sn/Sb-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols
Application of the Sn/Sb-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols：With Sn/Sb-GAC particle systems
Support type Sn/Sb-GAC particles prepared by standby embodiment 2 are granule electrode, using dimensional stable anode DSA electrodes as anode, using titanium plate as
Cathode, using NaCl as electrolyte, builds bipolar type three-dimensional electrochemical reactor, and the 4- Chlorophenols concentration is 200mg/L,
Simulated wastewater volume 225mL, electrolyte concentration 2.5g/L, the plate spacing between cathode and anode is 2.5cm, kinetic current is
1.25A, granule electrode dosage 12g.Three-dimensional electrochemical reaction is carried out under electrochemical oxidation process, three-dimensional electrochemical reaction
Temperature is 45 degrees Celsius, and 4- chlorophenols are first degraded to the intermediate product of hydroxyl free radical, are finally degraded to carbon dioxide and water.
Proceed to half then in electrochemical reaction, reaction solution is carried out to also want to chromatography detection, obtains 4- chlorine described in Fig. 6
Liquid chromatogram in phenol degradation process, in Fig. 6：1. oxalic acid；2. fumaric acid；3. hydroquinone；4. 1,4-benzoquinone；5.4- chlorine
Catechol, Fig. 6 show mainly to generate during 4- chlorophenol degradations oxalic acid, fumaric acid, hydroquinone, 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 removal rates,
Using 4- chlorophenols removal rate, 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 removal rates are calculated as follows.
4- chlorophenol removal rate y (%)：
In formula：C0For 4- chlorophenols initial concentration (mg/L), CtFor the concentration (mg/L) of t moment 4- chlorophenols.
After testing, the removal rate of 4- chlorophenols reaches more than 85.6% in the present embodiment 4- Chlorophenols.
Application Example 3 of the Sn/Sb-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols
Application of the Sn/Sb-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols：With Sn/Sb-GAC particle systems
Support type Sn/Sb-GAC particles prepared by standby embodiment 3 are granule electrode, using dimensional stable anode DSA electrodes as anode, using titanium plate as
Cathode, with K2SO4For electrolyte, bipolar type three-dimensional electrochemical reactor is built, the 4- Chlorophenols concentration is 300mg/L,
Simulated wastewater volume 250mL, electrolyte concentration 3g/L, the plate spacing between cathode and anode is 3cm, kinetic current is
1.5A, granule electrode dosage 15g.Three-dimensional electrochemical reaction is carried out under electrochemical oxidation process, three-dimensional electrochemical reaction
Temperature is 50 degrees Celsius, and 4- chlorophenols are first degraded to the intermediate product of hydroxyl free radical, are finally degraded to carbon dioxide and water.
Proceed to half then in electrochemical reaction, reaction solution is carried out to also want to chromatography detection, obtains 4- chlorine described in Fig. 6
Liquid chromatogram in phenol degradation process, in Fig. 6：1. oxalic acid；2. fumaric acid；3. hydroquinone；4. 1,4-benzoquinone；5.4- chlorine
Catechol, Fig. 6 show mainly to generate during 4- chlorophenol degradations oxalic acid, fumaric acid, hydroquinone, 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 removal rates,
Using 4- chlorophenols removal rate, 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 removal rates are calculated as follows.
4- chlorophenol removal rate y (%)：
In formula：C0For 4- chlorophenols initial concentration (mg/L), CtFor the concentration (mg/L) of t moment 4- chlorophenols.
After testing, the removal rate of 4- chlorophenols reaches 84.1% in the present embodiment 4- Chlorophenols.
Application Example 4 of the Sn/Sb-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols
Application of the Sn/Sb-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols：With Sn/Sb-GAC particle systems
Support type Sn/Sb-GAC particles prepared by standby embodiment 4 are granule electrode, using dimensional stable anode DSA electrodes as anode, using titanium plate as
Cathode, using KCl as electrolyte, builds bipolar type three-dimensional electrochemical reactor, and the 4- Chlorophenols concentration is 400mg/L,
Simulated wastewater volume 275mL, electrolyte concentration 3.5g/L, the plate spacing between cathode and anode is 3.5cm, kinetic current is
1.75A, granule electrode dosage 18g.Three-dimensional electrochemical reaction is carried out under electrochemical oxidation process, three-dimensional electrochemical reaction
Temperature is 55 degrees Celsius, and 4- chlorophenols are first degraded to the intermediate product of hydroxyl free radical, are finally degraded to carbon dioxide and water.
Proceed to half then in electrochemical reaction, reaction solution is carried out to also want to chromatography detection, obtains 4- chlorine described in Fig. 6
Liquid chromatogram in phenol degradation process, in Fig. 6：1. oxalic acid；2. fumaric acid；3. hydroquinone；4. 1,4-benzoquinone；5.4- chlorine
Catechol, Fig. 6 show mainly to generate during 4- chlorophenol degradations oxalic acid, fumaric acid, hydroquinone, 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 removal rates,
Using 4- chlorophenols removal rate, 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 removal rates are calculated as follows.
4- chlorophenol removal rate y (%)：
In formula：C0For 4- chlorophenols initial concentration (mg/L), CtFor the concentration (mg/L) of t moment 4- chlorophenols.
After testing, the removal rate of 4- chlorophenols reaches 90.8% in the present embodiment 4- Chlorophenols.
Application Example 5 of the Sn/Sb-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols
Application of the Sn/Sb-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols：With Sn/Sb-GAC particle systems
Support type Sn/Sb-GAC particles prepared by standby embodiment 5 are granule electrode, using dimensional stable anode DSA electrodes as anode, using titanium plate as
Cathode, with Na2SO is electrolyte, builds bipolar type three-dimensional electrochemical reactor, the 4- Chlorophenols concentration is 500mg/
L, simulated wastewater volume 300mL, electrolyte concentration 4g/L, the plate spacing between cathode and anode is 4cm, kinetic current is
2A, granule electrode dosage 20g.Three-dimensional electrochemical reaction, the temperature of three-dimensional electrochemical reaction are carried out under electrochemical oxidation process
Spend for 60 degrees Celsius, 4- chlorophenols are first degraded to the intermediate product of hydroxyl free radical, are finally degraded to carbon dioxide and water.
Proceed to half then in electrochemical reaction, reaction solution is carried out to also want to chromatography detection, obtains 4- chlorine described in Fig. 6
Liquid chromatogram in phenol degradation process, in Fig. 6：1. oxalic acid；2. fumaric acid；3. hydroquinone；4. 1,4-benzoquinone；5.4- chlorine
Catechol, Fig. 6 show mainly to generate during 4- chlorophenol degradations oxalic acid, fumaric acid, hydroquinone, 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 removal rates,
Using 4- chlorophenols removal rate, 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 removal rates are calculated as follows.
4- chlorophenol removal rate y (%)：
In formula：C0For 4- chlorophenols initial concentration (mg/L), CtFor the concentration (mg/L) of t moment 4- chlorophenols.
After testing, the removal rate of 4- chlorophenols reaches 86.5% in the present embodiment 4- Chlorophenols.
Claims (10)
1.Sn/Sb-GAC particles, it is characterised in that：Sn/Sb-GAC the particles are that Sn, Sb metal ion are used infusion process
Support type Sn/Sb-GAC the particles being prepared by loading modification granular activated carbon.
2. Sn/Sb-GAC particles according to claim 1, it is characterised in that：Support type Sn/Sb-GAC particle the systems
Preparation Method specific steps include：First by SnCl4·5H2O、SbCl3It is dissolved in organic alcohol solvent and obtains mixed solution, then by GAC
Be immersed in mixed solution, shaking table 150-200r/min concussion 2 it is small when more than, obtain support type Sn/Sb-GAC particle crude products, so
Drying, 300-500 DEG C of roasting can obtain support type Sn/Sb-GAC particles afterwards.
3. Sn/Sb-GAC particles according to claim 1 or 2, it is characterised in that：SnCl4·5H2O、SbCl3With GAC's
Mass ratio is：8~16：0.4~2：60~80.
4. Sn/Sb-GAC particles according to claim 1 or 2, it is characterised in that：Granular activated carbon pretreatment is further included,
The granular activated carbon pretreatment is that granular activated carbon is boiled to clean, drying with a large amount of deionized waters.
5. a kind of Sn/Sb-GAC particles as described in claim 1-4 is any are in three-dimensional electrochemical reaction treatment 4- Chlorophenols
In application, it is characterised in that：Using support type Sn/Sb-GAC particles as granule electrode, using dimensional stable anode DSA electrodes as anode,
Using titanium plate as cathode, 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.
6. application of the Sn/Sb-GAC particles according to claim 5 in three-dimensional electrochemical reaction treatment 4- Chlorophenols,
It is characterized in that：The electrolyte that the three-dimensional electrochemical reaction uses is Na2SO4、NaCl、K2SO4, one kind in KCl.
7. the answering in three-dimensional electrochemical reaction treatment 4- Chlorophenols of the Sn/Sb-GAC particles according to claim 5 or 6
With, it is characterised in that：In the three-dimensional electrochemical reaction, the 4- Chlorophenols concentration is 100-500mg/L, and simulation is useless
Water volume 200-300mL, electrolyte concentration 2-4g/L, the plate spacing between cathode and anode is 2-4cm, kinetic current 1-
2A, granule electrode dosage 10-20g.
8. application of the Sn/Sb-GAC particles according to claim 7 in three-dimensional electrochemical reaction treatment 4- Chlorophenols,
It is characterized in that：The temperature of the three-dimensional electrochemical reaction is 40-60 DEG C.
9. application of the Sn/Sb-GAC particles according to claim 5 in three-dimensional electrochemical reaction treatment 4- Chlorophenols,
It is characterized in that：In the 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 the hydroxyl free radical, 4- chlorine catechol, hydroquinone,
Mixing more than one or both of fumaric acid, oxalic acid.
10. Sn/Sb-GAC particles according to claim 5 answering in three-dimensional electrochemical reaction treatment 4- Chlorophenols
With, it is characterised in that：The removal rate of 4- chlorophenols reaches more than 83% in the 4- Chlorophenols.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110282704A (en) * | 2019-05-07 | 2019-09-27 | 广东省测试分析研究所（中国广州分析测试中心） | A kind of electrochemical modification filler for water process |
| CN115893594A (en) * | 2022-12-08 | 2023-04-04 | 辽宁大学 | Preparation method and application of modified activated carbon particle electrode loaded with tin and antimony |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110282704A (en) * | 2019-05-07 | 2019-09-27 | 广东省测试分析研究所（中国广州分析测试中心） | A kind of electrochemical modification filler for water process |
| CN110282704B (en) * | 2019-05-07 | 2022-03-04 | 广东省测试分析研究所（中国广州分析测试中心） | Electrochemical modified filler for water treatment |
| CN115893594A (en) * | 2022-12-08 | 2023-04-04 | 辽宁大学 | Preparation method and application of modified activated carbon particle electrode loaded with tin and antimony |
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