CN107902727A - Sb-GAC particles and its application in 4 Chlorophenol of three-dimensional electrochemical reaction treatment - Google Patents

Sb-GAC particles and its application in 4 Chlorophenol of three-dimensional electrochemical reaction treatment Download PDF

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CN107902727A
CN107902727A CN201711132080.6A CN201711132080A CN107902727A CN 107902727 A CN107902727 A CN 107902727A CN 201711132080 A CN201711132080 A CN 201711132080A CN 107902727 A CN107902727 A CN 107902727A
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gac
chlorophenols
electrochemical reaction
dimensional electrochemical
particles
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李媚
廖安平
覃琴
陈熠嘉
谢树明
蓝平
黄招阳
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Guangxi University for Nationalities
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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
    • 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
    • C02F1/46114—Electrodes in particulate form or with conductive and/or non conductive particles between them
    • 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
    • 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
    • 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
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
    • 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

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Abstract

The present invention discloses Sb-GAC particles, which is the support type Sb-GAC particles that Sb metal ions are prepared using infusion process by loading modification granular activated carbon.Using support type 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 Sb-GAC particles, the removal rate of 4 chlorophenols can reach more than 85%.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

Sb-GAC particles and its application in three-dimensional electrochemical reaction treatment 4- Chlorophenols
Technical field
The invention belongs to technical field of sewage, more particularly to Sb-GAC particles are prepared and its reacted in three-dimensional electrochemical Handle the application in 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 Sb-GAC particles prepare and its at three-dimensional electrochemical reaction Manage the application in 4- Chlorophenols.
In order to realize the above-mentioned purpose of the present invention, technical scheme is as follows
Sb-GAC particles, the particle are to be prepared into Sb metal ions by loading modification granular activated carbon using infusion process Support type Sb-GAC the particles arrived.
Further as technical solution is improved, above-described Sb-GAC particles, the support type Sb-GAC particles Preparation method specific steps include：First by SbCl3It is dissolved in organic alcohol solvent and obtains mixed solution, then GAC is immersed in mixed Close solution in, shaking table 150-200r/min concussion 2 it is small when more than, obtain support type Sb-GAC particle crude products, then drying, 300- 500 DEG C of roastings can obtain support type Sb-GAC particles.
Further as technical solution is improved, in above-described Sb-GAC particle preparation methods, shaking table frequency Rate is 150-200r/min, and the calcination temperature is 300-500 DEG C.
Further as technical solution is improved, above-described Sb-GAC particles, SbCl3Mass ratio with GAC is：1: 50~1:30.
Further as technical solution is improved, and above-described Sb-GAC particles, further include granular activated carbon pretreatment, The granular activated carbon pretreatment is 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 Sb-GAC particle preparation methods, the drying temperature Spend for 100-110 DEG C.
Application of the Sb-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols described in any of the above, with load Type Sb-GAC particles are granule electrode, using dimensional stable anode DSA electrodes as anode, using titanium plate as cathode, and the three-dimensional electricity of structure bipolar type Chemical reactor, under electrochemical oxidation process carry out three-dimensional electrochemical reaction, by 4- chlorophenols be finally degraded to carbon dioxide and Water.
Further as technical solution is improved, and above-described Sb-GAC particles are in three-dimensional electrochemical reaction treatment 4- chlorine Application in phenol waste water, the electrolyte that three-dimensional electrochemical reaction uses is Na2SO4、NaCl、K2SO4, in KCl one Kind.
Further as technical solution is improved, and above-described Sb-GAC particles are in three-dimensional electrochemical reaction treatment 4- chlorine Application in phenol waste water, in three-dimensional electrochemical reaction, the 4- Chlorophenols concentration is 100-500mg/L, simulation Wastewater volume 200-300mL, electrolyte concentration 2-4g/L, the plate spacing between cathode and anode is 2-4cm, kinetic current is 1-2A, granule electrode dosage 10-20g.
Further as technical solution is improved, and above-described Sb-GAC particles are in three-dimensional electrochemical reaction treatment 4- chlorine Application in phenol waste water, the temperature of three-dimensional electrochemical reaction is 40-60 DEG C.
Further as technical solution is improved, and above-described Sb-GAC particles are in three-dimensional electrochemical reaction treatment 4- chlorine 4- chlorophenols, in three-dimensional electrochemical reaction, are first degraded to the intermediate product of hydroxyl free radical by the application in phenol waste water, Finally it is degraded to carbon dioxide and water；The intermediate product 1,4-benzoquinone of the hydroxyl free radical, 4- chlorine catechol, to benzene two Mixing more than one or both of phenol, fumaric acid, oxalic acid.
Further as technical solution is improved, and above-described Sb-GAC particles are in three-dimensional electrochemical reaction treatment 4- chlorine Application in phenol waste water, the removal rate of 4- chlorophenols reaches more than 85% in the 4- Chlorophenols.
The invention has the advantages that：
The present invention is constructed three-dimensional electrochemical reactor using Sb-GAC particles as granule electrode and 4- chlorophenols is aoxidized Degraded, three-dimensional electrochemical reactor make it compared to its work of ordinary two dimensional electrochemical reactor due to the addition of third dimension electrode The area of electrode greatly increases, and electrolytic efficiency is improved, simultaneously because interparticle spacing is small so that between material Mass transfer velocity is also improved.Using granular activated carbon as carrier it is relatively low compared to other carriers its prices, derive from a wealth of sources, Activated carbon has the characteristics that specific surface area is beaten, hole is flourishing, highly effective and safe at the same time.The granule electrode compared with other granule electrodes Preparation process is simple, and particle may be reused, simultaneously because its carrier is activated carbon, it adsorbs the ability of organic pollution Higher than other granule electrodes, the processing cost of 4- Chlorophenols is greatly reduced.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of Sb-GAC particles.
Fig. 2 schemes for Sb-GAC particle surface elemental analyses EDS.
Fig. 3 is Sb-GAC granule electrode XRD diagram
Fig. 4 is the analysis oxygen polarization curve of Sb-GAC granule electrodes
Fig. 5 is the cyclic voltammetry curve figure of 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
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) press or mass ratio is：1:50.SbCl is weighed successively3And GAC.
(3) first by SbCl3It is dissolved in organic alcohol solvent and obtains mixed solution, then GAC is immersed in mixed solution, shakes When bed 150r/min concussions 2 are small, support type Sb-GAC particle crude products are obtained, then drying, 300 DEG C of roastings can obtain support type Sb-GAC particles.
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) press or mass ratio is：1:40.SbCl is weighed successively3And GAC.
(3) first by SbCl3It is dissolved in organic alcohol solvent and obtains mixed solution, then GAC is immersed in mixed solution, shakes When bed 175r/min concussions 4 are small, support type Sb-GAC particle crude products are obtained, then drying, 400 DEG C of roastings can obtain support type Sb-GAC particles.
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) press or mass ratio is：1:30.SbCl is weighed successively3And GAC.
(3) first by SbCl3It is dissolved in organic alcohol solvent and obtains mixed solution, then GAC is immersed in mixed solution, shakes When bed 200r/min concussions 8 are small, support type Sb-GAC particle crude products are obtained, then drying, 500 DEG C of roastings can obtain support type Sb-GAC particles.
The physicochemical property of support type 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) photograph of Sb-GAC particles is as shown in Figure 1, Fig. 1 shows that Sb-GAC surfaces are distributed cotton-shaped loaded article.
Sb-GAC particle surface elemental analyses EDS is schemed as shown in Fig. 2, Fig. 2 shows successfully to have loaded corresponding Sb on GAC Metal oxide.
Sb-GAC granule electrodes XRD diagram is as shown in figure 3, Fig. 3 shows not find Sb element obvious characteristic diffraction maximums, but energy Spectrum analysis detects the presence of Sb elements, shows containing sb oxide, into unformed armorphous fractions distribution in GAC surfaces.
The analysis oxygen polarization curve of Sb-GAC granule electrodes is as shown in figure 4, Fig. 4 shows Sb-GAC granule electrodes in Xi Yang areas Electric current is between 1.6V-1.7V.Oxygen evolution potential is an important factor for influencing organic pollution electrochemical degradation efficiency, when electrode is analysed When oxygen current potential is low, it is electrochemically reacted and analysis oxygen side reaction easily occurs, so that the reduction of organic pollutant removal efficiency is caused, 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 participate in organic Pollutant removal, improves electrochemical reaction current efficiency.
The cyclic voltammetry curve figure of Sb-GAC granule electrodes is as shown in figure 5, Fig. 5 shows that Sb-GAC occur before oxygen evolution potential Oxidation peak, to illustrate 4- chlorophenols there occurs Direct Catalytic Oxidation oxidation reaction when these load type active carbons are granule electrode. During direct oxidation, pollutant is attracted to electrode surface first, then shifts the removing that is degraded by electronics.
Further, embodiment 2, embodiment 3 are chosen, preparation-obtained support type Sb-GAC particles carry out and embodiment The identical detection of the 1 support type Sb-GAC particles prepared, load of the result that all embodiments detect with applying the preparation of example 1 The corresponding every detection of type Sb-GAC particles is identical, and illustrates that prepared product reappearance is fabulous.
Application Example 1 of the Sb-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols
Application of the Sb-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols：Prepared and implemented with Sb-GAC particles Support type Sb-GAC particles prepared by example 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, and simulation is useless Water volume 200mL, electrolyte concentration 2g/L, the plate spacing between cathode and anode is 2cm, kinetic current 1A, particle electricity Pole dosage 10g.Three-dimensional electrochemical reaction is carried out under electrochemical oxidation process, the temperature of three-dimensional electrochemical reaction is Celsius for 40 4- chlorophenols, are first degraded to the intermediate product of hydroxyl free radical, are finally degraded to carbon dioxide and water by degree.
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 85.3% in the present embodiment 4- Chlorophenols.
Application Example 2 of the Sb-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols
Application of the Sb-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols：Prepared and implemented with Sb-GAC particles Support type Sb-GAC particles prepared by example 2 are granule electrode, using dimensional stable anode DSA electrodes as anode, using titanium plate as cathode, with NaCl is electrolyte, builds bipolar type three-dimensional electrochemical reactor, and the 4- Chlorophenols concentration is 200mg/L, and simulation is useless Water volume 225mL, electrolyte concentration 2.5g/L, the plate spacing between cathode 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, 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 88.2% in the present embodiment 4- Chlorophenols.
Application Example 3 of the Sb-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols
Application of the Sb-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols：Prepared and implemented with Sb-GAC particles Support type Sb-GAC particles prepared by example 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, and simulation is useless Water volume 250mL, electrolyte concentration 3g/L, the plate spacing between cathode and anode is 3cm, kinetic current .5A, particle electricity Pole dosage 15g.Three-dimensional electrochemical reaction is carried out under electrochemical oxidation process, the temperature of three-dimensional electrochemical reaction is Celsius for 50 4- chlorophenols, are first degraded to the intermediate product of hydroxyl free radical, are finally degraded to carbon dioxide and water by degree.
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 86.7% in the present embodiment 4- Chlorophenols.
Application Example 4 of the Sb-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols
Application of the Sb-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols：Prepared and implemented with Sb-GAC particles Support type Sb-GAC particles prepared by example 1 are granule electrode, using dimensional stable anode DSA electrodes as anode, using titanium plate as cathode, with KCl is 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 3.54cm, kinetic current 1.75A, Granule electrode dosage 18g.Three-dimensional electrochemical reaction is carried out under electrochemical oxidation process, the temperature of three-dimensional electrochemical reaction is 55 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 89.1% in the present embodiment 4- Chlorophenols.
Application Example 5 of the Sb-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols
Application of the Sb-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols：Prepared and implemented with Sb-GAC particles Support type Sb-GAC particles prepared by example 2 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 500mg/L, and simulation is useless Water volume 300mL, electrolyte concentration 4g/L, the plate spacing between cathode and anode is 4cm, kinetic current 2A, particle electricity Pole dosage 20g.Three-dimensional electrochemical reaction is carried out under electrochemical oxidation process, the temperature of three-dimensional electrochemical reaction is Celsius for 60 4- chlorophenols, are first degraded to the intermediate product of hydroxyl free radical, are finally degraded to carbon dioxide and water by degree.
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 90.3% in the present embodiment 4- Chlorophenols.

Claims (10)

1.Sb-GAC particles, it is characterised in that：Sb-GAC the particles are that Sb metal ions are passed through load using infusion process Support type Sb-GAC the particles that modification granular activated carbon is prepared.
2. Sb-GAC particles according to claim 1, it is characterised in that：Support type Sb-GAC particle the preparation methods Specific steps include：First by SbCl3It is dissolved in organic alcohol solvent and obtains mixed solution, then GAC is immersed in mixed solution, More than when shaking table 150-200r/min concussions 2 are small, support type Sb-GAC particle crude products are obtained, then drying, 300-500 DEG C of roasting It can obtain support type Sb-GAC particles.
3. Sb-GAC particles according to claim 1 or 2, it is characterised in that：SbCl3Mass ratio with GAC is：1:50~ 1:30。
4. Sb-GAC particles according to claim 1 or 2, it is characterised in that：Granular activated carbon pretreatment is further included, it is described Granular activated carbon pretreatment be that granular activated carbon is boiled with a large amount of deionized waters to clean, drying.
5. a kind of Sb-GAC particles as described in claim 1-4 is any are in three-dimensional electrochemical reaction treatment 4- Chlorophenols Using, it is characterised in that：Using support type Sb-GAC particles as granule electrode, using dimensional stable anode DSA electrodes as anode, using titanium plate as Cathode, builds bipolar type three-dimensional electrochemical reactor, three-dimensional electrochemical reaction is carried out under electrochemical oxidation process, by 4- chlorophenols Finally it is degraded to carbon dioxide and water.
6. application of the Sb-GAC particles according to claim 5 in three-dimensional electrochemical reaction treatment 4- Chlorophenols, its It is characterized in that：The electrolyte that the three-dimensional electrochemical reaction uses is Na2SO4、NaCl、K2SO4, one kind in KCl.
7. application of the Sb-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols according to claim 5 or 6, It is characterized in that：In described 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, kinetic current 1- 2A, granule electrode dosage 10-20g.
8. application of the Sb-GAC particles according to claim 7 in three-dimensional electrochemical reaction treatment 4- Chlorophenols, its It is characterized in that：The temperature of the three-dimensional electrochemical reaction is 40-60 DEG C.
9. application of the Sb-GAC particles according to claim 5 in three-dimensional electrochemical reaction treatment 4- Chlorophenols, its It is characterized in that：In the three-dimensional electrochemical reaction, 4- chlorophenols are first degraded to the intermediate product of hydroxyl free radical, most final decline Solve as carbon dioxide and water；It is the intermediate product 1,4-benzoquinone of the hydroxyl free radical, 4- chlorine catechol, hydroquinone, anti- Mixing more than one or both of butene dioic acid, oxalic acid.
10. application of the Sb-GAC particles according to claim 5 in three-dimensional electrochemical reaction treatment 4- Chlorophenols, its It is characterized in that：The removal rate of 4- chlorophenols reaches more than 85% in the 4- Chlorophenols.
CN201711132080.6A 2017-11-15 2017-11-15 Sb-GAC particles and its application in 4 Chlorophenol of three-dimensional electrochemical reaction treatment Pending CN107902727A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101186361A (en) * 2007-12-17 2008-05-28 江苏省环境科学研究院 Three-dimensional electrode reactor and method for processing chlorobenzene waste water by using the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101186361A (en) * 2007-12-17 2008-05-28 江苏省环境科学研究院 Three-dimensional electrode reactor and method for processing chlorobenzene waste water by using the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李沅知等: "三维电极反应器用负载型活性炭粒子电极的研究", 《安全与环境学报》 *

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