CN103739043B - A kind of granule electrode of photochemical catalysis three-dimensional electrode/electro-Fenton system and preparation method - Google Patents
A kind of granule electrode of photochemical catalysis three-dimensional electrode/electro-Fenton system and preparation method Download PDFInfo
- Publication number
- CN103739043B CN103739043B CN201410041766.4A CN201410041766A CN103739043B CN 103739043 B CN103739043 B CN 103739043B CN 201410041766 A CN201410041766 A CN 201410041766A CN 103739043 B CN103739043 B CN 103739043B
- Authority
- CN
- China
- Prior art keywords
- electrode
- electro
- gac
- preparation
- altogether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000008187 granular material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 claims abstract description 15
- 238000007146 photocatalysis Methods 0.000 claims abstract description 14
- 238000002203 pretreatment Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 22
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 15
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229910017061 Fe Co Inorganic materials 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 239000012982 microporous membrane Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000010953 base metal Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000002525 ultrasonication Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 21
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 230000015556 catabolic process Effects 0.000 abstract description 11
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 description 18
- 239000003153 chemical reaction reagent Substances 0.000 description 13
- 229910002651 NO3 Inorganic materials 0.000 description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 9
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 9
- 229940043267 rhodamine b Drugs 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000005273 aeration Methods 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 230000005611 electricity Effects 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000005276 aerator Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Landscapes
- Water Treatment By Electricity Or Magnetism (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses a kind of granule electrode and preparation method of photochemical catalysis three-dimensional electrode/electro-Fenton system, and this granule electrode is mixed P25 altogether by activated carbon supported bimetal and formed; First its preparation method is the pre-treatment of gac, obtains ultrasonic-Nitric Acid Modified gac; Then carry out the preparation that P25 mixed altogether by bimetal, then ultrasonic-Nitric Acid Modified gac and bimetal are mixed P25 altogether and carry out load, obtain the granule electrode for visible light photocatalysis three-dimensional electrode/electro-Fenton system.Preparation method of the present invention is simple, and the granule electrode obtained has visible ray photoelectrocatalysis effect, can fast and efficient degradation organic pollutant; And obvious visible light photocatalysis and three-dimensional electrode/electro-Fenton associated treatment effect can be obtained in visible light catalytic three-dimensional electrode/electro-Fenton system.
Description
Technical field
The invention belongs to water treatment and field of water pollution control, relate to the fast degradation technology of hardly degraded organic substance in waste water, refer more particularly to a kind of granule electrode and preparation method of photochemical catalysis three-dimensional electrode/electro-Fenton system.
Background technology
The combination of photochemical catalysis and electrocatalysis technology is the study hotspot processing Persistent organic pollutants thing at present, the combination of the two, both the problem of the difficult separation of catalyzer in photochemical catalysis, the easy compound in electron hole, practical application had been solved, solving again in electrocatalysis can current efficiency is low, energy consumption is high limitation, the two be combined in multinomial research to be proved to be and have associated treatment effect.
Three-diemsnional electrode is that particle filled composite electrode forms third electrode between traditional two-dimensional electrode electrolytic bath electrode plate, compared with two-dimensional electrode, three-diemsnional electrode substantially increases the specific surface area of reactor and current efficiency, improve mass-transfer efficiency between electrode, thus raising degradation efficiency, be than two-dimensional electrode more preferably electrocatalytic oxidation method.Three-dimensional electrode/electro-Fenton technology is on three-diemsnional electrode basis, by carbonaceous cathodes surface aeration and additional Fe
2+, Fenton's reaction can be formed in system, act synergistically with three-diemsnional electrode electrocatalysis and accelerate rate of contaminant degradation; The combination of photochemical catalysis simultaneously and Fenton technology is also the method for efficient degradation organic pollutant, the Synergistic degradation effect of the two is also proved to be, but photochemical catalysis and three-dimensional electrode/electro-Fenton treating processes is collaborative, and especially visible light catalytic three-dimensional electrode/electro-Fenton process there is not yet realization.
By the combination of three-diemsnional electrode electrocatalysis technology and photocatalysis technology, its key is to develop new granule electrode, this granule electrode not only will have electrocatalysis function, and will have photocatalysis performance, can realize the collaborative of electrocatalysis and photocatalytic effect in systems in which.At present for the research of using three-dimensional electrodes system granule electrode PhotoelectrocatalytiPerformance Performance, mostly concentrate on ultraviolet catalytic, not there is visible ray PhotoelectrocatalytiPerformance Performance.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, one is provided to have visible ray PhotoelectrocatalytiPerformance Performance, and can realize the granule electrode of the photochemical catalysis three-dimensional electrode/electro-Fenton system of the synergistic effect of visible light photocatalysis and three-dimensional electrode/electro-Fenton process, another object of the present invention is to provide the preparation method providing above-mentioned granule electrode.
For achieving the above object, technical scheme of the present invention is as follows:
A granule electrode for photochemical catalysis three-dimensional electrode/electro-Fenton system, this granule electrode is mixed P25 altogether by activated carbon supported bimetal and is formed;
Above-described gac is granulated active carbon or columnar activated carbon.
The particle diameter of above-described granulated active carbon is 3 ~ 5mm; The diameter of described columnar activated carbon is 3 ~ 5mm, and length-to-diameter ratio is 1 ~ 5:1.
Above-described bimetal is that two kinds in base metal Fe, Co, Ni, Al, Cu, Sn, Zn, Mn are mixed altogether.
Above-described bimetal is preferably Fe-Ni and mixes altogether or Fe-Co mixes altogether.
A preparation method for the granule electrode of photochemical catalysis three-dimensional electrode/electro-Fenton system, the method comprises the following steps:
(1) pre-treatment of gac: be soaked in dilute acid soln by the gac washing away most of Heisui River, is washed till neutrality after boiling 30min, then in dilute alkaline soln, is washed till neutrality after boiling 30min, obtains the gac cleaned up; By clean gac supersound process 2 times, each 0.5 ~ 1h, then dry 10 ~ 12h at 105 ~ 120 DEG C, obtains supersonic modifying gac; Be impregnated into by supersonic modifying gac in salpeter solution and carry out the oxidation modification that duration is 1 ~ 2h, then scalping is filtered, and is washed till neutrality with deionized water, and at 105 ~ 120 DEG C, dry 10 ~ 12h, obtains ultrasonic-Nitric Acid Modified gac;
(2) preparation of P25 mixed altogether by bimetal: get after P25 carries out vigorous stirring mixing, use ultrasonic disperse 30min, add two kinds of metal nitrates successively, magnetic agitation 30min, through 0.45um filtering with microporous membrane after ultrasonic lower load 1 ~ 2h, at 105 ~ 120 DEG C, dry 10 ~ 12h, then grinds, finally at 350 ~ 450 DEG C of calcining 2 ~ 4h, namely obtain bimetal and mix P25 altogether;
(3) preparation of granule electrode: bimetal prepared by step (2) is mixed altogether P25 dispersion in deionized water, after vigorous stirring dispersion, bimetal after dispersion is mixed altogether P25 and step (1) ultrasonic-Nitric Acid Modified gac and the mass ratio dip loading 2 ~ 4h under ultrasound environments by 0.2 ~ 2:100, scalping is clean with deionized water rinsing after filtering, dry 10 ~ 12h at 105 ~ 120 DEG C, at 350 ~ 450 DEG C of calcining 2 ~ 4h, obtain activated carbon supported bimetallic-modified P25 granule electrode, namely for the granule electrode of visible light photocatalysis three-dimensional electrode/electro-Fenton system.
Diluted acid described in above step (1) is sulfuric acid, and concentration is 0.01 ~ 0.05mol/L; Described diluted alkaline is sodium hydroxide, and concentration is 0.01 ~ 0.05mol/L; The concentration of described nitric acid is 3 ~ 10mol/L.
Above step (1) and the ultrasonic power described in step (2) are 75 ~ 105W, and frequency is 20 ~ 40kHZ; Load ultrasonic power described in step (3) is 60 ~ 75W, and frequency is 20kHZ.
P25 described in above step (2) is the P25 after activation; Activation temperature is 300 ~ 400 DEG C, and soak time is 2 ~ 4h.
The two kinds of metal nitrate mol ratios added in above step (2) are 1:1; The two kinds of metal nitrate total amounts added and the mol ratio of P25 are 0.4 ~ 10:100.
Above-described metal nitrate is analytical pure nitrate reagent.
Relative to prior art, beneficial effect of the present invention is as follows:
1, the present invention adopts diluted acid and diluted alkaline to clean gac respectively, eliminates the solid impurity in gac and greasy dirt, improves activated carbon surface adsorption activity, improves granule electrode to the degradation capability being adsorbed on surface organic matter.
2, the present invention adopts and ultrasonicly carries out modification to gac, effectively can improve activated carbon pore size, central hole structure is increased, be conducive to the area load of catalyzer, reduce because catalyst cupport causes space to block, improve the adsorptive power of loading type granule electrode.
3, normal activated carbon belongs to non-polar adsorbent, the present invention adopts nitric acid to carry out modification to activated carbon surface, changes activated carbon surface oxygen-containing functional group, makes activated carbon surface have certain polarity, add the absorption of granule electrode to water Semi-polarity pollutent, add TIO simultaneously
2in the tack of activated carbon surface.
4, the granule electrode in the present invention can effectively reduce electron-hole compound in visible ray three-dimensional electrode/electro-Fenton system, improve visible ray photoelectrocatalysis efficiency, rapidly and efficiently degradable organic pollutant, and obvious visible light photocatalysis and three-dimensional electrode/electro-Fenton associated treatment effect can be obtained.
5, the present invention is as the granule electrode for visible light catalytic three-dimensional electrode/electro-Fenton system, has visible ray PhotoelectrocatalytiPerformance Performance, also can be used in general three dimensional electrode photo electrocatalysis system, have associated treatment effect equally; In preparation process to gac after ultrasonic-Nitric Acid Modified, granule electrode all has absorption to polarity and nonpolar organic pollutants, is applicable to process various Persistent organic pollutants, has the advantages such as use range is wide, energy consumption is low, easy to maintenance, social benefit is remarkable, has a extensive future.
Accompanying drawing explanation
Fig. 1 is visible light catalytic three-dimensional electrode/electro-Fenton reaction unit schematic diagram
Accompanying drawing identifies: 1-visible light source, 2-glass electrolyzer, 3-positive plate, 4-negative plate, 5-insulating barrier, the activated carbon supported granule electrode of 6-, 7-micropore aeration pipe, 8-aerator, 9-D.C. regulated power supply, 10-camera bellows.
Fig. 2 is the contrast effect figure of the electrocatalysis of granule electrode prepared by normal activated carbon and the present invention and two kinds of reaction process of visible ray photoelectrocatalysis;
Accompanying drawing identifies: a-normal activated carbon granule electrode photoelectrocatalysis effect, b-normal activated carbon granule electrode electrocatalysis effect, activated carbon supported Fe-Ni prepared by c-embodiment 1 mixes P25 granule electrode electrocatalysis effect altogether, and activated carbon supported Fe-Ni prepared by d-embodiment 1 mixes P25 granule electrode photoelectrocatalysis effect altogether.
Fig. 3 is that visible light photocatalysis, three-diemsnional electrode electricity Fenton and visible light catalytic three-dimensional electrode/electro-Fenton three kinds of processes are to the design sketch of the degraded of 20mg/L rhodamine B.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment 1:
The granule electrode of the photochemical catalysis three-dimensional electrode/electro-Fenton system of the present embodiment is 3 ~ 5mm by particle diameter, and length-to-diameter ratio is that the columnar activated carbon supported bi-metallic Fe-Ni of 1:1 mixes P25 composition altogether.
Its preparation method is:
(1) pre-treatment of gac: the gac washing away most of Heisui River being soaked in volumetric concentration is in the sulphuric acid soln of 0.01mol/L, neutrality is washed till after boiling 30min, then be in the sodium hydroxide solution of 0.01mol/L in volumetric concentration, be washed till neutrality after boiling 30min, obtain the gac cleaned up; Be 75W by clean gac at power, frequency is process 2 times in the ultrasonic environment of 20kHZ, each 0.5h, and then dry 12h at 105 DEG C, obtains supersonic modifying gac; Supersonic modifying gac being impregnated into volumetric concentration is carry out the oxidation modification that duration is 2h in the salpeter solution of 5mol/L, then filters, is then washed till neutrality with deionized water, dry 12h at 105 DEG C, obtain ultrasonic-Nitric Acid Modified gac;
(2) Fe-Ni mixes the preparation of P25 altogether: overactivation temperature of learning from else's experience is 400 DEG C, soak time is after the P25 after 2h activation carries out vigorous stirring mixing, be 105W at power, frequency is disperse 30min in the ultrasound environments of 40kHZ, add successively and analyze pure Fe nitrate reagent and analytical pure W metal nitrate reagent, two kinds of metal nitrate mol ratios are 1:1, the analysis pure Fe nitrate reagent added and the mol ratio of analytical pure W metal nitrate reagent total amount and P25 are 1:100, magnetic agitation 30min, be 75W at power, frequency is through 0.45um filtering with microporous membrane after the ultrasonic environment doping 2h of 40kHZ, dry 12h at 120 DEG C, then grind, finally at 450 DEG C of calcining 2h, namely obtain bimetal Fe-Ni and mix P25 altogether,
(3) preparation of granule electrode: Fe-Ni prepared by step (2) is mixed altogether P25 dispersion in deionized water, after vigorous stirring dispersion, Fe-Ni after dispersion is mixed altogether P25 and step (1) ultrasonic-Nitric Acid Modified gac and dip loading 2h under be 75W frequency being the ultrasound environments of 20kHZ by the mass ratio of 1:100 at power, scalping is clean with deionized water rinsing after filtering, dry 12h at 120 DEG C, at 450 DEG C of calcining 2h, namely obtain for visible light photocatalysis three-dimensional electrode/electro-Fenton system, there is the activated carbon supported Fe-Ni modification P25 granule electrode of visible ray PhotoelectrocatalytiPerformance Performance.
Embodiment 2:
The activated carbon supported Fe-Ni that contrast normal activated carbon granule electrode and embodiment 1 obtain mixes P25 granule electrode altogether, and whether the granule electrode investigating preparation has visible ray PhotoelectrocatalytiPerformance Performance.
Get 40g granule electrode and carry out saturated adsorption experiment in rhodamine B solution, until be issued to adsorption equilibrium in 20mg/L concentration.Adsorb saturated after granule electrode be filled in the visible light catalytic three-dimensional electrode/electro-Fenton reactor shown in Fig. 1, positive plate is titanium plate, and negative plate is graphite cake.Adding concentration is that the rhodamine B solution 400ml of 20mg/L carries out contaminant degradation experiment.Control voltage of supply 30V, aeration rate 1.5L/min, anhydrous sodium sulphate dosage 5g/L, pH value of solution is 3.
For getting rid of the impact of electric Fenton, investigating the visible ray PhotoelectrocatalytiPerformance Performance of granule electrode, in experimentation, not adding Fe
2+, the electrocatalysis of granule electrode of normal activated carbon and preparation and two kinds of reaction process of visible ray photoelectrocatalysis are contrasted.Result as shown in Figure 2 and Table 1.
Table 1 different granule electrode electrocatalysis and light-catalysed effect comparison table
The 60min clearance of curve a and b is respectively 64.17% and 60.52%, illustrates that gac is as granule electrode, and photoelectrocatalysis effect is under visible light little, and visible ray does not almost have katalysis to three dimensional electrode photo electrocatalysis system.The removal effect of the 60min of correlation curve b and c can be found out (b:60.52%, c:71.88%), and the granule electrode prepared for the present invention is not when having additional light source, and its electrocatalysis characteristic is better than normal activated carbon.Correlation curve a and d removal effect can be found out (a:64.17%, d:88.41%), and granule electrode prepared by the present invention, compared with normal activated carbon, has good PhotoelectrocatalytiPerformance Performance under visible light.Correlation curve c and d effect can be found out, and ((c:71.88%, d:88.41%), the existence of visible ray can significantly improve the removal speed of pollutent, proves that this granule electrode has visible ray PhotoelectrocatalytiPerformance Performance.
Embodiment 3:
Adopt the activated carbon supported Fe-Ni of preparation in embodiment 1 to mix P25 granule electrode altogether and carry out saturated adsorption process, until no longer adsorb under the rhodamine B solution of 20mg/L, be filled in the visible light catalytic three-dimensional electrode/electro-Fenton reactor shown in Fig. 1 after saturated process, this device positive plate is titanium plate, and negative plate is graphite cake.Control voltage of supply 30V, aeration rate 1.5L/min, anhydrous sodium sulphate dosage 5g/L, pH value of solution is 3, Fe
2+dosage 0.05mmol/L.Investigate visible light photocatalysis (no power respectively, add light source), three-diemsnional electrode electricity Fenton (energising, do not add light source) (the energising of visible light catalytic three-dimensional electrode/electro-Fenton, add light source) three kinds of processes, contrast three kinds of processes to the degradation effect of 20mg/L rhodamine B, experimental result as shown in Figure 3.
As can be seen from Fig. 3, the granule electrode prepared by the present invention has the PhotoelectrocatalytiPerformance Performance under visible ray, and has the synergy of certain visible light photocatalysis and three-dimensional electrode/electro-Fenton process.The visible light photocatalytic degradation effect of 60min is 12.22%; In three-dimensional electrode/electro-Fenton system, this granule electrode and positive plate show good electrocatalysis effect, and 60min clearance arrives 77.68%; In visible light catalytic using three-dimensional electrodes system, 60min clearance reaches 96.64%, its processing rate be greater than adding of visible light catalytic and three-dimensional electrode/electro-Fenton process and, demonstrate adding of visible ray, make three-diemsnional electrode electricity Fenton and visible light catalytic have associated treatment effect, the 60min processing rate of three-dimensional electrode/electro-Fenton process is improve 24.4%.
Embodiment 4:
The granule electrode of the photochemical catalysis three-dimensional electrode/electro-Fenton system of the present embodiment, mixes P25 altogether by Supported On Granular Activated Carbon bimetal Fe-Ni and forms, and wherein, the particle diameter of granulated active carbon is 3 ~ 5mm.
Its preparation method is:
(1) pre-treatment of gac: the gac washing away most of Heisui River being soaked in volumetric concentration is in the sulphuric acid soln of 0.05mol/L, neutrality is washed till after boiling 30min, then be in the sodium hydroxide solution of 0.05mol/L in volumetric concentration, be washed till neutrality after boiling 30min, obtain the gac cleaned up; Be 75W by clean gac at power, frequency is process 2 times in the ultrasonic environment of 40kHZ, each 1h, and then dry 12h at 105 DEG C, obtains supersonic modifying gac; Supersonic modifying gac being impregnated into volumetric concentration is carry out the oxidation modification that duration is 1h in the salpeter solution of 10mol/L, then filters, is then washed till neutrality with deionized water, dry 12h at 105 DEG C, obtain ultrasonic-Nitric Acid Modified gac;
(2) Fe-Ni mixes the preparation of P25 altogether: overactivation temperature of learning from else's experience is 400 DEG C, soak time is after the P25 after 4h activation carries out vigorous stirring mixing, be 90W at power, frequency is disperse 30min in the ultrasonic environment of 40kHZ, add successively and analyze pure Fe nitrate reagent and analytical pure W metal nitrate reagent, two kinds of metal nitrate mol ratios are 1:1, the analysis pure Fe nitrate reagent added and the mol ratio of analytical pure W metal nitrate reagent total amount and P25 are 10:100, magnetic agitation 30min, be 75W at power, frequency is through 0.45um filtering with microporous membrane after the ultrasonic environment load 1.5h of 20kHZ, dry 12h at 120 DEG C, then grind, finally at 350 DEG C of calcining 2h, namely obtain bimetal Fe-Ni and mix P25 altogether,
(3) preparation of granule electrode: Fe-Ni prepared by step (2) is mixed altogether P25 dispersion in deionized water, after vigorous stirring dispersion, Fe-Ni after dispersion is mixed altogether P25 and step (1) ultrasonic-Nitric Acid Modified gac and dip loading 2h under be 75W frequency being the ultrasonic environment of 20kHZ by the mass ratio of 0.2:100 at power, scalping is clean with deionized water rinsing after filtering, dry 12h at 120 DEG C, at 350 DEG C of calcining 4h, namely obtain the activated carbon supported Fe-Ni modification P25 granule electrode with visible ray PhotoelectrocatalytiPerformance Performance.
Be filled in the visible light catalytic three-diemsnional electrode electro-Fenton reactor shown in Fig. 1 after saturated for the granule electrode made absorption, loading level is 100g/L, and adding concentration is that the rhodamine B solution 400ml of 20mg/L carries out contaminant degradation experiment.Control voltage of supply 30V, aeration rate 1.5L/min, anhydrous sodium sulphate dosage 5g/L, pH value of solution is 3.React visible light photocatalysis after 60min minute, three-diemsnional electrode electricity Fenton, visible light catalytic three-dimensional electrode/electro-Fenton three kinds of processes are 9.78%, 68.87%, 98.92% to the clearance of rhodamine B.
Embodiment 5:
The granule electrode of the photochemical catalysis three-dimensional electrode/electro-Fenton system of the present embodiment, by being 3 ~ 5mm by particle diameter, length-to-diameter ratio is that the columnar activated carbon supported bi-metallic Fe-Co of 5:1 mixes P25 composition altogether
(1) pre-treatment of gac: the gac washing away most of Heisui River being soaked in volumetric concentration is in the hydrochloric acid soln of 0.01mol/L, neutrality is washed till after boiling 30min, then be in the sodium hydroxide solution of 0.01mol/L in volumetric concentration, be washed till neutrality after boiling 30min, obtain the gac cleaned up; Be 105W by clean gac at power, frequency is process 2 times in the ultrasonic environment of 20kHZ, each 1h, and then dry 10h at 120 DEG C, obtains supersonic modifying gac; Supersonic modifying gac being impregnated into volumetric concentration is carry out the oxidation modification that duration is 2h in the salpeter solution of 3mol/L, then filters, is then washed till neutrality with deionized water, dry 10h at 120 DEG C, obtain ultrasonic-Nitric Acid Modified gac;
(2) Fe-Co mixes the preparation of P25 altogether: overactivation temperature of learning from else's experience is 400 DEG C, soak time is after the P25 after 4h activation carries out vigorous stirring mixing, be 75W at power, frequency is disperse 30min in the ultrasonic environment of 20kHZ, add successively and analyze pure Fe nitrate reagent and analytical pure metal Co nitrate reagent, two kinds of metal nitrate mol ratios are 1:1, the analysis pure Fe nitrate reagent added and the mol ratio of analytical pure metal Co nitrate reagent total amount and P25 are 0.4:100, magnetic agitation 30min, be 105W at power, frequency is through 0.45um filtering with microporous membrane after the ultrasound environments load 1h of 40kHZ, dry 10h at 105 DEG C, then grind, finally at 450 DEG C of calcining 4h, namely obtain bimetal Fe-Co and mix P25 altogether,
(3) preparation of granule electrode: Fe-Co prepared by step (2) is mixed altogether P25 dispersion in deionized water, after vigorous stirring dispersion, Fe-Co after dispersion is mixed altogether P25 and step (1) ultrasonic-Nitric Acid Modified gac and dip loading 2h under be 60W frequency being the ultrasound environments of 20kHZ by the mass ratio of 2:100 at power, scalping is clean with deionized water rinsing after filtering, dry 10h at 105 DEG C, at 400 DEG C of calcining 2h, namely obtain the activated carbon supported Fe-Co modification P25 granule electrode with visible ray PhotoelectrocatalytiPerformance Performance.
Be filled in the visible light catalytic three-diemsnional electrode electro-Fenton reactor shown in Fig. 1 after saturated for the granule electrode made absorption, loading level is 100g/L, and adding concentration is that the rhodamine B solution 400ml of 20mg/L carries out contaminant degradation experiment.Control voltage of supply 30V, aeration rate 1.5L/min, anhydrous sodium sulphate dosage 5g/L, pH value of solution is 3.React visible light photocatalysis after 60min minute, three-diemsnional electrode electricity Fenton, visible light catalytic three-dimensional electrode/electro-Fenton three kinds of processes are 9.12%, 74.32%, 94.21% to the clearance of rhodamine B.
Claims (7)
1. a granule electrode for photochemical catalysis three-dimensional electrode/electro-Fenton system, is characterized in that: this granule electrode is mixed P25 altogether by activated carbon supported bimetal and formed;
Described gac is granulated active carbon or columnar activated carbon;
The particle diameter of described granulated active carbon is 3 ~ 5mm; The diameter of described columnar activated carbon is 3 ~ 5mm, and length-to-diameter ratio is 1 ~ 5;
Described bimetal is that two kinds in base metal Fe, Co, Ni, Al, Cu, Sn, Zn, Mn are mixed altogether.
2. the granule electrode of a kind of photochemical catalysis three-dimensional electrode/electro-Fenton system according to claim 1, is characterized in that: described bimetal is that Fe-Ni mixes altogether or Fe-Co mixes altogether.
3. a preparation method for the granule electrode of photochemical catalysis three-dimensional electrode/electro-Fenton system, is characterized in that: the method comprises the following steps:
(1) pre-treatment of gac: be soaked in dilute acid soln by the gac washing away most of Heisui River, is washed till neutrality after boiling 30min, then in dilute alkaline soln, is washed till neutrality after boiling 30min, obtains the gac cleaned up; By clean gac ultrasonication 2 times, each 0.5 ~ 1h, then dry 10 ~ 12h at 105 ~ 120 DEG C, obtains supersonic modifying gac; Be impregnated into by supersonic modifying gac in salpeter solution and carry out the oxidation modification that duration is 1 ~ 2h, then filter, be then washed till neutrality with deionized water, at 105 ~ 120 DEG C, dry 10 ~ 12h, obtains ultrasonic-Nitric Acid Modified gac;
(2) preparation of P25 mixed altogether by bimetal: get after P25 carries out vigorous stirring mixing, 30min is disperseed by ultrasonic wave, add two kinds of metal nitrates successively, magnetic agitation 30min, under ultrasonic wave after load 1 ~ 2h through 0.45um filtering with microporous membrane, at 105 ~ 120 DEG C, dry 10 ~ 12h, then grinds, finally at 350 ~ 450 DEG C of calcining 2 ~ 4h, namely obtain bimetal and mix P25 altogether;
(3) preparation of granule electrode: bimetal prepared by step (2) is mixed altogether P25 dispersion in deionized water, after vigorous stirring dispersion, bimetal after dispersion is mixed altogether P25 and step (1) ultrasonic-Nitric Acid Modified gac and the mass ratio dip loading 2 ~ 4h under ultrasonic environment by 0.2 ~ 2:100, scalping is clean with deionized water rinsing after filtering, dry 10 ~ 12h at 105 ~ 120 DEG C, at 350 ~ 450 DEG C of calcining 2 ~ 4h, obtain activated carbon supported bimetallic-modified P25 granule electrode, namely for the granule electrode of visible light photocatalysis three-dimensional electrode/electro-Fenton system.
4. the preparation method of the granule electrode of a kind of photochemical catalysis three-dimensional electrode/electro-Fenton system according to claim 3, is characterized in that: sulfuric acid or the hydrochloric acid of to be volumetric concentration the be 0.01 ~ 0.05mol/L of the diluted acid described in step (1); Described diluted alkaline is sodium hydroxide volumetric concentration is 0.01 ~ 0.05 mol/L; The volumetric concentration of described nitric acid is 3 ~ 10mol/L.
5. the preparation method of the granule electrode of a kind of photochemical catalysis three-dimensional electrode/electro-Fenton system according to claim 3, is characterized in that: step (1) and the hyperacoustic power described in step (2) are 75 ~ 105W, and frequency is 20 ~ 40kHZ; Hyperacoustic power described in step (3) is 60 ~ 75W, and frequency is 20kHz.
6. the preparation method of the granule electrode of a kind of photochemical catalysis three-dimensional electrode/electro-Fenton system according to claim 3, is characterized in that: the P25 described in step (2) is the P25 after activation; Activation temperature is 400 DEG C, and soak time is 2 ~ 4 h.
7. the preparation method of the granule electrode of a kind of photochemical catalysis three-dimensional electrode/electro-Fenton system according to claim 3, is characterized in that: the mol ratio of two kinds of metal nitrates described in step (2) is: 1:1; The total amount of the two kinds of metal nitrates added and the mol ratio of P25 are: 0.4 ~ 10:100.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410041766.4A CN103739043B (en) | 2013-09-06 | 2014-01-28 | A kind of granule electrode of photochemical catalysis three-dimensional electrode/electro-Fenton system and preparation method |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310403325.X | 2013-09-06 | ||
CN201310403325 | 2013-09-06 | ||
CN201310403325X | 2013-09-06 | ||
CN201410041766.4A CN103739043B (en) | 2013-09-06 | 2014-01-28 | A kind of granule electrode of photochemical catalysis three-dimensional electrode/electro-Fenton system and preparation method |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103739043A CN103739043A (en) | 2014-04-23 |
CN103739043B true CN103739043B (en) | 2015-07-29 |
Family
ID=50496137
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410041766.4A Expired - Fee Related CN103739043B (en) | 2013-09-06 | 2014-01-28 | A kind of granule electrode of photochemical catalysis three-dimensional electrode/electro-Fenton system and preparation method |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103739043B (en) |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104045132B (en) * | 2014-06-23 | 2016-03-02 | 北京师范大学 | Can be used for the three-dimensional porous membrane electrode of photoelectric-synergetic effect Fenton system |
CN106145282B (en) * | 2015-03-23 | 2019-08-13 | 中国矿业大学(北京) | A kind of pretreatment unit of high-concentration waste water |
CN106467323B (en) * | 2015-08-18 | 2019-06-11 | 同济大学 | A kind of copper-iron-carbon silica aerogel electrode preparation method |
CN105110423B (en) * | 2015-09-08 | 2017-05-24 | 同济大学 | Carbon-aerogel-carried bimetal organic framework electro-Fenton cathode and preparation method thereof |
CN105293487A (en) * | 2015-09-23 | 2016-02-03 | 大连理工大学 | Method for preparing modified activated carbon and capacitive deionization electrode |
CN105540819B (en) * | 2016-01-29 | 2019-02-19 | 中国矿业大学 | A kind of method of support modification preparation ozone catalyst processing organic wastewater with difficult degradation thereby |
CN105748566B (en) * | 2016-05-06 | 2020-02-07 | 中南林业科技大学 | Eucommia ulmoides extract slow-release agent |
CN106495283A (en) * | 2016-11-21 | 2017-03-15 | 北京益清源环保科技有限公司 | There is electro-catalysis to remove Modified Activated Carbon aerogel particles electrode and the preparation method of phenol function |
CN106495290A (en) * | 2016-11-21 | 2017-03-15 | 北京益清源环保科技有限公司 | There is electro-catalysis to remove modified graphite granule electrode and the preparation method of benzoquinone function |
CN106495282A (en) * | 2016-11-21 | 2017-03-15 | 北京益清源环保科技有限公司 | There is electro-catalysis to remove modified activated carbon granule electrode and the preparation method of benzoquinones function |
CN106495286A (en) * | 2016-11-21 | 2017-03-15 | 北京益清源环保科技有限公司 | There is electro-catalysis to remove modified titanium foam granule electrode and the preparation method of benzoquinone function |
CN106495280A (en) * | 2016-11-21 | 2017-03-15 | 北京益清源环保科技有限公司 | There is electro-catalysis to remove improved ferroferric oxide granule electrode and the preparation method of phenol function |
CN106495279A (en) * | 2016-11-21 | 2017-03-15 | 北京益清源环保科技有限公司 | There is electro-catalysis to remove modified nickel foam granule electrode and the preparation method of chlorophenol function |
CN106495285A (en) * | 2016-11-21 | 2017-03-15 | 北京益清源环保科技有限公司 | There is electro-catalysis to remove modified nickel foam granule electrode and the preparation method of pyridine functional |
CN106495278A (en) * | 2016-11-21 | 2017-03-15 | 北京益清源环保科技有限公司 | There is electro-catalysis to remove modified titanium foam granule electrode and the preparation method of phenol function |
CN113582297A (en) * | 2021-07-29 | 2021-11-02 | 北京林业大学 | Preparation method and application of nickel-iron double-element loaded particle electrode |
CN113716655B (en) * | 2021-09-10 | 2022-11-22 | 吉林建筑大学 | Ferronickel bimetal three-dimensional electrode particle filler and preparation method and application thereof |
CN114314762B (en) * | 2021-10-11 | 2023-07-18 | 西南石油大学 | Nano ZnO/pyrolusite composite particle electrode and preparation method thereof |
CN115739089A (en) * | 2022-03-28 | 2023-03-07 | 贵州大学 | Preparation and application method of Co-OBC nano catalyst |
CN116143252A (en) * | 2023-03-23 | 2023-05-23 | 昆明理工大学 | Device for treating coffee preliminary processing wastewater by three-dimensional electrode-electro-Fenton coupling |
CN116143249B (en) * | 2023-04-07 | 2024-04-02 | 哈尔滨工业大学水资源国家工程研究中心有限公司 | Preparation method and application of photoelectrocatalysis three-dimensional particle electrode with high electron transfer efficiency based on modified biochar |
CN117654231B (en) * | 2023-12-14 | 2024-07-05 | 延边大学 | Three-dimensional electrode reactor and method for treating chlorobenzene by cooperation of three-dimensional electrode reactor and persulfate |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN202346797U (en) * | 2011-08-22 | 2012-07-25 | 上海电力学院 | Three-phase three-dimensional electrode photoelectric catalysis reactor |
-
2014
- 2014-01-28 CN CN201410041766.4A patent/CN103739043B/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN202346797U (en) * | 2011-08-22 | 2012-07-25 | 上海电力学院 | Three-phase three-dimensional electrode photoelectric catalysis reactor |
Non-Patent Citations (2)
Title |
---|
掺杂纳米TiO_2光催化性能的研究;吴树新等;《物理化学学报》;20040229;第20卷(第02期);138-143 * |
硝酸改性活性炭负载TiO2及其催化降解甲苯性能;章冬冬等;《化学反应工程与工艺》;20130430;第29卷(第2期);125-133 * |
Also Published As
Publication number | Publication date |
---|---|
CN103739043A (en) | 2014-04-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103739043B (en) | A kind of granule electrode of photochemical catalysis three-dimensional electrode/electro-Fenton system and preparation method | |
CN103539229B (en) | Particle electrode for efficiently removing various organic compounds and preparation method thereof | |
CN104925913B (en) | For removing catalyst particle electrode of hardly degraded organic substance and ammonia nitrogen and its preparation method and application in decontamination sewage | |
CN103539227B (en) | Preparation process of Ag-supported and MnO2-CeO2 doped activated alumina particle electrode containing CuO interlayer | |
CN101905154B (en) | Method for improving efficiency of visible light response doping-type M-TiO2/AC photocatalyst | |
CN103962094B (en) | A kind of ordered structure nanometer γ-Al 2o 3the preparation method of chemical modification diatomite adsorbant | |
CN101486499B (en) | Apparatus for photoelectric catalytic oxidation of subaqueous organics by solar energy | |
CN103586026A (en) | Carbon supported catalyst for ozone oxidation, and preparation method and use thereof | |
CN108423776A (en) | A kind of method that removing heavy metals and organic matter are removed in capacitive deionization coupling electro-catalysis collaboration | |
CN103449563B (en) | Method for removing organic matter under synergy of visible light photoelectric catalysis and three-dimensional electrode/electro-fenton | |
CN103435134B (en) | A kind of based on CNTs/Fe 3o 4three-dimensional electricity-Fenton improves the method for blue charcoal wastewater biodegradability | |
CN107469834A (en) | A kind of ZnS/CuS nanometer sheets composite photo-catalyst preparation method | |
Tang et al. | A novel S-scheme heterojunction in spent battery-derived ZnFe2O4/g-C3N4 photocatalyst for enhancing peroxymonosulfate activation and visible light degradation of organic pollutant | |
CN105293688A (en) | System for removing nitrate nitrogen in water in electro-catalysis mode through coupling biology positive electrode | |
CN106693910A (en) | Preparation, application and regeneration methods of hydroxyl magnesium@oxidized graphene supported carbon fiber cloth | |
CN104829019A (en) | Photo-electric organic wastewater co-processing method based on graphene material and device thereof | |
CN103159260A (en) | Preparation method and application of molecular-level-thickness HNb3O8 nanosheet | |
Chen et al. | Efficient degradation of ciprofloxacin by Cu2O/g-C3N4 heterostructures with different morphologies driven under the visible light | |
CN113441142B (en) | Preparation method and application of oxygen vacancy-rich graphene-loaded porous nano ferroelectric oxide catalyst | |
CN114409028B (en) | Three-dimensional particle electrode for wastewater treatment and preparation method thereof | |
Zhao et al. | Effective and continuous degradation of pollutants via carbon felt loaded with Co3O4 as three-dimensional electrode: Collaboration between ROS | |
CN109626513A (en) | The method that photocatalytic fuel cell couples degradation of contaminant with persulfate and improves electricity production | |
CN102513091A (en) | Preparation method for graphene self-assembled nanometer bismuth vanadate photocatalyst | |
CN107021583B (en) | Porous titanium ozone aerator with ozone heterogeneous catalysis-electrocatalysis function | |
CN103551164B (en) | Nitrogenous sulphur oxygen helerocyclics is had to eelctro-catalyst and the preparation method of efficient catalytic degradation function |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150729 |